JP2908968B2 - Derivatives of cyclohexane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a derivative of cyclohexane useful as a liquid crystal material, and more particularly to a liquid crystal compound having an alkenyl group at a molecular terminal and a liquid crystal composition having the compound.

[0002]

2. Description of the Related Art Display devices using liquid crystals are widely used in watches, calculators and the like. These liquid crystal display devices utilize the optical anisotropy and dielectric anisotropy of a liquid crystal material.
The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase. Among them, a liquid crystal phase using the nematic liquid crystal phase is most widely used. In response to the electro-optic effect applied to liquid crystal displays,
There are display devices such as TN (twisted nematic) type, DS (dynamic scattering) type, guest, host type, and DAP type. Is desirable. Many liquid crystal compounds are already known, but at present, no single liquid crystal material satisfies such conditions, and several liquid crystal materials or non-liquid crystal materials are mixed for practical use. These substances are required to be stable to moisture, light, heat, air and the like. Particularly recently, thin film transistors (TF
The importance of a substance having low optical anisotropy as a material for a liquid crystal display element for an active matrix system represented by the T) system is increasing. Further, the liquid crystal material is required to have as much compatibility as possible at low temperatures with many existing liquid crystal materials.

Heretofore, the following compounds have been known as compounds similar to the compounds of the present invention.

[0004]

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[0005]

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These compounds, in particular (I), (II),
(III), (VI) and (VII) are reported to have a large dielectric anisotropy Δε, have a low viscosity, and have an effect of lowering the threshold voltage without increasing the viscosity. According to those studies, it has been found that the value of Δε is relatively small and the threshold voltage cannot be sufficiently reduced.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a derivative of cyclohexane which is a liquid crystal compound having a low viscosity and capable of sufficiently lowering the threshold voltage.

[0008]

The present inventors have studied to solve the above-mentioned problems, and as a result, have found that a compound having a novel structure and improved properties as compared with a known liquid crystal compound is obtained. Upon finding out, the present invention has been completed. The cyclohexane derivative of the present invention has the general formula (I)

[0009]

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(Wherein X represents a fluorine atom or a trifluoromethyl group, or a trifluoromethoxy group or a difluoromethoxy group, -A- is 1,4-cyclohexylene or 1,4-phenylene, and -B- is 1 , 4-cyclohexylene, 1 represents 0, 1 or 2, m represents 0, 1 or 2, l + m ≧ 1, Z represents —CH
₂ CH ₂ — or a single bond, n represents an integer of 0 to 4, R represents a hydrogen atom or a linear or branched alkyl group of 1 to 7, and when R is an alkyl group, a double bond Is a trans configuration) and a liquid crystal composition containing at least one of the cyclohexane derivatives.

The compounds having an alkenyl substituent reported so far have a ratio of elastic constants (K ₃₃ / K ₁₁ ) as compared with compounds having a normal alkyl substituent as reported in various articles. It is large and is suitable as a liquid crystal material for STN display elements. Features of liquid crystal compounds provided by the present invention, as surprising fact, despite having alkenyl substituents, the ratio of the elastic constants (K ₃₃
/ K ₁₁ ) is smaller than that of the compound having a normal alkyl substituent. It is known from the following publications a), b) and c) that a material having a small K ₃₃ / K ₁₁ has a steep electro-optical characteristic of the TN mode and exhibits excellent multiplex characteristics. a) J. Nehring, Advan
ce in Liquid Crystal Research and Applications (ed.
L. Bata)., P1155, Pergamon Press (1980). b) G. Baur, Th
e Physics and Chemistry of Liquid Crystal Devices
(ed. GJprokel)., P61, Plenum (1980). c) Y.Takahashi,
T. Uchida and M. Wada, Mol. Cryst. Liq. Cryst., 66, 171 (1
981). Further, since the compound of the present invention is chemically stable, it is possible to prepare a composition capable of driving at a low voltage and having excellent multiplex properties by using the compound of the present invention.

[0012] Formula a compound of (I) may be mentioned compounds represented by formula Ia~I g (definition of each symbol are the same as formula (I)).

[0013]

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Among the compounds of the above formulas, particularly preferred compounds are exemplified.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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The compound of the present invention wherein R in the formula (I) is an alkyl group is in a trans form due to the steric structure of the double bond to which R is bonded. As the alkyl group for R, a linear group having 1 to 7 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are more preferable. The liquid crystal composition provided by the present invention comprises, in addition to the component (A) containing at least one compound represented by the formula (I), one compound having a high dielectric constant anisotropy of preferably ΔΔ ≧ 5. The component (B) containing the above, | Δε | <5
(C) containing at least one compound having a low dielectric constant anisotropy, component (D) containing at least one compound having a clearing point higher than 80 ° C., and optionally other components (E). ).

Particularly preferred compounds as the component (B) are shown below.

[0022]

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[0023]

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Here, R represents an alkyl or alkenyl group having 1 to 10 carbon atoms, and one or two non-adjacent carbon atoms of the group may be replaced by an oxygen atom. Particularly preferred compounds as the component (C) are shown below.

[0025]

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[0026]

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[0027]

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Here, R and R 'represent an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two non-adjacent carbon atoms of the group may be replaced by an oxygen atom. Particularly preferred compounds as the component (D) are shown below.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Here, R and R 'represent an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and one or two non-adjacent carbon atoms of the group may be replaced by an oxygen atom. Particularly preferred compounds as the component (E) are shown below.

[0040]

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[0041]

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Here, R represents an alkyl or alkenyl group having 1 to 10 carbon atoms, and one or two non-adjacent carbon atoms of the group may be replaced by an oxygen atom. The composition according to the present invention preferably contains one or more of the compounds represented by the formula (I) at a ratio of 0.1 to 40% by weight in view of excellent liquid crystal properties.

[Preparation of Compound] The compound of the present invention has the general formula (II)

[0044]

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(Wherein X represents a fluorine atom or a trifluoromethyl group, or a trifluoromethoxy group or a difluoromethoxy group, -A- is 1,4-cyclohexene or 1,4-phenylene, and -B- is 1,
4-cyclohexylene, 1 represents 0, 1 or 2;
m represents 0, 1 or 2, l + m ≧ 1, Z represents —CH ₂ CH ₂ — or a single bond, and n represents an integer of 0 to 4) and an aldehyde derivative represented by the general formula (III )

[0046]

Embedded image R ₃ ′ P ＝ CH—R (III) (wherein, R represents a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, and R ′ represents an alkyl group, an aryl group or (Representing an aralkyl group).
c Reaction Vol. 14, 270 (196
5)).

The compounds of the invention formed by the reaction of the general formulas (II) and (III) are generally obtained as a mixture of their stereoisomers, which can be separated, for example, by column chromatography. If necessary, the mixture can be converted into the compound of the present invention by a method known per se. That is, after the mixture is brominated with triphenylphosphine-bromine, the resulting halide can be converted to a mixture containing the compound of the present invention in a significant proportion by reduction.

In the process for producing the compound of the present invention, general formula (II)
The reaction of the compound of the formula (III) with the compound of the formula (III) can be carried out by a method known per se.
For example, a compound (III) obtained by reacting a corresponding phosphonium salt with potassium-t-butoxide, sodium methoxide, lithium diisopropylamide, n-butyllithium, sodium hydride, pyridine, triethylamine or the like may be used. it can.
This reaction and the subsequent reaction with compound (II) are generally performed in an organic solvent. As a solvent that can be used in this reaction, any solvent that does not inhibit the reaction may be used. It can be used as a single solvent or a mixed solvent. The reaction temperature can be selected from the range from -50 degrees to the boiling point of the solvent used. The reaction is preferably carried out at −30 ° C. to room temperature. However, when the concentration of the raw materials in the reaction mixture is high, the reaction should be carried out at a low temperature.
Degree is preferred.

The compound represented by the general formula (II) as a starting material for synthesizing the compound of the present invention can be produced by various methods represented by the following (1) to (5).

[0050]

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[0051]

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[0052]

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(Wherein, R represents the same meaning as described above, X represents a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group, or a difluoromethoxy group, 1 is 0, 1 or 2, and m is 0, 1 or 2; 1 + m ≧ 1; -Z- represents -CH ₂ CH ₂ -or a single bond; n represents an integer of 0 to 4;
and n ′ represents 0 or 1. )

[0054]

The compounds of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Synthesis of 5- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -2E-pentene (Compound No. 1) (1) Magnesium 1 in 100 ml of THF under nitrogen flow
7.1 g are suspended therein, and 400 ml of THF is added therein.
A solution in which 162 g of 4,5-trifluorobromobenzene was dissolved was added dropwise, and the mixture was stirred at room temperature for 1 hour. 100 g of 1,4-cyclohexanedione monoethylene ketal
A solution dissolved in 400 ml of HF was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 1 l of a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with 1 l of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
166.2 g of 1,1-ethylenedioxy-4-hydroxy-4- (3 ', 4', 5'-trifluorophenyl) cyclohexane was obtained.

(2) 1,1-Ethylenedioxy-4-hydroxy-4- (3 ′, 4 ′,
5'-trifluorophenyl) cyclohexane 166.
After dissolving 2 g, 20 g of p-toluenesulfonic acid monohydrate was added thereto and stirred for 1 hour under reflux. The reaction solution was washed with 500 ml of water, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1,1-ethylenedioxy-4- (3 ', 4', 5'-trifluorophenyl) was removed. 102.6 g of -3-cyclohexene was obtained.

(3) 100 g of 1,1-ethylenedioxy-4- (3 ', 4', 5'-trifluorophenyl) -3-cyclohexene was dissolved in 1 liter of ethanol, and 40 g of palladium / carbon (5%) was dissolved. In addition, the mixture was stirred under a hydrogen atmosphere to perform catalytic reduction. After the reaction is completed, the catalyst is filtered off,
The organic layer was distilled off under reduced pressure to obtain 95 g of 1,1-ethylenedioxy-4- (3 ', 4', 5'-trifluorophenyl) cyclohexane.

(4) 95.02 g of 1,1-ethylenedioxy-4- (3 ', 4', 5'-trifluorophenyl) cyclohexane, 82.7 g of formic acid and 20 m of toluene
The mixture was heated and stirred for 2 hours under distillation. The reaction solution was added to 500 ml of water, and extracted with 1 liter of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to give 4- (3 ',
63.1 g of 4 ', 5'-trifluorophenyl) cyclohexanone was obtained. m. p. 123.5 ° C.

[0059] (5) 2-(1 ', 3', - dioxane-2 'Iru) ethyltriphenylphosphonium bromide 48.6g suspension liquid THF250ml of stirring under nitrogen gas stream, 0 ° C. To the cooled potassium over t -Butoxide14.
9 g were added in small portions. After stirring the reaction solution at room temperature for 1 hour, 4- (3 ', 4', 5'-trifluorophenyl)
A solution of 20 g of cyclohexanone in 100 ml of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 500 ml of water and extracted with 1 l of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure , and the concentrated residue was chromatographed on silica gel with ethyl acetate / heptane (1: 5).
3 ', 4', 5'-trifluorophenyl-4- (2 '
There were obtained 24.9 g of-(1 ", 3" -dioxane-2 "-yl) ethylidene) cyclohexane.

(6) 3 ', 4', 5'-trifluorophenyl-4- (2 '-(1 ", 3" -dioxane-2 "
-Yl) ethylidene) cyclohexane 24.9 g was dissolved in ethanol 200 ml, and palladium / carbon (5%) was dissolved.
15 g was added, and the mixture was stirred under a hydrogen atmosphere to perform catalytic reduction. After completion of the reaction, the catalyst was filtered off, and the filtrate was distilled off under reduced pressure.
3 ′, 4 ′, 5′-
12. trifluorophenyl-4- (2 '-(1 ", 3" -dioxan-2 "-yl) ethyl) cyclohexane
2 g were obtained.

