JPH0930995A - 1,2-dicyclohexylpropane derivative - Google Patents

Abstract

(57) [Summary] (Correction) [Solution] General formula (I) Specifically, for example And a liquid crystal composition containing the compound. [Effect] This compound has excellent liquid crystallinity, can be easily produced industrially, and is extremely stable chemically. Moreover,
Compared with the case of a liquid crystal compound having a corresponding 1,2-dicyclohexylethane skeleton, the addition to the base liquid crystal has almost the same electro-optical characteristics, and in addition, it is difficult to precipitate crystals even at low temperature. Have. Therefore, it is useful as a practical liquid crystal display material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel liquid crystal compound, a 1,2-dicyclohexylpropane derivative and a liquid crystal composition containing the same.

[0002]

2. Description of the Related Art Liquid crystal display elements have been used in various measuring instruments such as watches and calculators, panels for automobiles, word processors, electronic organizers, printers, computers, televisions and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and FLC (ferroelectric liquid crystal). ) And the like, and as the drive method, the conventional static drive has become more common and multiplex drive has become more common, and the simple matrix method, and recently the active matrix method has been put into practical use. According to these display methods and drive methods, various characteristics are required as a liquid crystal material,
(1) A wide temperature range and (2) a low viscosity are important required characteristics common to all systems. Of these, (1) includes (1a) the maximum temperature of the nematic phase (T
_NI ) is high, and (1b) the melting point is low, and phase separation such as crystallization or precipitation hardly occurs.

[0003] To date, no liquid crystal compound satisfying such required properties alone has been known, and in fact, it is used as a mixture of various liquid crystal compounds. Although a wide variety of liquid crystal compounds have been developed so far, it is assumed that the above conditions (1) and (2) can be relatively satisfied.
A 3- or 4-ring liquid crystal compound having dicyclohexylethane (hereinafter, referred to as CEC structure) in its central skeleton (core) is also relatively used.

A compound having this CEC structure is T _NI
Is relatively high and its viscosity is also relatively low. However, its low temperature characteristics have never been satisfactory.

In order to lower the melting point of the liquid crystal material, it is effective to mix a large number of compounds to increase the number of constituent components of the liquid crystal composition, and increase the number of components without changing the characteristics of the liquid crystal composition. For this purpose, a method of using a plurality of homologues in which the carbon number of the terminal alkyl group is changed is generally used. However, in most cases, it is difficult to prevent crystals from precipitating at a low temperature even in the case of a liquid crystal compound having a CEC structure in its core by mixing only homologues.

Therefore, while having the same characteristics as the liquid crystal compound having a CEC structure in its core, its melting point is lowered or it is difficult to crystallize even at low temperature and the compatibility with other liquid crystal compounds is improved. A compound was desired.

[0007]

In order to meet the above-mentioned objects, the problem to be solved by the present invention is a liquid crystal which is a 1,2-dicyclohexylpropane derivative in which a branched methyl group is further introduced into the ethylene group in the CEC structure. Another object of the present invention is to provide a liquid crystal composition having a low viscosity and a wide liquid crystal temperature range by using the same, and to prevent precipitation and phase separation from occurring particularly at low temperatures.

[0008]

According to the present invention, there is provided a compound represented by the following general formula (I):

[0009]

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(Wherein R ¹ represents an alkyl group having 1 to 12 carbon atoms, n represents an integer of 1 or 2, X ¹ ,
X ² and X ³ each independently represent a hydrogen atom or a fluorine atom, and Y is —CH ₂ CH ₂ —, —COO—, —OCO.
_{-, - CH 2 O -,} - OCH 2 -, 1,4- cyclohexylene group, one or two represent may also be 1,4-phenylene group or a single bond be substituted by fluorine atoms, Z
Hydrogen atom, a fluorine atom, a chlorine atom, -CN, -R ^{2,
_{-OR 2, -OCN, -CF 3,}} -OCF 3, -OCF 2 H
Or represents -OCH ^₂ CF _3, R ₂ is -C 1-1
2 represents an alkyl group having 2 to 2 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and the cyclohexane ring has a trans configuration. However, when Y represents a 1,4-cyclohexylene group, or a 1,4-phenylene group optionally substituted by one or two fluorine atoms, n represents 1. ) 1,2-dicyclohexyl propane derivative represented by