(7) 3 ', 4', 5'-trifluorophenyl-4- (2 '-(1 ", 3" -dioxane-2 "
Iru) ethyl) cyclohexane 13g in formic acid 10 g,
Toluene (2 ml) was added, and the mixture was heated and stirred for 2 hours under reflux. The reaction solution was added to 50 ml of water, and 100 ml of ethyl acetate was added.
, And the organic layer is dried over anhydrous magnesium sulfate.
Concentrate under reduced pressure and concentrate 3- (4 '-(3 ", 4", 5 "-
10.7 g of trifluorophenyl) cyclohexyl) propionaldehyde were obtained.

[0062] (8) suspended solution THF50ml of ethyltriphenylphosphonium bromide 11.2g was stirred under a stream of nitrogen, potassium chromatography t- butoxide 4.2g was cooled to 0 ℃ was added portionwise. After stirring the reaction solution for 1 hour at room temperature, 3- (4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) propionaldehyde 6
A solution of 7.8 g of THF in 20 ml was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 50 ml of water and extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and chromatographed on silica gel with ethyl acetate / heptane (1: 5) to give 5- (4'-
4.09 g of (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -2-pentene was obtained.

(9) 5- (4 '-(3 ", 4", 5 "-
To a solution of 4.09 g of trifluorophenyl) cyclohexyl) -2-pentene in 50 ml of methylene chloride were added 7.7 g of m-chloroperbenzoic acid and 6.2 g of potassium carbonate, and the mixture was stirred in an ice bath for 2 hours. After completion of the reaction, the reaction mixture was added to 50 ml of water and extracted with 100 ml of methylene chloride. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure and concentrated to 5- (4 '-(3 ", 4", 5 "-trifluorophenyl).
Cyclohexyl) -2,3-epoxypentane 3.84
g was obtained.

(10) 5- (4 '-(3 ", 4", 5 ")
To a suspension of 3.84 g of -trifluorophenyl) cyclohexyl) -2,3-epoxypentane in 100 ml of benzene was added 12.3 g of dibromotriphenylphosphorane , and the mixture was heated and stirred for 2 hours under reflux. After the reaction, water 1
The mixture was extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and ethyl acetate / heptane (1: 5) on silica gel.
Chromatography treatment is performed with 5- (4 '-(3 ", 4",
5 "-trifluorophenyl) cyclohexyl) -2,
3.33 g of 3-dibromopentane were obtained.

(11) 5- (4 '-(3 ", 4", 5 ")
3.2 g of zinc powder was added to a solution of 3.33 g of -trifluorophenyl) cyclohexyl) -2,3-dibromopentane in 50 ml of acetic acid, and the mixture was stirred at room temperature overnight. After the completion of the reaction, the solid was separated by filtration, the filtrate was added to 50 ml of water, and extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, chromatographed on silica gel with ethyl acetate / heptane (1: 5), and recrystallized with heptane to give 5- (4 '-(3 "). ,
4 ", 5" -trifluorophenyl) cyclohexyl)
320 mg of -2E-pentene was obtained. m. p. 13.
8-16.9C.

Example 2 Synthesis of 4-trans- (3 ', 4', 5'-trifluorophenyl) cyclohexylethene (Compound No.
2) (1) suspended solution THF200ml of methoxymethyl triphenylphosphonium chloride 36.4g was stirred under a stream of nitrogen, potassium chromatography t- butoxide 12g while cooling to 0 ℃ was added portionwise. After stirring the reaction solution at room temperature for 1 hour, a solution of 20 g of 4- (3 ′, 4 ′, 5-trifluorophenyl) cyclohexanone in 100 ml of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 100 ml of water and extracted with 200 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and chromatographed on silica gel with ethyl acetate / heptane (1: 5).
18.25 g of 4- (3 ', 4', 5'-trifluorophenyl) methoxymethylenecyclohexane was obtained.

(2) 4- (3 ', 4', 5'-trifluorophenyl) methoxymethylenecyclohexane
To 5 g, 40 ml of THF and 20 ml of 2N hydrochloric acid were added, and the mixture was heated and stirred for 2 hours under reflux. After the reaction is completed, 200m of water
and extracted with 500 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure,
6.5 g of 4- (3 ', 4', 5'-trifluorophenyl) cyclohexanecarbaldehyde was obtained.

[0068] (3) a suspension solution of THF20ml of methyltriphenylphosphonium bromide 2.7g was stirred under nitrogen stream at room temperature the reaction solution was added potassium over t- butoxide 1.1g gradually while cooling to 0 ℃ After stirring for 1 hour with 1.5 g of 4- (3 ', 4', 5'-trifluorophenyl) cyclohexanecarbaldehyde in THF
5 ml solution was added dropwise. The reaction mixture was warmed to room temperature,
Stirring was further performed for 2 hours. After completion of the reaction, the reaction mixture was added to 50 ml of water and extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, chromatographed on silica gel with ethyl acetate / heptane (1: 5), and recrystallized from heptane to give 4-trans- (3 ′, 4 ′, 4 ′). 1.05 g of 5'-trifluorophenyl) cyclohexylethene was obtained. m. p. 20.3 ~
21.3 ° C.

Example 3 Synthesis of 4-trans- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexylethene (Compound No. 3) (1) Under a nitrogen stream, magnesium was added to 20 ml of THF.
4g was suspended therein, and 3,5-
Difluoro-4-trifluoromethylbromobenzene 4
A solution in which 0 g was dissolved was added dropwise, and the mixture was stirred at room temperature for 1 hour. A solution of 20 g of 1,4-cyclohexanedione monoethylene ketal dissolved in 100 ml of THF was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 200 ml of a saturated aqueous solution of ammonium chloride was added, and 500 ml of ethyl acetate was added.
Extracted with l. The organic layer is dried over magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain 23 g of 1,1-ethylenedioxy-4-hydroxy-4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexane.

(2) 23 g of 1,1-ethylenedioxy-4-hydroxy-4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexane was dissolved in 200 ml of toluene, and p-toluenesulfonic acid was added to this solution. 5 g of hydrate was added, and the mixture was stirred for 1 hour under reflux. After cooling, the reaction solution was washed with 200 ml of water, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1,1-ethylenedioxy-4- (3 ', 5'-difluoro-4'-) was removed. 17.3 g of (trifluoromethylphenyl) -3-cyclohexene were obtained.

(3) 1,1-Ethylenedioxy-4- (3 ′, 5′difluoro-4 ′) was added to 200 ml of ethanol.
-Trifluoromethylphenyl) -3-cyclohexene (17.3 g) was dissolved, and palladium / carbon (5%) 5 g
Was added thereto, and the mixture was stirred under a hydrogen atmosphere to perform catalytic reduction. After completion of the reaction, the catalyst was separated by filtration, and the organic layer was distilled off under reduced pressure.
15.7 g of 1-ethylenedioxy-4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexane was obtained.

(4) 1,5.7 g of 1,1-ethylenedioxy-4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexane and 11.3 g of formic acid
g and toluene (5 ml) were added, and the mixture was heated and stirred for 2 hours under reflux. The reaction solution was added to 50 ml of water, and ethyl acetate 100
Extracted in ml. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 12.0 g of 4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexanone.

[0073] (5) suspension solution THF20ml of methoxymethyl triphenylphosphonium chloride 7g was stirred under a stream of nitrogen, was added potassium over t- butoxide 2.9g gradually while cooling to 0 ° C.. Reaction solution at room temperature
After stirring for 4 hours, 4- (3 ', 5'-difluoro-4'
-Trifluoromethylphenyl) cyclohexanone 4.
7 g of a 30 ml solution of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After the reaction,
The mixture was added to 100 ml of water and extracted with 200 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and chromatographed on silica gel with ethyl acetate / heptane (1: 5) to give 4- (3 ', 5'-difluoro-4'-trifluoro). 2.06 g of (methylphenyl) methoxymethylenecyclohexane was obtained.

(6) 10 ml of THF and 10 ml of 2N hydrochloric acid were added to 2.06 g of 4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) methoxymethylenecyclohexane, and the mixture was heated and stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was added to 20 ml of water and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 4- (3 ', 5'-difluoro-4'
Thus, 1.99 g of (trifluoromethylphenyl) cyclohexanecarbaldehyde was obtained.

[0075] (7) a suspension solution of THF10ml of methyltriphenylphosphonium bromide 3g stirred under a stream of nitrogen, was added potassium over t- butoxide 1.2g gradually while cooling to 0 ° C.. After the reaction solution was stirred at room temperature for 1 hour, a solution of 1.99 g of 4- (3 ', 5'-difluoro-4'-trifluoromethylphenyl) cyclohexanecarbaldehyde in 5 ml of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 20 ml of water and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure . The concentrated residue was chromatographed on silica gel with ethyl acetate / heptane (1: 5) and recrystallized with heptane to give 4-trans- (3 ', 5). 300 mg of '-difluoro-4'-trifluoromethylphenyl) cyclohexylethene were obtained.

The following compounds are produced according to the above procedures. Compound No. 4.3- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -2E-propene 5.3- (4'-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl ) -1-Propene 6.4- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -1-butene
m. p. 16.8-19.3 ° C 7.4- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -2E-butene 8.4- (4'-trans- (3", 4 ", 5 "-trifluorophenyl) cyclohexyl) -3E-butene 9.5- (4'-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) -1-pentene 10.5- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -3E-pentene

11.5- (4'-trans- (3 ",
4 ", 5" -trifluorophenyl) cyclohexyl)
-4E-pentene 12.6- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -1-hexene 13.6- (4'-trans- (3", 4 ", 5" -tri- Fluorophenyl) cyclohexyl) -2E-hexene 14.6- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -3E-hexene 15.6- (4'-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) -4E-hexene 16.7- (4'-trans- (3 ', 4 ", 5" -trifluorophenyl) cyclohexyl) -2E-heptene 17.7- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -3E-heptene 18.7- (4'-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) -4E-heptene 19.8- (4'-trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -3E-octene 20.8- (4 ' -Trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) -4E-octene

21.9- (4'-trans- (3 ",
4 ", 5" -trifluorophenyl) cyclohexyl)
-4E-nonene 22.3- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -2E-propene 23.3- (4'-trans- (3", 5 "difluoro-4"-) Trifluoromethylphenyl) cyclohexyl) -1-propene 24.4- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -1-butene 25.4- (4'-trans- (3", 5 "-difluoro-4" -trifluoromethylphenyl) cyclohexyl) -2E-butene 26.4- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -3E-butene 27.5- ( 4'-trans- (3 ", 5" difluoro-4 " Trifluoromethylphenyl) cyclohexyl) -1-pentene 28.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -2E-pentene 29.5- (4'-trans- (3", 5 "-difluoro-4" -trifluoromethylphenyl) cyclohexyl-3E-pentene 30.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4E-pentene

31.6- (4'-trans- (3 ",
5 "-difluoro-4" -trifluoromethylphenyl) cyclohexyl) -1-hexene 32.6- (4'-trans (3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -2E-hexene 33.6- ( 4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -3E-hexene 34.6- (4'-trans- (3", 5 "difluoro-4" -trifluoromethylphenyl) cyclohexyl)- 4E-Hexene 35.7- (4'-trans- (3 ", 5" -difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -2E-heptene 36.7- (4'-trans- (3", 5 "difluoro-4" -tri) Fluoromethylphenyl) cyclohexyl ) -3E-Heptene 37.7- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4E-heptene 38.8- (4'-trans- (3", 5 "difluoro-4"-) Trifluoromethylphenyl) cyclohexyl) -3E-octene 39.8- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4E-octene 40.9- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethylphenyl) cyclohexyl) -4E-nonene

41.2- (4'-trans- (3 ",
5 "-difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) ethene 42.3- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -2E-propene 43.3- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -1-propene 44.4- (4'-trans (3", 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -1 butene 45. 4- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -2E-butene 46.4- (4'-trans- (3", 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl ) 3E-butene 47.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -1-pentene 48.5- (4'-trans- (3", 5 "difluoro-4" -triene) Fluoromethoxyphenyl) cyclohexyl) -2E-pentene 49.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -3E-pentene 50.5- (4'-trans- (3", 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -4E-pentene

51.6- (4'-trans- (3 ",
5 "-difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -1-hexene 52.6- (4'-trans- (3 ', 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) -2E-hexene 53.6- ( 4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -3E-hexene 54.6- (4'-trans- (3", 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl)- 4E-Hexene 55.7- (4'-trans- (3 ", 5" -difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -2E-heptene 56.7- (4'-trans- (3", 5 "difluoro-4" -tri) Fluoromethoxyphenyl) Clohexyl) -3E-heptene 57.7- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4E-heptene 58.8- (4'-trans- (3", 5 "difluoro-4") -Trifluoromethoxyphenyl) cyclohexyl) -3E-octene 59.8- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4E-octene 60.9- (4'-trans- ( 3 ", 5" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) -4E-nonene

61.2- (4'-trans- (3 ",
5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl) ethene 62.3- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -2E-propene 63.3- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -1-propene 64.4- (4'-trans- (3", 5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl) -1butene 65.4- (4 '-Trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -2E-butene 66.4- (4'-trans- (3", 5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl) -3E-butene 67.5- (4′-trans- (3 ″, 5 ″ difluoro-4 ″ difluoromethoxyphenyl) cyclohexyl) -1-pentene 68.5- (4′-trans- (3 ″, 5 ″ difluoro-4 ″ difluoromethoxyphenyl) cyclohexyl ) -2E-pentene 69.5- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -3E-pentene 70.5- (4'-trans- (3", 5 "difluoro-4"-) Difluoromethoxyphenyl) cyclohexyl) -4E-pentene

71.6- (4'-trans- (3 ",
5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl) -1-hexene 72.6- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -2E-hexene 73.6- (4 ' -Trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -3E-hexene 74.6- (4'-trans- (3", 5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl) -4E-hexene 75 0.7- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -2E-heptene 76.7- (4'-trans- (3", 5 "difluoro-4" difluoromethoxyphenyl) cyclohexyl ) -3E-Heptene 77.7- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -4E-heptene 78.8- (4'-trans- (3", 5 "difluoro-4" difluoro Methoxyphenyl) cyclohexyl) -3E-octene 79.8- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) -4E-octene 80.9- (4'-trans- (3", 5 "Difluoro-4" difluoromethoxyphenyl) cyclohexyl) -4E-nonene

Example 4 2- (4'-trans- (4 "-trans- (3 '",
Synthesis of 4 ′ ″, 5 ″ ″-trifluorophenyl) cyclohexyl) cyclohexyl) ethene (Compound No.
81) (1) 11.6 g of cut magnesium (0.477 mo)
l) was placed in a 2 L three-necked flask, and THF was introduced under a nitrogen stream.
100 ml, and while stirring, 91.6 g (0.434 mol) of 3,4,5-trifluorobromobenzene T
A 200 ml solution of HF was added dropwise at a rate keeping the temperature at 30 ° C., and after completion of the addition, the mixture was stirred at room temperature for 2 hours. Then add 4
THF containing 94 g (0.395 mol) of 4,4'-dicyclohexanedione monoethylene acetal
The solution was added dropwise over 45 minutes so as to keep the temperature at 30 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours and left overnight.

Thereafter, the reaction solution was stirred again, a saturated aqueous solution of ammonium chloride was added thereto little by little, and the resulting solution was extracted three times with 400 ml of ethyl acetate. Concentration gave 125 g (GC 79%) of 4-hydroxy-4- (3 ', 4', 5'-trifluorophenyl) dicyclohexaneethylene acetal as a tan solid. This was used for the next reaction without purification.

(2) 2 equipped with a Dean-Stark apparatus
125 g of the above-mentioned reaction product was dissolved in 500 ml of toluene in an L three-necked flask, and 6.5 g of Amberlist-15 was added thereto, followed by stirring for 4 hours while heating and distilling. After completion of the reaction, the solution was cooled to room temperature, Amberlist-15 was filtered off, and the filtrate was concentrated under reduced pressure. The residue was separated and purified by silica gel chromatography to obtain 85 g of 4- (3 ', 4', 5'-trifluorophenyl) -3'dicyclohexene-4-one ethylene acetal. It has a melting point of 107.0-11.
4.0 ° C.

(3) 66 g of 4- (3 ', 4', 5'-trifluorophenyl) -3'dicyclohexene-4-one ethylene acetal was placed in a 1 L three-necked flask.
And a mixed solvent of ethyl acetate / ethanol (3: 1) 50
0 ml was added for dissolution. To this solution was added 5 g of a palladium-carbon (5 wt%) catalyst, and the mixture was stirred under a hydrogen gas atmosphere. When the absorption of hydrogen was no longer observed, the stirring was stopped and the catalyst was removed by filtration. The resulting solution was concentrated under reduced pressure to obtain a clear oil. This was purified by recrystallization from ethanol, and trans-4- (3 ', 4', 5 '
There was obtained 24 g of (trifluorophenyl) dicyclohexane-4-one ethylene acetal. It has a melting point of 1.
01.0 to 104.5 ° C.

(4) Trans-4- (3 ', 4', 5'-trifluorophenyl) dicyclohexane-4-one ethylene acetal 24 g in a 200 ml eggplant flask
It was placed and dissolved by adding toluene 100 ml, and then stirred for 4 hours under heating refluxing added formic acid 15.6g to this solution. After completion of the reaction, the mixture was cooled to room temperature, and 200 ml of ethyl acetate was added thereto, followed by washing with water. After the organic layer was dried over magnesium sulfate, it was concentrated under reduced pressure to obtain white crystals . Recrystallization purification This is from n- heptane, 4-(trans-4 'by chromatography (3 ", 4", 5 "over-trifluorophenyl) cyclohexyl) was obtained cyclohexanone 17 g. This material had a melting point of 96.7～ 99.6 ° C.

(5) 16.5 g of methoxymethyltriphenylphosphonium chloride was placed in a 300 ml three-necked flask.
And 100 ml of THF was added to suspend the mixture, and potassium-t-butoxide 6.5 was maintained at a temperature of -10 ° C or lower.
g was added. The mixture was stirred at -10 ° C for 1 hour, and then 4- (trans-4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) cyclohexanone 10
g of THF (80 ml) was added dropwise at a rate keeping -10 ° C. The mixture was stirred at this temperature for 1 hour and further at room temperature for 2 hours. After completion of the reaction, 100 ml of water was added and 100 ml of ethyl acetate were added.
The mixture was extracted three times with water and the organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a white solid. This was isolated and purified by silica gel column chromatography, and 4- (trans-4 '-(3 ", 4",
This gave 10.2 g of 5 "-trifluorophenyl) cyclohexyl) methoxymethylenecyclohexane, which had a melting point of 78.4-81.2 ° C.

(6) 10.2 g of 4- (trans-4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) methoxymethylenecyclohexane was placed in a 300 ml eggplant flask, and dissolved by adding 80 ml of THF. After the reaction was completed, the mixture was cooled to room temperature, added with 30 ml of water, extracted three times with 50 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. This gave 6 g of a clear oil 4- (trans-4 '-(3 ", 4", 5 "-trifluorophenyl) cyclohexyl) cyclohexanecarbaldehyde. This was used for the next reaction without purification.

(7) 14.0 g of methyltriphenylphosphonium bromide was placed in a 300 ml three-necked flask, and 100 ml of THF was added to suspend the mixture. The mixture was stirred at −10 ° C. for 1 hour, and a solution of 8.5 g of 4- (trans-4 ′-(3 ″, 4 ″, 5 ″ -trifluorophenyl) cyclohexanecarbaldehyde) in 100 ml of THF was added at a temperature of −10 ° C. After the reaction was completed, 100 ml of water was added, and the mixture was extracted three times with 100 ml of ethyl acetate, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Then, the mixture was concentrated under reduced pressure to obtain a white solid, which was isolated by silica gel column chromatography, purified by recrystallization using ethanol, and trans- (4- (trans-4 ′-( 3.8 g of 3 ", 4", 5 "-trifluorophenyl) cyclohexyl) cyclohexyl) ethene were obtained. This shows a liquid crystal phase and CN points 57.1 to 58.
The temperature was 8 ° C and the NI point was 69.2 to 71.3 ° C.

The following compounds are produced according to the above procedures. Compound No. 82.3- (4'-trans- (4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -2E-propene 83.3- (4'-trans- (4 "-trans- (3 ′ ″, 4 ″ ″, 5 ″ ″-trifluorophenyl) cyclohexyl) cyclohexyl) -1-propene mp. 30.8-31.2 DEG C. 84.4- (4'-trans- (4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -1butene CN point 64 0.1 ° C, NI point 99.1 ° C 85.4- (4'-trans- (4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -2E-butene 86.4- (4'-trans- (4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -3E-butene 87.5- (4'-trans- (4 " -Trans- (3 '", 4'", 5 "-trifluorophenyl) cyclohexyl) cyclohexyl) -1-pentene 88.5- (4'-trans- (4" -trans- (3 '", 4'", 5 '"-trifluorophenyl) cyclohexyl) cyclohexyl) -2E-pentene 89.5- (4'-trans- (4" -trans- (3'", 4 '", 5'"- Trifluorophenyl) cyclohexyl) cyclohexyl) -3E-pentene 90.5- (4'-trans (4 "-trans (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -4E-pentene CN point 91.9-92.3, NI point 110.4-1
11.1 ° C

91.6- (4'-trans- (4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -1-hexene 92.6- (4'-trans ( 4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -2E-hexene 93.6- (4'-trans- (4 "-trans- (3 '", 4'", 5 '"-trifluorophenyl) cyclohexyl) cyclohexyl) -3E-hexene 94.6- (4'-trans- (4" -trans- (3 ", 4", 5 "-trifluorophenyl) cyclohexyl) cyclohexyl) -4E-hexene 95.7- (4'-trans- (4 "-trans- (3", 4 ", 5""-trifluorophenyl) Enyl) cyclohexyl) cyclohexyl) -2E-heptene 96.7- (4'-trans- (4 "-trans (3", 4 ", 5" -trifluorophenyl) cyclohexyl) cyclohexyl) -3E-heptene 97.7- (4'-trans- (4 "-trans- (3 '", 4'",5" -trifluorophenyl) cyclohexyl) cyclohexyl) -4E-heptene 98.8- (4'-trans- (4 "-trans (3"") , 4 '", 5'"-trifluorophenyl) cyclohexyl) cyclohexyl) -3E-octene 99.8- (4'-trans- (4 "-trans- (3 '", 4'",5""-trifluorophenyl ) Cyclohexyl) cyclohexyl) -4E-octene 100.9- (4'-trans- (4 "- Ransu (3 '', 4 '', 5 '' over-trifluorophenyl) cyclohexyl) cyclohexyl) over 4E- nonene

101.2- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) ethene 102.3- (4'-trans- (4 "-Trans- (3 '", 5'"difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -2E-propene 103.3- (4'-trans- (4" -trans- (3 '", 5'" difluoro-4 "" -Trifluoromethylphenyl) cyclohexyl) cyclohexyl) -1-propene 104.4- (4'-trans- (4 "-trans- (3", 5 "difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -1buten 105.4- (4'- Trans (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -2Ebutene 106.4- (4'-trans- (4 "-trans (3 '", 5'"Difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -3E-butene 107.5- (4'-trans- (4" -trans- (3 "", 5 "difluoro-4""-trifluoromethylphenyl) Cyclohexyl) cyclohexyl) -1-pentene 108.5- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -2E-pentene 109.5- ( 4'-trans (4 "-tra Trans (3 '", 5'" difluoro-4 "'-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -3E-pentene 110.5- (4'-trans- (4" -trans- (3'", 5 '" difluoro-4 "" -Trifluoromethylphenyl) cyclohexyl) cyclohexyl) -4E-pentene