In the compound of the general formula (I) according to the present invention, Y is a 1,4-cyclohexylene group, a 1,4-phenylene group optionally substituted by one or two fluorine atoms, or a single bond. Is preferred.

At this time, Z is a fluorine atom, a chlorine atom, a cyano group, a linear alkyl group and an alkoxyl group having 1 to 7 carbon atoms, an alkenyl group and an alkenyloxy group having 3 to 7 carbon atoms, CF _3, -OCF _3, -OCF
Preferably ₂ H or -OCH ₂ CF _3, fluorine atom, chlorine atom, -CF _3, -OCF _3, -OCF ₂ H or -OCH ₂
CF ₃ is particularly preferable, a fluorine atom or —OCF ₃ is more preferable, and a fluorine atom is still more preferable.

Further, at this time, R ¹ has ¹ to 7 carbon atoms.
It is preferable that it is a linear alkyl group of
It is preferable that n is 1 and Y is a single bond. The general formula (I) may include a large number of compounds depending on the selection of R ¹ , n, X ¹ , X ² , X ³ , Y and Z. (Ia) to general formula (Id)

[0014]

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(Wherein R ¹ , X ¹ , X ² , X ³ and Z have the same meanings as in formula (I), and X ⁴ and X ⁵ each independently represent a hydrogen atom or a fluorine atom. .) Are preferred, and among them, the tricyclic compound of the general formula (Ia) is most preferred. Further, among the compounds represented by the general formula (Ia), the compound represented by the general formula (Iaa)
~ General formula (Ial)

[0016]

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(Wherein R ^a and R ^b each independently represent a straight-chain alkyl group having 1 to 7 carbon atoms) are preferred, and compounds represented by the general formula (Iab) and the general formula (Iac) are preferred. ) And a compound represented by the general formula (Iad) are particularly preferable.

The compound of the general formula (I) has R ¹ , n,
^{X 1, X 2, X 3} , Y and Z, in particular can be produced as follows according to their Y and Z. i) Y = single bond, —CH ₂ CH ₂ —, 1,4-cyclohexylene group, 1,4-phenylene group optionally substituted by 1 or 2 fluorine atoms, general formula (II)

[0019]

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(Wherein R ¹ and n have the same meanings as in the general formula (I), and W is --MgCl, --MgBr,
-Represents MgI or a lithium atom. ) And an organometallic reagent represented by the general formula (III)

[0021]

[Chemical 6]

(In the formula, X ¹ and X ² have the same meanings as in formula (I), Y ¹ is a single bond, —CH ₂ CH
_2- , 1,4-cyclohexylene group, 1,4-phenylene group optionally substituted by 1 or 2 fluorine atoms, Z ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, or -CF ₃ represents -OCF _3, -OCH ₂ CF _3, alkyl or alkoxyl group. It can be obtained by reacting with a cyclohexanone derivative represented by), dehydrating the obtained cyclohexanol in the presence of an acid catalyst, and then hydrogenating this. Alternatively, in the general formula (II), W is -P instead of the organometallic reagent of the general formula (II).
A Wittig reagent prepared from a Ph ₃ ⁺ phosphonium salt and a base may be used.