111.6- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -1-hexene 112.6- (4'-trans- (4 "-trans- (3 '", 5'"difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -2E-hexene 113.6- (4'-trans- (4" -trans- (3 '", 5'"Difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -3E-hexene 114.6- (4'-trans- (4" -trans- (3 ", 5" difluoro-4 ""-trifluoromethylphenyl) Cyclohexyl) cyclohexyl) -4E-hexene 115 0.7- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -2E-heptene 116.7- (4'-trans- (4 "-trans- (3 ′ ″, 5 ″ ″ difluoro-4 ″ ″-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -3E-heptene 117.7- (4′-trans- (4 ″ -trans- (3 ″, 5 ″ ″ difluoro-4 ″ ″) -Trifluoromethylphenyl) cyclohexyl) cyclohexyl) -4E-heptene 118.8- (4'-trans- (4 "-trans- (3", 5 "difluoro-4""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -3E -Octene 119.8- (4'-to Trans- (4 "-trans (3", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -4E-octene 120.9- (4'-trans- (4 "-trans (3 '", 5 "" Difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) cyclohexyl) -4E-nonene

121.2- (4'-trans- (4 "-trans- (3", 5 "-difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) cyclohexyl) ethene 122.3- (4'-trans- (4 "-trans- (3 '", 5'"difluoro-4'"-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-12E-Propene 123.3- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-1-propene 124.4- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-1-butene 125.4- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-12E-butene 126.4- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-3E-butene 127.5- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-1-pentene 128.5- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 '"-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-12E-pentene 129.5- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-3E-pentene 130.5- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-4E-penten

131.6- (4'-trans- (4 "-trans- (3"",5""difluoro-4""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl) -1-hexene 132.6- (4'- Trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-13E-hexene 133.6- (4'-trans- (4 "-trans- (3"",5""difluoro-4""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-3E-Hexene 134.6- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-4E-hexene 135.7- (4'-trans- (4 "-trans- (3", 5 "difluoro-4" -trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-2E-heptene 136.7- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-13E-heptene 137.7- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-14E-heptene 138.8- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-13E-octene 139.8- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-4E-octene 140.9- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) cyclohexyl)
-4E-Nonen

141.2- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) ethene 142.3- (4'-trans- ( 4 ″ -trans- (3 ′ ″, 5 ′ ″ difluoro-4 ′ ″ difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -2E-propene 143.3- (4′-trans- (4 ″ -trans- (3 ′ ″, 5 ′ ″ difluoro- 4 '"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -1-propene 144.4- (4'-trans- (4" -trans- (3 ", 5"difluoro-4'"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) −
1-butene 145.4- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 '"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -2E-butene 146.4- (4'-trans- (4 ″ -trans- (3 ′ ″, 5 ′ ″ difluoro-4 ′ ″ difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -3E-butene 147.5- (4′-trans- (4′-trans- (3 ′ ″, 5 ′ "Difluoro-4 '" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -1-pentene 148.5- (4'-trans- (4 "-trans- (3", 5 "difluoro-4'" difluoromethoxyphenyl) cyclohexyl) Cyclohexyl) -2E-pentene 149.5 (4'-trans- (4 "-trans- (3", 5 "-difluoro-4" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -3E-pentene 150.5- (4'-trans- (4 "-trans- ( 3 '", 5"' difluoro-4 '"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -4E-pentene

151.6- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -1-hexene 152.6- (4'-trans -(4 "-trans- (3 '", 5 ""difluoro-4'"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -2E-hexene 153.6- (4'-trans- (4" -trans- (3 '", 5 '"Difluoro-4'" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -3E-hexene 154.6- (4'-trans- (4 "-trans- (3 '", 5'"difluoro-4'" difluoromethoxyphenyl) Cyclohexyl) cyclohexyl) -4E-hexene 155 0.7- (4'-trans- (4 "-trans- (3", 5 "" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -4E-heptene 156.7- (4'-trans- (4" -Trans- (3 ', 5'"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -3E-heptene 157.7- (4'-trans- (4 "-trans- (3'", 5 '"difluoro-4'"Difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -4E-heptene 158.8- (4'-trans- (4" -trans- (3 ", 5" difluoro-4 '"difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -3E -Octene 159.8- (4'-to Lance- (4 "-trans- (3", 5 "" difluoro-4 "difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -4E-octene 160.9- (4'-trans- (4" -trans (3 '", 5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) cyclohexyl) -4E-nonene

Example 5 2- (4'-trans- (2 "-(3 '", 4'",
Synthesis of 5 ′ ″-trifluorophenyl) ethyl) cyclohexyl) ethene (Compound No. 161) (1) 234 g of 3,4,5-trifluorobenzyltriphenylphosphonium bromide in tetrahydrofuran 5
The 00 ml of the suspension was stirred under a nitrogen stream, and 32.4 g of sodium methoxide was added little by little at room temperature. After the reaction solution was stirred at room temperature for 1 hour, a solution of 50 g of 4-formylcyclohexanone in 250 ml of tetrahydrofuran was added dropwise. After stirring at room temperature for 2 hours, the mixture was added to 1 l of water and extracted with 1 l of ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent is concentrated under reduced pressure and 4- (2 '-(3 ", 4", 5-trifluorophenyl) ethenyl)
71 g of cyclohexanone were obtained.

(2) 4- (2 '-(3 ", 4", 5 "-trifluorophenyl) ethenyl) cyclohexanone 7
1 g was dissolved in 500 ml of ethanol, 2.0 g of palladium / carbon (5%) was added, and the mixture was stirred and hydrogenated under a hydrogen atmosphere until hydrogen absorption was completed. After the reaction, remove the catalyst.
After filtration, the filtrate was concentrated under reduced pressure to give 4- (2 '-(3 ",
70 g of 4 ", 5" -trifluorophenyl) ethyl) cyclohexanone were obtained.

(3) A suspension of 112.3 g of methoxymethyltriphenylphosphonium chloride in 300 ml of THF was stirred under a stream of nitrogen, and 45.4 g of potassium t-butoxide was added little by little while cooling to 0 ° C. Was. After the reaction solution was stirred at room temperature for 1 hour, 4- (2 ′-(3 ″,
A solution of 70 g of 4 ", 5" -trifluorophenyl) ethyl) cyclohexanone in 200 ml of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours.
After the completion of the reaction, 500 ml of ethyl acetate was added to 500 ml of water.
Extracted with l. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and chromatographed on silica gel with ethyl acetate / heptane (1: 5) to give 4- (2 '-(3 ", 4", 5). ″ -Trifluorophenyl) ethyl)
53.7 g of methoxymethylenecyclohexane was obtained.

(4) 4- (2 '-(3 ", 4", 5 "-trifluorophenyl) ethyl) methoxymethylenecyclohexane (20 g) was mixed with 100 ml of THF and 100 ml of 2N hydrochloric acid.
Then, the mixture was heated and stirred for 2 hours under reflux. After completion of the reaction, the reaction mixture was added to 300 ml of water and extracted with 300 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 17 g of 4- (2 '-(3 ", 4", 5 "-trifluorophenyl) ethyl) cyclohexanecarbaldehyde.

[0104] (5) a suspension solution of THF50ml of methyltriphenylphosphonium bromide 27g stirred under a stream of nitrogen, was added potassium over t- butoxide 10.6g gradually while cooling to 0 ° C.. After stirring the reaction solution at room temperature for 1 hour, a solution of 17 g of 4- (2 '-(3 ", 4", 5 "-trifluorophenyl) ethyl) cyclohexanecarbaldehyde in 50 ml of THF was added dropwise, and the reaction mixture was warmed to room temperature. After completion of the reaction, the reaction mixture was added to water (100 ml), extracted with ethyl acetate (100 ml), the organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure , and the concentrated residue was concentrated on silica gel. Ethyl acetate/
After chromatographic treatment with heptane (1: 5), recrystallization from heptane gave 2- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) ethene. 9 g were obtained.

The following compounds are prepared according to the above procedure. Compound No. 162.3- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -1-propene 163.3- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -2E-propene 164.4- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -1-butene 165.4- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -2E-butene 166.4- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -3E-butene 167.5- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -1-pentene 168.5- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -2E-pentene 169.5- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -3E-pentene 170.5- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -4E-pentene

171.6- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) -1-hexene 172.6- (4'-trans ( 2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -2E-hexene 173.6- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -3E-hexene 174.6- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -4E-hexene 175.7- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -2E-heptene 176.7- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -3E-heptene 177.7- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -4E-heptene 178.8- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -3E-octene 179.8- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -4E-octene 180.9- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) -4E-nonene

181.2- (4'-trans- (2 "-(3", 5 "-difluoro-4" -trifluoromethylphenyl) ethyl) cyclohexyl) ethene 182.3- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -2E-propene 183.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -1-propene 184.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -1-butene 185.4- (4'-trans (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -2E-butene 186.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -3E-butene 187.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -1-pentene 188.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -2E-pentene 189.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -3E-pentene 190.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -4E-pentene

191.6- (4'-trans- (2 "-(3 '", 5 "" difluoro-4 "-trifluoromethylphenyl) ethyl) cyclohexyl) -1-hexene 192.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -2E-hexene 193.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -3E-hexene 194.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -4E-hexene 195.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -2E-heptene 196.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -3E-heptene 197.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -4E-heptene 198.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -3E-octene 199.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -4E-octene 200.9- (4'-trans (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethylphenyl) ethyl) cyclohexyl) -4E-nonene

201.2- (4'-trans- (2 "-(3", 5 "-difluoro-4" -trifluoromethoxyphenyl) ethyl) cyclohexyl) ethene 202.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -2E-propene 203.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-propene 204.4- (4'-trans (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-butene 205.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -2Ebutene 206.4- (4'-trans (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -3E-butene 207.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-pentene 208.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -2E-pentene 209.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -3E-pentene 200.5- (4'-trans (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -4E-pentene

211.6- (4'-trans- (2 "-(3", 5 "-difluoro-4" -trifluoromethoxyphenyl) ethyl) cyclohexyl) -1-hexene 212.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -2E-hexene 213.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -3E-hexene 214.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -4E-hexene 215.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -2E-heptene 216.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -3E-heptene 217.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -4E-heptene 218.8- (4'-trans (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -3E-octene 219.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -4E-octene 220.9- (4'-trans (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxyphenyl) ethyl) cyclohexyl) -4E-nonene

221.2- (4'-trans- (2 "-(3", 5 "-difluoro-4'-difluoromethoxyphenyl) ethyl) cyclohexyl) ethene 222.3- (4'-trans- (2"ー (3 ′ ″,
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -2E-propene 223.3- (4'-trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -1-propene 224.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -1butene 225.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) -2E-butene 226.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -3E-butene 227.5- (4'-trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -1-pentene 228.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -2E-pentene 229.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -3E-pentene 230.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -4E-pentene

231.6- (4'-trans- (2 "-(3 '", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) -1-hexene 232.6- (4'-trans ( 2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -2E-hexene 233.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -3E-hexene 234.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -4E-hexene 235.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) cyclohexyl) ethyl) -2E-heptene 236.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -3E-heptene 237.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -4E-heptene 238.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -3E-octene 239.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -4E-octene 240.9- (4'-trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxyphenyl) ethyl) cyclohexyl) -4E-nonene

Example 6 Synthesis of 2- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) ethene (Compound No. 241) (1) A suspension of 21.8 g of triethylphosphonoacetate in 50 ml of tetrahydrofuran was stirred under a nitrogen stream, and 11.8 g of potassium-t-butoxide was added little by little at room temperature. After stirring the reaction solution at room temperature for 1 hour,
A solution of 20 g of-(3 ', 4', 5'-trifluorophenyl) cyclohexanone in 50 ml of THF was added dropwise. After stirring at room temperature for 2 hours, 100 ml of water was added, and ethyl acetate was added.
Extracted with 00 ml. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 183 g of 4- (3 ', 4', 5'-trifluorophenyl) ethoxycarbonylmethylenecyclohexane.

(2) Dissolve 18.3 g of 4- (3 ', 4', 5'-trifluorophenyl) ethoxycarbonylmethylenecyclohexane in 100 ml of ethanol, add 5 g of palladium / carbon (5%), stir, add hydrogen Hydrogen was added under an atmosphere until hydrogen absorption was completed. After completion of the reaction, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure to give 4- (3 ′,
17.2 g of 4 ', 5'-trifluorophenyl) ethoxycarbonylmethylcyclohexane was obtained.

(3) To a solution of 17.2 g of 4- (3 ', 4', 5'-trifluorophenyl) ethoxycarbonylmethylcyclohexane in 100 ml of tetrahydrofuran was added 2.2 g of lithium aluminum hydride, and the mixture was stirred at room temperature for 2 hours. . After completion of the reaction, 100 ml of ethyl acetate was added little by little, and 50 ml of 2N hydrochloric acid was further added. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 10.4 g of 4- (3 ', 4', 5'-trifluorophenyl) -1- (2'-hydroxyethyl) cyclohexane.

(4) 10.4 g of 4- (3 ', 4', 5'-trifluorophenyl) -1- (2'-hydroxyethyl) cyclohexane was added to 15 ml of a 47% aqueous HBr solution.
Was added and the mixture was stirred under reflux for 2 hours. The reaction solution is 50 ml of water
And extracted with 100 ml of ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 10.4 g of 4- (3 ', 4', 5'-trifluorophenyl) -1- (2'-bromoethyl) cyclohexane.

(5) In a nitrogen gas stream, place a mug in 10 ml of THF.
0.7 g of cesiumAdd, Into which 50ml of THF
4- (3 ', 4', 5'-trifluorophenyl) -1
Dissolve 9.8 g of-(2'-bromoethyl) cyclohexane
The dissolved solution was added dropwise and stirred at room temperature for 1 hour.next
1,4-cyclohexanedione monoethylene ketal 4
g in 30 ml of THF was added dropwise at room temperature.
Stir for 1 hour. After completion of the reaction, saturated aqueous ammonium chloride
Add 100 ml of solution and extract with 100 ml of ethyl acetate.
Was. Dry the organic layer over magnesium sulfate and evaporate the solvent under reduced pressure.
Distill off and remove 1,1-ethylenedioxy-4-hydroxy
-4- (2 '-(4 "-(3'", 4 '", 5'"
Trifluorophenyl) cyclohexyl) ethylcyclohexane
8.2 g of xane were obtained.

(6) Paratoluene in 100 ml of toluene
2.5 g of sulfonic acid-hydrate and 1,1-ethylenedioxy-4-hydroxy-4- (2 '-(4 "-(3", 4 ", 5" -trifluorophenyl) cyclohexyl) ethylcyclohexane After dissolving 8.2 g, the mixture was stirred under reflux for 1 hour.
l. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1,1-ethylenedioxy- (2 '-(4 "-(3"",4"",5""-trifluorophenyl) 6.7 g of cyclohexyl) ethyl) -3-cyclohexene were obtained.

(7) 1,1-Ethylenedioxy- (2 '-(4 "-(3'", 4 '",
6.7 g of 5 ′ ″-trifluorophenyl) cyclohexyl) ethyl) -3-cyclohexene was dissolved, 1 g of palladium / carbon (5%) was added, and catalytic reduction was carried out under a hydrogen atmosphere. Separate by filtration and decompress the organic layer.
After concentrating , 1,1-ethylenedioxy- (2 ′-(4 ″)
-(3 '", 4'", 5 '"-trifluorophenyl)
6.2 g of cyclohexyl) ethyl) cyclohexane were obtained.

(8) 1,1-ethylenedioxy- (2 ′
-(4 "-(3 '", 4'",5" -trifluorophenyl) cyclohexyl) ethyl) cyclohexane6.
5 g of formic acid and 2 ml of toluene were added to 2 g, and the mixture was heated and stirred for 2 hours under reflux. The reaction solution was poured into 20 ml of water and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 4.9 g of fluorophenyl) cyclohexyl) ethyl) cyclohexanone were obtained.

[0121] (9) Potassium suspension solution THF50ml of methoxymethyl triphenylphosphonium chloride 6.2g was stirred under a stream of nitrogen, while cooling to 0 ℃ over t-
2 g of butoxide were added in small portions. Reaction solution at room temperature
After stirring for 4 hours, 4.9 g of 4- (2 '-(4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) ethyl) cyclohexanone 4.9 g of T
A 20 ml solution of HF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After the reaction is completed,
The mixture was extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and chromatographed on silica gel with ethyl acetate / heptane (1: 5) to give 4- (2 '-(4 "-trans- (3'"). 3.8 g of, 4 '", 5'"-trifluorophenyl) cyclohexyl) ethyl) methoxymethylenecyclohexane was obtained.

(10) 4- (2 '-(4 "-trans- (3", 4 ", 5" -trifluorophenyl) cyclohexyl) ethyl) methoxymethylenecyclohexane (3.8 g) was treated with 10 ml of THF and 10 ml of 2N hydrochloric acid. In addition, the mixture was heated and stirred for 2 hours under distillation. After completion of the reaction, the reaction mixture was added to 50 ml of water and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 4- (2 '-(4 "-trans- (3'",
3.5 g of 4 '", 5"'-trifluorophenyl) cyclohexyl) ethyl) cyclohexanecarbaldehyde
I got

(11) A suspension of 3.5 g of methyltriphenylphosphonium bromide in 20 ml of THF was stirred under a nitrogen stream, cooled to 0 ° C., and 13 g of potassium-t-butoxide was added little by little. After the reaction solution was stirred at room temperature for 1 hour, 4- (2 '-(4 "-trans- (3'",
3.5 g of 4 '", 5"'-trifluorophenyl) cyclohexyl) ethyl) cyclohexanecarbaldehyde
Was added dropwise in a THF (20 ml) solution. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction,
0 ml, and extracted with 100 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, chromatographed on silica gel with ethyl acetate / heptane (1: 5), and recrystallized from heptane to give 2- (4 ').
-Trans (2 "-(4 '"-Trans (3 "",
There were obtained 2.2 g of 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -ethene.

The following compounds are produced according to the above procedures. Compound No. 242.3- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -1
-Propene 243.3- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -2
E-propene 244.4- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -1
Butene 245.4- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -2
E-butene 246.4- (4'-trans- (2 "-(4 '"-trans (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -3
E-butene 247.5- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -1
-Pentene 248.5- (4'-trans- (2 "-(4'-trans- (3"",4"",5""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -2
E-pentene 249.5- (4'-trans- (2 "-(4'-trans- (3"",4"",5""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -3
E-pentene 250.5- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -4
E-pentene

251.6- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -1-hexene 252.6 -(4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -2
E-hexene 253.6- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -3
E-hexene 254.6- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -4
E-hexene 255.7- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -2
E-heptene 256.7- (4'-trans- (2 "-(4'-trans- (3"",4"",5""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -3
E-heptene 257.7- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -4
E-heptene 258.8- (4'-trans- (2 "-(4'-trans- (3"",4"",5""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -3
E-octene 259.8- (4'-trans- (2 "-(4" -trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -4
E-octene 260.9- (4'-trans- (2 "-(4 '"-trans- (3 "", 4 "", 5 ""-trifluorophenyl) cyclohexyl) ethyl) cyclohexyl) -4
E-nonene

261.2- (4'-trans- (2 "-(4'-trans- (3"",5""difluoro-4""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) ethene 262.3- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-propene 263.3- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -1-propene 264.4- (4'-trans- (2 "-( 4 '"-trans- (3"",5""difluoro-4""-trifluoromethylphenyl) Clohexyl) ethyl) cyclohexyl) -1-butene 265.4- (4'-trans (2 "-(4" -trans (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl ) -2E-butene 266.4- (4'-trans- (2 "-(4'-trans- (3"",5""difluoro-4""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-butene 267.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -1-pentene 268.5- ( 4'-trans (2 "-(4 '"-trans (3 "", 5 "" Lulow 4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-pentene 269.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "") Trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-pentene 270.5- (4'-trans (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl ) Cyclohexyl) ethyl) cyclohexyl) -4E-pentene

271.6- (4'-trans- (2 "-(4'-trans- (3"",5""difluoro-4""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -1-hexene 272. 6- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-hexene 273.6- (4 '-Trans- (2 "-(4'"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-hexene 274.6- (4'-trans ( 2 "-(4 '"-trans (3 "", 5 "" difluoro-4 ""-trifluoromethyl Enyl) cyclohexyl) ethyl) cyclohexyl) -4E-hexene 275.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) Ethyl) cyclohexyl) -2E-heptene 276.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl)- 3E-Heptene 277.7- (4'-trans- (2 "-(4'-trans- (3"",5""difluoro-4""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-heptene 278.8 -(4'-trans- (2 "-(4 '"-trans 3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-octene 279.8- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-octene 280.9- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro- 4 ""-trifluoromethylphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-nonene

281.2- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) ethene 282.3- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -2E-propene 283.3- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -1-propene 284.4- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -1-butene 285.4- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -2E-butene 286.4- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -3E-butene 287.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -1-pentene 288.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -2E-pentene 289.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -3E-pentene 290.5- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -4E-pentene

291.6- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -1-hexene 292. 6- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -2E-hexene 293.6- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -3E-hexene 294.6- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -4E-hexene 295.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -2E-heptene 296.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -3E-heptene 297.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -4E-heptene 298.8- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -3E-octene 299.8- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -4E-octene 300.9- (4'-trans (2 "-(4" -trans- (3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) cyclohexyl) ethyl)
Cyclohexyl) -4E-nonene

301.2- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) ethene 302.3- ( 4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-propene 303.3- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -1-propene 304.4- (4'-trans- (2 "-(4'" -Trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) Clohexyl) ethyl) cyclohexyl) -1-butene 305.4- (4'-trans- (2 "-(4" -trans (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -30E-Butene 306.4- (4'-trans- (2 "-(4'-trans- (3"",5""difluoro-4""difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-butene 307. 5- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -1-pentene 308.5- (4'- Trans (2 "-(4 '"-Trans (3 "", 5 "" Luoro 4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-pentene 309.5- (4'-trans- (2 "-(4""-trans-(3"",5""difluoro-4""-) Difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-pentene 310.5- (4'-trans (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl ) Ethyl) cyclohexyl) -4E-pentene

311.6- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -1-hexene 312.6 -(4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -2E-hexene 313.6- (4'- Trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-hexene 314.6- (4'-trans- (2 "- (4 '"-trans (3"",5""difluoro-4""difluoromethoxy Enyl) cyclohexyl) ethyl) cyclohexyl) -4E-hexene 315.7- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl ) Cyclohexyl) -2E-heptene 316.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-heptene 317.7- (4'-trans- (2 "-(4" -trans- (3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-heptene 318.8- (4 '-Trans- (2 "-(4'"-trans 3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -3E-octene 319.8- (4'-trans- (2 "-(4 '"-trans (3 "", 5 "" Difluoro-4 "" Difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-octene 320.9- (4'-trans- (2 "-(4 '"-trans- (3 "", 5 "" difluoro-4 ") "Difluoromethoxyphenyl) cyclohexyl) ethyl) cyclohexyl) -4E-nonene

Example 7 Synthesis of 2- (4'-trans- (4 "-trans (2 '-(3"",4"",5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) ethene (Compound No. 321) (1) A suspension of 51.5 g of 3,4,5-trifluorobenzyltriphenylphosphonium bromide in 100 ml of tetrahydrofuran was stirred under a nitrogen stream, and 6.2 g of sodium methoxide was added little by little at room temperature. added. After stirring the reaction solution at room temperature for 1 hour, a solution of 20 g of 4- (4'-formylcyclohexyl) cyclohexanone in 50 ml of tetrahydrofuran was added dropwise. After stirring at room temperature for 2 hours,
The solution was added to 250 ml of water, and extracted with 500 ml of ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure to give 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethenyl) cyclohexyl) cyclohexanone 2
2.5 g were obtained.