Here, Z in the general formula (I) is -OR.
^Two, -OCN, -OCF_Three, -OCF _TwoH or -OCH_TwoC
F_ThreeEtc., in the general formula (III), Z¹Is -O
CH _ThreeWas similarly reacted with a compound of
Trimethylsilyl bromide, hydrobromic acid, boron tribromide or
Is treated with aluminum chloride-dimethyl sulfide, etc.
And in the general formula (I), Z is —OH.
It is also possible to obtain and derive from the compound of oh). Immediately
Then, in the presence of a base represented by the general formula (Ioh), R^Two-W^Two(R^Two
Represents the same meaning as in formula (I), and W^TwoIs salt
Elemental atom, bromine atom, iodine atom or p-toluene
It represents a leaving group such as a sulfonyl group. ) To react with
Therefore, in the general formula (I), Z is -OR.^TwoCompound
Obtainable. Also, R^Two-W^TwoInstead of BrCN
Or TsOCH_TwoCF_Three(Ts is p-toluenesulfo
Represents a nyl group. ) By using the general formula (I)
Z is -OCN or -OCH_TwoCF_ThreeCompound of
Can be obtained. In addition, the general formula (Ioh) is dithio
Fluoride ion present after making carbamate
Under the general formula by reacting with a halonium ion generator
In (I), Z is -OCF_ThreeTo obtain the compound
Wear. Further, the general formula (Ioh) is changed to a formate ester.
After that, the dust such as DAST (dimethylaminosulfur trifluoride)
By reacting with a priming agent, in the general formula (I)
Z is -OCF_TwoCompounds of H can be obtained.

When Z is --CN, the general formula (I
In the same manner, using a compound in which Z is a hydrogen atom in II) to obtain a compound of the general formula (Ih) in which Z is a hydrogen atom in the general formula (I), bromination or iodination, and then Cyanide with copper (I) cyanide, or by reacting with magnesium to form a Grignard reagent, and reacting with carbon dioxide, Z in general formula (I)
A compound of general formula (Icooh) is obtained, wherein is —COOH. It can be obtained by converting this into an acid chloride, reacting with ammonia to form an amide, and then dehydrating it.

When Z is -R ² , the general formula (I
It can be obtained by reacting h) with the corresponding acid chloride in the presence of a Lewis acid, and then reducing the carbonyl group. ii) In the case of Y = -COO- The organometallic reactant of the general formula (II)

[0026]

[Chemical 7]

Cyclohexanone-1,4-dione of the general formula (IV)

[0028]

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A cyclohexanone derivative of the formula (wherein R ¹ and n have the same meanings as in formula (I)) is obtained. This is represented by the general formula (V)

[0030]

## STR00009 ## By reacting with a Wittig reagent of CH ₃ OCH = PPh ₃ (V), the resulting cyclohexanecarbaldehyde derivative is oxidized to give a compound of the general formula (VI)

[0031]

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Cyclohexanecarboxylic acid of the formula (wherein R ¹ and n have the same meanings as in formula (I)) is obtained. This was converted to an acid chloride with thionyl chloride and then converted to the general formula (VII)

[0033]

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(Wherein X ¹ , X ² , X ³ and Z have the same meanings as in formula (I)) and the phenol derivative is obtained in the presence of a basic substance. it can. Or replace with acid chloride,
It can also be obtained by using the general formula (VI) and reacting in the presence of a condensing agent. iii) In the case of Y = -OCO- The cyclohexanone derivative of the general formula (IV) is reduced with lithium aluminum hydride or sodium borohydride to give the general formula (VIII).

[0035]

[Chemical 12]

A cyclohexanol derivative represented by the formula (wherein R ¹ and n have the same meanings as in formula (I)) is obtained. This is represented by the general formula (IX)

[0037]

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(Wherein X ¹ , X ² , X ³ and Z have the same meanings as in formula (I)) and are reacted in the same manner as in ii). be able to. iv) Y = -OCH ₂ - when the cyclohexanol derivatives of the general formula (VIII) of the alcoholate with a base, which the general formula (X)

[0039]