(2) 22.5 g of 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethenyl) cyclohexyl) cyclohexanone
Was dissolved in 250 ml of ethanol, 5 g of palladium / carbon (5%) was added, and the mixture was stirred and hydrogenated under a hydrogen atmosphere until hydrogen absorption was completed. After the reaction is completed, the catalyst is filtered off.
The filtrate is concentrated under reduced pressure to give 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) cyclohexanone 2
0.4 g was obtained.

[0134] (3) a suspension solution of THF50ml of methoxymethyl triphenylphosphonium chloride 23g was stirred under a stream of nitrogen, potassium chromatography t- butoxide 8.2g was cooled to 0 ℃ was added portionwise. After stirring the reaction solution at room temperature for 1 hour, a solution of 20.4 g of 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) cyclohexanone in 100 ml of THF was added. It was dropped. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, add water 2
The mixture was poured into 50 ml, and extracted with 250 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and ethyl acetate / heptane (1: 5) on silica gel.
And chromatographically treated with 4- (4'-trans- (2 ")
-(3 '", 4'", 5 '"-trifluorophenyl)
15.6 g of ethyl) cyclohexyl) methoxymethylenecyclohexane were obtained.

(4) 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) methoxymethylenecyclohexane was mixed with 15.6 g of THF and 30 ml of 2N hydrochloric acid. In addition, the mixture was heated and stirred for 2 hours under distillation. After completion of the reaction, the reaction mixture was added to 100 ml of water and extracted with 100 ml of ethyl acetate.
The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 4- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluorophenyl) ethyl) cyclohexyl) cyclohexanecarbaldehyde 13.7
g was obtained.

[0136] (5) a suspension solution of THF50ml of methyltriphenylphosphonium bromide 15.2g stirred under a stream of nitrogen, was added potassium over t- butoxide 5.3g gradually while cooling to 0 ° C.. After the reaction solution was stirred at room temperature for 1 hour, 4- (4'-trans- (2 "-(3", 4 ", 5" -trifluorophenyl) ethyl) cyclohexyl) cyclohexanecarbaldehyde 13.7 g of THF 50 ml was added. The solution was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the mixture was poured into 100 ml of water and extracted with 100 ml of ethyl acetate. The organic layer is dried over anhydrous magnesium sulfate,
The mixture was concentrated under reduced pressure, chromatographed on silica gel with ethyl acetate / heptane (1: 5), and recrystallized from heptane to give 2- (4'-trans- (4 "-trans- (2 '"-(3 ""). , 4 ″ ″, 5 ″ ″-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) ethene 8.2 g was obtained.

The following compounds are produced according to the above procedures. Compound No. 322.3- (4'-trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -1-propene 323.3- (4 '-Trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -2E-propene 324.4- (4'-trans- (4 "-Trans- (2 '"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -1butene 325.4- (4'-trans- (4 "-trans (2'" -(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -2E-butene 326.4- (4'-tra Trans (4 "-trans- (2 '-(3"",4"",5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -3E-butene 327.5- (4'-trans- (4" -trans- (2 '"-(3"",4"",5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -1-pentene 328.5- (4'-trans- (4" -trans- (2'"-( 3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -2E-pentene 329.5- (4'-trans- (4 "-trans- (2 '"-(3 "", 4 ") ", 5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -3E-pentene 330.5- (4'-trans- (4" -tolane) Sue (2 '"-(3"",4"",5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl)-
4E-Pentene

331.6- (4'-trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -1-hexene 332.6 -(4'-trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -2E-hexene 333.6- (4'- Trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -3E-hexene 334.6- (4'-trans- (4 "-trans- (2 ′ ″-(3 ″ ″, 4 ″ ″, 5 ″ ″-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -4E-hexene 335 0.7- (4'-trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -2E-heptene 336.7- (4 ' -Trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -3E-heptene 337.7- (4'-trans- (4 "-trans- (2 ′ ″-(3 ″ ″, 4 ″ ″, 5 ″ ″-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -4E-heptene 338.8- (4′-trans- (4 ″ -trans- (2 ′ ″-( 3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -3E-octene 339.8- (4'-to Trans (4 "-trans (2 '-(3"",4"",5""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl)-
4E-octene 340.9- (4'-trans- (4 "-trans- (2"-(3 "", 4 "", 5 ""-trifluorophenyl) ethyl) cyclohexyl) cyclohexyl) -4E-nonene

341.2- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) ethene 342.3- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-propene 343.3- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-propene 344.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-butene 345.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-butene 346.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-butene 347.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-pentene 348.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-pentene 349.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-pentene 350.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-pentene

351.6- (4'-trans- (4 "-trans- (2 '-(3"",5""difluoro-4""-trifluoromethylphenyl) ethyl) cyclohexyl) cyclohexyl) -1-hexene 352. 6- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-hexene 353.6- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-hexene 354.6- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-hexene 355.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-heptene 356.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-heptene 357.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-heptene 358.8- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-octene 359.8- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-octene 360.9- (4'-trans (4 "-trans (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethylphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-nonene

361.2- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) ethene 362.3- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -2E-propene 363.3- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -1-propene 364.4- (4'-trans- (4 "-trans- ( 2 '"-(3"",5""difluoro-4""-trifluoromethoxy Nyl) ethyl) cyclohexyl) cyclohexyl) -1-butene 365.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl ) Cyclohexyl) -2E butene 366.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -3E -Butene 367.5- (4'-trans- (4 "-trans (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -1-pentene 368.5 -(4'-trans- (4 "-trans (2 '"-(3 " , 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -2E-pentene 369.5- (4'-trans- (4 "-trans- (2 '-(3"",5""difluoro- 4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -3E-pentene 370.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "") Trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -4E-pentene

371.6- (4'-trans- (4 "-trans- (2 '-(3"",5""difluoro-4""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -1-hexene 6- (4'-trans- (4 "-trans- (2 '-(3"",5""difluoro-4""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -2E-hexene 373.6- (4 '-Trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -3E-hexene 374.6- (4'-trans- ( 4 "-trans- (2 '"-(3 "", 5 "" difluoro-4 ""-trifluoro Toxylphenyl) ethyl) cyclohexyl) cyclohexyl) -4E-hexene 375.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl ) Cyclohexyl) cyclohexyl) -2E-heptene 376.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) 37E-heptene 377.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -4E-heptene 378. 8- (4'-trans -(2 '"-(3"",5""difluoro-4""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -3E-octene 379.8- (4'-trans- (4" -trans (2'"-(3"",5""difluoro-4""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -4E-octene 380.9- (4'-trans- (4" -trans- (2 '-(3 "", 5 "" difluoro-4 ""-trifluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -4E-nonene

381.2- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) ethene 382.3- ( 4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-propene 383.3- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-propene 384.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-butene 385.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-butene 386.4- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-butene 387.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -1-pentene 388.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-pentene 389.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-pentene 390.5- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-pentene

391.6- (4'-trans- (4 "-trans- (2 '-(3"",5""difluoro-4""difluoromethoxyphenyl) ethyl) cyclohexyl) cyclohexyl) -1-hexene 392.6 -(4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-hexene 393.6- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-hexene 394.6- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-hexene 395.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -2E-heptene 396.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-heptene 397.7- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-heptene 398.8- (4'-trans- (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -3E-octene 399.8- (4'-trans (4 "-trans- (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-octene 400.9- (4'-trans (4 "-trans (2"-(3 "", 5 "" difluoro-4 "" difluoromethoxyphenyl) ethyl) cyclohexyl)
Cyclohexyl) -4E-nonene

Example 8 Synthesis of 2- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-biphenyl) cyclohexyl) ethene (Compound No. 401) (1) 4- (3 ", 4" , 5 "-trifluorophenyl) -3'dicyclohexene-4-one 20 g of ethylene acetal and 16.7 g of DDQ were dissolved in 200 m of toluene.
and stirred under reflux for 4 hours. The precipitated insoluble material was separated by filtration, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified by column chromatography on silica gel (developing solvent; ethyl acetate / heptane = 1/5) to give 4- (3 ′,
13.9 g of 4 ', 5'-trifluoro-4 "-biphenyl) cyclohexane-4-one ethylene acetal was obtained.

(2) 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) cyclohexane-4-one
10 g of formic acid and 2 ml of toluene were added to 13.9 g of ethylene acetal, and the mixture was heated and stirred for 2 hours under reflux. The reaction solution was added to 50 ml of water, and extracted with 50 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 11.5 g of 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) cyclohexanone.

[0147] (3) a suspension solution of THF50ml of methoxymethyl triphenylphosphonium chloride 13.6g was stirred under a stream of nitrogen, potassium while cooling to 0 ℃ over t
48 g of butoxide were added in small portions. After the reaction solution was stirred at room temperature for 1 hour, 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) cyclohexanone 11.5
g of THF in 50 ml was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 100 ml of water and extracted with 100 ml of ethyl acetate.
The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and dried on silica gel with ethyl acetate / heptane (1: 1).
Chromatography treatment was performed in 5) to obtain 8.8 g of 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) methoxymethylenecyclohexane.

(4) To 8.8 g of 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) methoxymethylenecyclohexane was added 50 ml of THF and 50 ml of 2N hydrochloric acid, and the mixture was heated and stirred under reflux for 2 hours. Thereafter, the mixture was added to 100 ml of water and extracted with 100 ml of ethyl acetate.
The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 4- (3 ', 4', 5'-trifluoro-4 "
-Biphenyl) cyclohexanecarbaldehyde 7.5
g was obtained.

(5) A suspension of 9 g of methyltriphenylphosphonium bromide in 20 ml of THF was stirred under a nitrogen stream, and while cooling to 0 ° C., 3.1 g of potassium-t-butoxide was added little by little. After stirring the reaction solution at room temperature for 1 hour, a solution of 7.5 g of 4- (3 ', 4', 5'-trifluoro-4 "-biphenyl) cyclohexanecarbaldehyde in 50 ml of THF was added dropwise, and the reaction mixture was heated to room temperature. After completion of the reaction, the mixture was stirred for 2 hours, added to water (100 ml), extracted with ethyl acetate (100 ml), the organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure , and the concentrated residue was concentrated on silica gel with ethyl acetate / heptane. Chromatographic treatment was performed at (1: 5), and recrystallization from heptane gave 2- (4'-trans- (3 ", 4", 5 "-trifluoro-4'-biphenyl) cyclohexyl).
4.6 g of ethene were obtained.

The following compounds are prepared according to the above procedures. Compound No. 402.3- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -1-propene 403.3- (4'-trans- (3 ", 4", 5 "-trifluoro-4') "-Biphenylyl) cyclohexyl) -2E-propene 404.4- (4'-trans (3", 4 ", 5" -trifluoro-4 '"-biphenylyl) cyclohexyl) -1-butene 405.4- (4'-trans- (3", 4 ", 5" -trifluoro-4 '"-biphenylyl) cyclohexyl) -2E-butene 406.4- (4'-trans- (3", 4 ", 5"-trifluoro-4'"-biphenylyl) cyclohexyl) -3E-butene 407.5- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-biphenyli ) Cyclohexyl) -1-pentene 408.5- (4'-trans- (3 ", 4", 5 "-trifluoro-4" -biphenylyl) cyclohexyl) -2E-pentene 409.5- (4'-trans- (3 ", 4") , 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -3E-pentene 410.5- (4'-trans (3 ", 4", 5 "-trifluoro-4'"-biphenylyl) cyclohexyl) -4E-pentene

411.6- (4'-trans- (3 ″,
4 ", 5" -trifluoro-4 '"-biphenylyl) cyclohexyl) -1-hexene 412.6- (4'-trans- (3", 4 ", 5" -trifluoro-4 "-biphenylyl) cyclohexyl) -2E-hexene 413.6- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -3E-hexene 414.6- (4'-trans- (3 ", 4", 5 "-trifluoro-4'"-biphenylyl) Cyclohexyl) -4E-hexene 415.7- (4'-trans- (3 ", 4", 5 "-trifluoro-4" -biphenylyl) cyclohexyl) -2E-heptene 416.7- (4'-trans- (3 ", 4") , 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -3E- Ten 417.7- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -4E-heptene 418.8- (4'-trans- (3 ", 4", 5 "-trifluoro-4 '"-Biphenylyl) cyclohexyl) -3E-octene 419.8- (4'-trans- (3', 4", 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -4E-octene 420.9- (4'-trans ( 3 ", 4", 5 "-trifluoro-4 '"-biphenylyl) cyclohexyl) -4E-nonene

421.2- (4'-trans- (3 ",
5 "difluoro-4" -trifluoromethyl-4 '"
-Biphenylyl) cyclohexyl) ethene 422.3- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4" -biphenylyl) cyclohexyl) -2E-propene 423.3- (4'-trans- (3 ", 5 "difluoro-4" -trifluoromethyl-4 '"-biphenylyl) cyclohexyl) -1-propene 424.4- (4'-trans- (3", 5 "difluoro-4"-trifluoromethyl-4'"-biphenylyl) cyclohexyl) -1 Butene 425.4- (4'-trans- (3 ', 5 "difluoro-4"-trifluoromethyl-4'"-biphenylyl) cyclohexyl) -2E butene 426.4- (4'-trans- (3", 5 "difluoro-4) "-Trifluoromethyl-4 '" Biphenylyl) cyclohexyl) -3E-butene 427.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4""-biphenylyl) cyclohexyl) -1-pentene 428.5- (4'-trans ( 3 ", 5" difluoro-4 "-trifluoromethyl-4 '"-biphenylyl) cyclohexyl) -2E-pentene 429.5- (4'-trans (3 ", 5" difluoro-4 "-trifluoromethyl-4'"-biphenylyl) cyclohexyl ) -3E-Pentene 430.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4""-biphenylyl) cyclohexyl) -4E-pentene

431.6- (4'-trans- (3 ″,
5 "difluoro-4" -trifluoromethyl-4 '"
-Biphenylyl) cyclohexyl) -1-hexene 432.6- (4'-trans- (3 ', 5 "difluoro-4"-trifluoromethyl-4'"-biphenylyl) cyclohexyl) -2E-hexene 433.6- (4'-trans ( 3 ", 5" difluoro-4 "-trifluoromethyl-4 '"-biphenylyl) cyclohexyl) -3E-hexene 434.6- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4'"-biphenylyl) Cyclohexyl) -4E-hexene 435.7- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4" -biphenylyl) cyclohexyl) -2E-heptene 436.7- (4'-trans- (3 ") , 5 "difluoro-4" -trifluoro Methyl-4 '"-biphenylyl) cyclohexyl) -3E-heptene 437.7- (4'-trans- (3", 5 "difluoro-4"-trifluoromethyl-4'"-biphenylyl) cyclohexyl) -4E-heptene 438.8- (4 ') -Trans (3 ", 5" difluoro-4 "-trifluoromethyl-4 '"-biphenylyl) cyclohexyl-3E-octene 439.8- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethyl-4'"-Biphenylyl) cyclohexyl) -4E-octene 440.9- (4'-trans- (3", 5 "difluoro-4" -trifluoromethyl-4 '"-biphenylyl) cyclohexyl) -4E-nonene

441.2- (4'-trans- (3 ",
5 "difluoro-4" -trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) ethene 442.3- (4'-trans- (3", 5 "difluoro-4"-trifluoromethoxy-4'"-biphenylyl) cyclohexyl) -2E -Propene 443.3- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4" -biphenylyl) cyclohexyl) -1-propene 444.4- (4'-trans- (3 ", 5" difluoro- 4 "-trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -1-butene 445.4- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4'"-biphenylyl) cyclohexyl) -2E-butene 446.4- (4'-trans (3 ", 5" difluoro-4 "-trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -3E-butene 447.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4'"-Biphenylyl) cyclohexyl) -1-pentene 448.5- (4'-trans- (3", 5 "difluoro-4" -trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -2E-pentene 449.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -3E-pentene 450.5- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4'"-Biphenylyl) cyclohexyl) -4E-pentene

451.6- (4'-trans- (3 ″,
5 "-difluoro-4" -trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -1-hexene 452.6- (4'-trans- (3", 5 "difluoro-4"-trifluoromethoxy-4'"-biphenylyl) cyclohexyl) -2E-hexene 453.6- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4" -biphenylyl) cyclohexyl) -3E-hexene 454.6- (4'-trans- (3 ") , 5 "Difluoro-4" -trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -4E-hexene 455.7- (4'-trans- (3", 5 "difluoro-4"-trifluoromethoxy-4'"-biphenylyl) Cyclohexyl) -2E-heptene 456.7- 4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy-4 '"-biphenylyl) cyclohexyl) -3E-heptene 457.7- (4'-trans- (3 ", 5" difluoro-4 "-trifluoromethoxy) C 4 '"-biphenylyl) cyclohexyl) -4E-heptene 458.8- (4'-trans- (3", 5 "difluoro-4"-trifluoromethoxy-4'"-biphenylyl) cyclohexyl) -3E-octene 459.8- ( 4'-trans- (3 ", 5" -difluoro-4 "-trifluoromethoxy-4" -biphenylyl) cyclohexyl) -4E-octene 460.9- (4'-trans- (3 ", 5" difluoro-4 "-trifluoro) Methoxy-4 '"-biphenylyl) cyclohexyl)- E- nonene

461.2- (4'-trans- (3 ",
5 "difluoro-4" difluoromethoxy-4 '"
-Biphenylyl) cyclohexyl) ethene 462.3- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -2E-propene 463.3- (4'-trans- (3 ", 5 "difluoro-4" difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -1-propene 464.4- (4'-trans- (3", 5 "difluoro-4"difluoromethoxy-4'"-biphenylyl) cyclohexyl) -1 Butene 465.4- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -2E butene 466.4- (4'-trans- (3 ", 5" difluoro-4) "Difluoromethoxy-4 '" Biphenylyl) cyclohexyl) -3E-butene 467.5- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -1-pentene 468.5- (4'-trans- ( 3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -2E-pentene 469.5- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4'"-biphenylyl) Cyclohexyl) -3E-pentene 470.5- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4" -biphenylyl) cyclohexyl) -4E-pentene

471.6- (4'-trans- (3 ″,
5 "difluoro-4" difluoromethoxy-4 '"
-Biphenylyl) cyclohexyl) -1-hexene 472.6- (4'-trans- (3 ', 5 "difluoro-4"difluoromethoxy-4'"-biphenylyl) cyclohexyl) -2E-hexene 473.6- (4'-trans ( 3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -3E-hexene 474.6- (4'-trans (3 ", 5" difluoro-4 "difluoromethoxy-4'"-biphenylyl) Cyclohexyl) -4E-hexene 475.7- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4" -biphenylyl) cyclohexyl) -2E-heptene 476.7- (4'-trans- (3 ") , 5 "difluoro-4" difluoro Toxic-4 '"-biphenylyl) cyclohexyl) -3E-heptene 477.7- (4'-trans- (3", 5 "difluoro-4"difluoromethoxy-4'"-biphenylyl) cyclohexyl) -4E-heptene 478.8- (4 ' -Trans- (3 ", 5" difluoro-4 "difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -3E-octene 479.8- (4'-trans- (3 ", 5" difluoro-4 "difluoromethoxy-4'"-Biphenylyl) cyclohexyl) -4E-octene 480.9- (4'-trans- (3", 5 "difluoro-4" difluoromethoxy-4 '"-biphenylyl) cyclohexyl) -4E-nonene

Example 9 2- (4'-trans- (2 "-(3 '", 4'",
5 '"-trifluoro-4'"-biphenyl) ethyl)
Synthesis of cyclohexyl) ethene (Compound No. 481) (1) 2 g of magnesium in 10 ml of THF under a nitrogen stream
Was added thereto, and a solution prepared by dissolving 19.0 g of 3,4,5-trifluorobromobenzene in 150 ml of THF was added dropwise thereto, followed by stirring at room temperature for 1 hour. 1,1-ethylenedioxy-4- (2 '-(4 "-oxocyclohexyl)
A solution of 20 g of ethyl) cyclohexane dissolved in 50 ml of THF was added dropwise, and the mixture was stirred at room temperature for 1 hour. After the reaction was completed, 200 ml of a saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with 500 ml of ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give 1,1-ethylenedioxy-4- (2 '-(4 "-hydroxy-4"-(3', 4 '", 5'"). Thus, 23.8 g of -trifluorophenyl) cyclohexyl) ethylcyclohexane was obtained.

(2) 1,1-Ethylenedioxy-4- (2 '-(4 "-hydroxy-4") was added to 250 ml of toluene.
-(3 '", 4'", 5 '"-trifluorophenyl)
23.8 g of cyclohexyl) ethyl) cyclohexane were dissolved therein, and p-toluenesulfonic acid monohydrate 5 was dissolved therein.
g was added, and the mixture was stirred for 1 hour under distillation. Water 2
After washing with 50 ml, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1,1-ethylenedioxy-4- (2 ′-(4 ″-(3 ′ ″, 4 ′ ″, 5 18.2 g of '"-trifluorophenyl) -3" -cyclohexenyl) ethyl) cyclohexane were obtained.

(3) 1,1-ethylenedioxy-4- (2 '-(4 "-(3", 4 ", 5" -trifluorophenyl) -3 "-cyclohexenyl) ethyl) cyclohexane 18.2 g and DDQ 14.1 g were dissolved in 250 ml of toluene, and the mixture was stirred under reflux for 4 hours.The precipitated insoluble material was separated by filtration, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (developing solvent; ethyl acetate / heptane = 1/5) to give 1,1.
-Ethylenedioxy-4- (2 '-(3 ", 4", 5 "
12.6 g of -trifluoro-4 '"-biphenyl) ethyl) cyclohexane were obtained.

(4) 1,1-ethylenedioxy-4- (2 '-(3 ", 4", 5 "-trifluoro-4'"
10 g of formic acid and 2 ml of toluene were added to 12.6 g of -biphenyl) ethyl) cyclohexane, and the mixture was heated and stirred for 2 hours under reflux. The reaction solution was added to 50 ml of water, and extracted with 50 ml of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 4- (2 '-(3 ",
10.0 g of 4 ", 5" -trifluoro-4 '"-biphenyl) ethyl) cyclohexanone was obtained.

(5) A suspension of 11.3 g of methoxymethyltriphenylphosphonium chloride in 50 ml of THF was stirred under a stream of nitrogen, and cooled to 0 ° C. with potassium-t.
4.1 g of butoxide were added in small portions. After stirring the reaction solution at room temperature for 1 hour, 4- (2 '-(3 ", 4",
A solution of 10.0 g of 5 "-trifluoro-4 '"-biphenyl) ethyl) cyclohexanone in 50 ml of THF was added dropwise. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, added to water 100 ml, the organic layer was extracted with ethyl acetate 200ml and dried over anhydrous magnesium sulfate, concentrated under reduced pressure, the concentrated residue on silica gel,
Chromatography treatment with ethyl acetate / heptane (1: 5) gave 7.5 g of 4- (2 '-(3 ", 4", 5 "-trifluoro-4" -biphenyl) ethyl) methoxymethylenecyclohexane.