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(Wherein X ¹ , X ² , X ³ and Z have the same meanings as in formula (I), W ³ is a chlorine atom,
Represents a bromine atom or an iodine atom. ) It can be obtained by reacting with a benzyl halide derivative. v) Y = -CH ₂ O- where the general formula (VI) further halogenating the alcohol obtained by reducing the cyclohexanecarboxylic acids or tosylated to formula obtained (XI)

[0041]

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(In the formula, R ¹ and n have the same meanings as in formula (I), and W ⁴ represents a chlorine atom, a bromine atom, an iodine atom or a leaving group such as a p-toluenesulfonyl group.) The compound (1) can be obtained by reacting the phenol derivative of the general formula (VII) in the presence of a basic substance.

The compounds of the present invention can be produced as described above, and Table 1 shows typical examples of the compounds represented by the general formula (I) thus produced.

[0044]

[Table 1]

(In the table, Cr represents a crystalline phase, N represents a nematic phase, and I represents an isotropic liquid phase.) The compounds (No. 1) shown in Table 1 are (No.
Formula (R-1) having a similar structure to the compound of 1) but containing no methyl branch

[0046]

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[0047] 4- (2-cyclohexylethyl) were compared T _NI of cyclohexylbenzene (CECP) a compound having a skeleton. The phase transition temperature of the formula (R-1) is as follows.

C 33 ° C. N 104 ° C. I (C represents a crystalline phase, N represents a nematic phase, and I represents an isotropic liquid phase.) The compound of the formula (R-1) and the compound (No. Comparing the compounds of 1), it can be seen that the nematic phase maximum temperature (T _NI ) of the compound of the present invention is slightly decreased even though the branched methyl group is introduced into the ethylene group of the linking group. . There have been few examples of introducing a methyl branching group into the linking group of a liquid crystal compound and comparing the transition temperatures thereof, but the following is an example of such comparison.

Formulas (A-1) and (A-2)

[0050]

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The phase transition temperature of the stilbene derivative represented by: Formula (A-1) C 80 ° C. S 80.5 ° C. N 1
26 ° C I Formula (A-2) C 209 ° C (N189 ° C) I (C, N and I have the same meanings as above, and S
Represents a smectic phase, and () represents a monotropic phase. ) On the other hand, formulas (B-1) and (B-2) in which a methyl group is introduced into formulas (A-1) and (A-2).

[0052]

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The phase transition temperature of the compound (1) was as follows. Formula (B-1) C ₁ 40 ° C. C ₂ 72 ° C. N 82
° C I Formula (B-2) C 106 ° C N 121 ° C I When these compounds are compared, the T of the compounds of the formula (B-1) and the formula (B-2) is changed by the introduction of a methyl branching group.
_NI has dropped by more than 30 degrees.

Therefore, it is surprising that the compound (No. 1) of the present invention maintains a high T _NI , and thus the methyl branching group which originally largely inhibits the liquid crystallinity is
It has been little known so far that the liquid crystallinity of a compound when it exists in an ethane bond sandwiched by cyclohexane rings does not deteriorate so much.

The most outstanding feature of the compound of general formula (I) of the present invention is its good solubility in other liquid crystal compounds. In particular, in the general formula (I), a compound in which Y is a single bond and Z is a fluorine atom or a trifluoromethyl group is a CECP containing no corresponding methyl branch.
The compatibility is further improved as compared with the skeleton compound, and a composition in which precipitation or phase separation hardly occurs can be more easily prepared, and is particularly useful.

Host liquid crystal (H) suitable for driving active matrix

[0057]

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The maximum temperature of the nematic liquid crystal of the formula (wherein the cyclohexane ring represents the trans configuration and "%" represents "% by weight") is 116.7 ° C, and a cell thickness of 6 is produced using this nematic liquid crystal. The threshold voltage (V _th ) of the 0.0 μm TM cell was 2.14V.