(6) 4- (2 '-(3 ", 4", 5 "-trifluoro-4" -biphenyl) ethyl) methoxymethylenecyclohexane was added to 7.5 g of THF and 50 ml of THF.
50 ml of N hydrochloric acid was added, and the mixture was heated and stirred for 2 hours under reflux. After completion of the reaction, the mixture was added to 100 ml of water,
Extracted with 0 ml. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 4- (2 '-(3 ",
5.8 g of 4 ", 5" -trifluoro-4 '"-biphenyl) ethyl) cyclohexylcarbaldehyde was obtained.

[0164] (7) a suspension solution of THF20ml of methyltriphenylphosphonium bromide 7.2g stirred under a stream of nitrogen, was added potassium over t- butoxide 1.6g gradually while cooling to 0 ° C.. After the reaction solution was stirred for 1 hour at room temperature, 4-(2 'chromatography (3 ", 4", 5 "trifluoride low 4'" over-biphenyl) ethyl) dropwise THF50ml solution of cyclohexane carbaldehyde 5.8 g. The reaction mixture was warmed to room temperature and stirred for another 2 hours. After completion of the reaction, the reaction mixture was added to 100 ml of water, and ethyl acetate was added.
Extracted with 00 ml. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, the concentrated residue on silica gel,
After chromatographic treatment with ethyl acetate / heptane (1: 5), recrystallization from heptane gave 2- (4'-trans- (2 "-(3", 4 ", 5" -trifluoro-4 '"-biphenyl) ethyl). 3.5 g of)) cyclohexyl) ethene were obtained.

The following compound is produced by repeating the same carbon-increasing reaction. 482.3- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -1-propene 483.3- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -2E-propene 484.4- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -1-butene 485.4- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -2E-butene 486.4- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -3E-butene 487.5- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -1-pentene 488.5- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -2E-pentene 489.5- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -3E-pentene 490.5- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -4E-pentene

491.6- (4'-trans- (2 "-(3", 4 ", 5" -trifluoro-4 "-biphenylyl) ethyl) cyclohexyl) -1-hexene 492.6- (4'-trans- (2 "-(3 '",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -2E-hexene 493.6- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -3E-hexene 494.6- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -4E-hexene 495.7- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -2E-heptene 496.7- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -3E-heptene 497.7- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -4E-heptene 498.8- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -3E-octene 499.8- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -4E-octene 500.9- (4'-trans- (2"-(3'",
4 '", 5"'-trifluoro-4 '"-biphenylyl) ethyl) cyclohexyl) -4E-nonene

501.2- (4'-trans- (2 "-(3", 5 "-difluoro-4" -trifluoromethyl-4 "-biphenylyl) ethyl) cyclohexyl) ethene 502.3- (4'- Trans (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-propene 503.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Propene 504.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -1
Buten 505.4- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-Buten 506.4- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-butene 507.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Pentene 508.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-pentene 509.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-pentene 510.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-pentene

511.6- (4'-trans- (2 "-(3", 5 "" difluoro-4 ""-trifluoromethyl-4 ""-biphenylyl) ethyl) cyclohexyl) -1-hexene 512.6- (4 '-Trans- (2 "-(3'",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-hexene 513.6- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-hexene 514.6- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-hexene 515.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-heptene 516.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-heptene 517.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-heptene 518.8- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-octene 519.8- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-octene 520.9- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethyl-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-nonene

521.2- (4'-trans- (2 "-(3", 5 "" difluoro-4 ""-trifluoromethoxy-4 ""-biphenylyl) ethyl) cyclohexyl) ethene 522.3- (4 ' -Trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-propene 523.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Propene 524.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
Buten 525.4- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-Buten 526.4- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-butene 527.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Pentene 528.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-pentene 529.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-pentene 530.5- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-pentene

531.6- (4'-trans- (2 "-(3", 5 "" difluoro-4 ""-trifluoromethoxy-4 "" biphenylyl) ethyl) cyclohexyl) -1-hexene 532.6- ( 4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-hexene 533.6- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-hexene 534.6- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-hexene 535.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-heptene 536.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-heptene 537.7- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-heptene 538.8- (4'-trans (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-octene 539.8- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-octene 540.9- (4'-trans- (2 "-(3 '",
5 '"Difluoro-4'"-trifluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-nonene

541.2- (4'-trans- (2 "-(3", 5 "" difluoro-4 "" difluoromethoxy-4 "" biphenylyl) ethyl) cyclohexyl) ethene 542.3- (4'- Trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-propene 543.3- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Propene 544.4- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
Butene 545.4- (4'-trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-butene 546.4- (4'-trans (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-butene 547.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -1
-Pentene 548.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-pentene 549.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-pentene 550.5- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-pentene

551.6- (4'-trans- (2 "-(3"",5""difluoro-4""difluoromethoxy-4""-biphenylyl) ethyl) cyclohexyl) -1-hexene 552.6- (4 '-Trans- (2 "-(3'",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-hexene 553.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-hexene 554.6- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-hexene 555.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -2
E-heptene 556.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-heptene 557.7- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-heptene 558.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -3
E-octene 559.8- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-octene 560.9- (4'-trans- (2 "-(3 '",
5 '"difluoro-4'" difluoromethoxy-4 '"-biphenylyl) ethyl) cyclohexyl) -4
E-Nonene Application Example 1

[0173]

Embedded image

Composition A comprising 85 parts by weight of Example 1
The NI point extrapolated from the liquid crystal composition to which 15 parts by weight of the compound of the present invention was added was -95.6 ° C., and the viscosity at 20 ° C. was 2.3 cp. The liquid crystal composition was sealed in a TN cell having a cell thickness of 8.7 μm, and the threshold voltage was measured.
Was 1.28V was. The elastic constant is K ₃₃ / K ₁₁
Was 1.99, and K ₃₃ / K ₂₂ was 2.69.

[0175]

Embedded image

As a comparative example, the NI point extrapolated from a liquid crystal composition obtained by adding 15 parts by weight of the comparative compound (B) to 85 parts by weight of the composition A is −59.6 ° C., and the viscosity at 20 ° C. is −1.0 cp Met. The liquid crystal composition was prepared using a cell thickness of 8.7.
It was sealed in a TN cell of μm and its threshold voltage was measured.
At that time, the voltage was 1.44V. The elastic constant of K ₃₃ / K ₁₁ is 1.
74, K ₃₃ / K ₂₂ was 2.07 Application Example 2 A liquid crystal composition obtained by adding 15 parts by weight of the compound of the present invention shown in Example 2 to 85 parts by weight of composition A used in Application Example 1 The NI point to be inserted is −119.6 ° C., and the cell thickness is 8.
The cell was sealed in a 7 μm TN cell and its threshold voltage was measured. The elastic constant of K ₃₃ / K ₁₁ is 1.
77, K ₃₃ / K ₂₂ was 2.53.

Application Example 3 The NI point extrapolated from a liquid crystal composition obtained by adding 15 parts by weight of the compound of the present invention shown in Example 4 to 85 parts by weight of composition A used in Application Example 1 is 57.1 ° C. The viscosity at 20 ° C. was 31.0 cp. Further, this liquid crystal composition was sealed in a TN cell having a cell thickness of 8.7 μm, and the threshold voltage was adjusted.
It was 1.55 V when measured . The elastic constant is K ₃₃ /
K ₁₁ is 2.00, K ₃₃ / K ₂₂ was 2.93.

[0178]

Embedded image

As a comparative example, the NI point extrapolated from a liquid crystal composition obtained by adding 15 parts by weight of the comparative compound (C) to 85 parts by weight of the composition A is 47.7 ° C., and the viscosity at 20 ° C. is 3
0.3 cp. The liquid crystal composition was prepared using a cell thickness of 8.8.
It was sealed in a TN cell of μm and its threshold voltage was measured.
At that time, the voltage was 1.48V. The elastic constant of K ₃₃ / K ₁₁ is 2.
11, K ₃₃ / K ₂₂ was 2.86

Application Example 4 The NI point extrapolated from a liquid crystal composition obtained by adding 15 parts by weight of the compound of the present invention shown in Example 3 to 85 parts by weight of the composition A used in Application Example 1 is −133.6 ° C. The liquid crystal composition was sealed in a TN cell having a cell thickness of 8.7 μm, and the threshold voltage was measured to be 1.00 V.

Application Example 5 Compound N was added to 85 parts by weight of composition A used in Application Example 1.
o. The NI point extrapolated from the liquid crystal composition containing 15 parts by weight of the compound of the present invention shown in FIG.
The viscosity at ° C was 29.0 cp. The liquid crystal composition was sealed in a TN cell having a cell thickness of 8.6 μm, and the threshold voltage was measured .

[0182]

The compound provided by the present invention has a low viscosity, and the addition of the compound can reduce the threshold voltage of the display device obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-217930 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 25/18 C07C 43/225 C09K 19 / 30 G02F 1/13 CA (STN)

Claims (9)

(57) [Claims] 1. A compound of the general formula (I)(Wherein X is a fluorine atom or a trifluoromethyl group,
Or a trifluoromethoxy group or difluorometh
-A- represents 1,4-cyclohexylene or
Is 1,4-phenylene, -B- is 1,4-cyclohexyl
L is 0, 1 or 2 and m is 0, 1 or
2, l + m ≧ 1 and Z is -CH _TwoCH_Two-Ma
Or n is a single bond, n is an integer of 0 to 4, R is hydrogen
Atom or 1 to 7 linear or branched alkyl group
Wherein, when R is an alkyl group, the double bond is in a trans configuration
A derivative of cyclohexane represented by the formula: 2. A derivative of cyclohexane according to claim 1, wherein -A- is 1,4-cyclohexylene, 1 is 1, m is 0, and Z is a single bond. 3. The derivative of claim 1, wherein -A- is 1,4-cyclohexylene, 1 is 2, m is 0, and Z is a single bond. 4. The cyclohexane derivative according to claim 1, wherein 1 represents 0, m represents 1, and Z is —CH ₂ CH ₂ —. 5. A derivative of cyclohexane according to claim 1, wherein -A- is 1,4-cyclohexylene, 1 is 1, m is 1, and Z is -CH ₂ CH _2- . 6. A derivative of cyclohexane according to claim 1, wherein -B- is 1,4-cyclohexylene, 1 is 0, m is 2, and Z is -CH ₂ CH _2- . 7. The cyclohexane derivative according to claim 1, wherein -A- is 1,4-phenylene, 1 is 1, m is 0, and Z is a single bond. 8. The method according to claim 1, wherein -A- is 1,4-phenylene, 1 represents 1, m represents 1, and Z represents -CH.
₂ A derivative of cyclohexane that is CH ₂ —. 9. At least one liquid crystalline compound and a compound represented by the general formula (I): (Wherein X is a fluorine atom or a trifluoromethyl group,
Or represents a trifluoromethoxy group or a difluoromethoxy group, -A- is 1,4-cyclohexylene or 1,4-phenylene, -B- is 1,4-cyclohexylene, and 1 is 0, 1 or 2. , M represents 0, 1 or 2, l + m ≧ 1, Z represents —CH ₂ CH ₂ — or a single bond, n represents an integer of 0 to 4, R represents a hydrogen atom or 1 to 7 A liquid crystal composition containing at least one cyclohexane derivative represented by the following formula: which represents a linear or branched alkyl group, and when R is an alkyl group, the double bond is in a trans configuration.