70% by weight of this host liquid crystal (H) and the first
When a liquid crystal composition (M-3) containing 30% by weight of the compound (No. 3) in the table was prepared, it showed a nematic phase at 102 ° C. or lower, and its decrease was slight. This (M
When -3) was stored at -20 ° C, precipitation of crystals and phase separation could not be observed even after 1 week or more. Also, (M
-3) was solidified at -60 ° C, and the melting temperature was measured to find -10 ° C.

A cell was similarly prepared using this (M-3), and V _th was measured. As a result, it was 1.86 V, which is greatly reduced as compared with the host liquid crystal (H). It is clear.

On the other hand, 70% by weight of host liquid crystal (H)
And a compound (R-2) having a structure similar to the compounds of (No. 3) but having a CECP skeleton containing no methyl branch.

[0062]

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A comparative composition (MR-2) was prepared consisting of 30% by weight of the compound of (MR-2) T _NI is 10
The temperature was 5 ° C, which was slightly higher than (M-3). However, when this (MR-2) was left at -20 ° C, partial precipitation of crystals was observed within one week. Further, it was solidified at −60 ° C. and its melting temperature was measured, and it was 0 ° C., which was higher than (M-3).

Next, a cell was similarly prepared using this (MR-2), and V _th was measured. As a result, it was 1.84 V, which was almost the same as (M-3). From the above, the compound of the present invention has excellent compatibility with conventional liquid crystal compounds, and when it is used as a liquid crystal composition, it is difficult to cause crystal precipitation or phase separation, and is useful for temperature expansion to a low temperature range. Understandable.

Therefore, the compound of the general formula (I) can be preferably used in the state of a mixture with other nematic liquid crystal compounds, especially as a material of a field effect display cell of TN type or STN type. In particular, the general formula (I)
Depending on the selection of Z in (1), it does not have a strong polar group in the molecule, and in this case, it is easy to obtain a large specific resistance and a high voltage holding ratio. You can In general, it is relatively difficult to lower the melting point by mixing only a non-polar liquid crystal compound or a fluorine-based liquid crystal compound, and thus the compound of the general formula (I) of the present invention is particularly useful. . The present invention also provides a liquid crystal composition containing at least one compound represented by formula (I) as a constituent component.

Preferred examples of the nematic liquid crystal compound which can be used in the composition by mixing with the compound of the general formula (I) are, for example, 4-substituted phenyl 4-substituted benzoate and 4-substituted benzoic acid. Cyclohexanecarboxylic acid 4-substituted phenyl, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenylyl, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4-substituted phenyl,
4- (4-substituted cyclohexyl) benzoic acid 4-substituted phenyl, 4- (4-substituted cyclohexyl) benzoic acid 4-substituted cyclohexyl, 4,4′-substituted biphenyl, 1-
(4-substituted cyclohexyl) -4-substituted benzene, 4,
4′-substituted bicyclohexane, 1- [2- (4-substituted cyclohexyl) ethyl] -4-substituted benzene, 1- (4
-Substituted cyclohexyl) -2- (4-substituted cyclohexyl) ethane, 4,4 "-substituted terphenyl, 4- (4-
(Substituted cyclohexyl) -4′-substituted biphenyl, 4-
[2- (4-substituted cyclohexyl) ethyl] -4'-substituted biphenyl, 4- (4-substituted phenyl) -4'-substituted bicyclohexane, 4- [2- (4-substituted cyclohexyl) ethyl] -4 ' -Substituted biphenyl, 4- [2- (4
-Substituted cyclohexyl) ethyl] cyclohexyl-4 '
-Substituted benzene, 4- [2- (4-substituted phenyl) ethyl] -4'-substituted bicyclohexane, 1- (4-substituted phenylethynyl) -4-substituted benzene, 1- (4-substituted phenylethynyl)- 4- (4-substituted cyclohexyl)
Examples include benzene, 2- (4-substituted phenyl) -5-substituted pyrimidine, 2- (4′-substituted biphenylyl) -5-substituted pyrimidine, and compounds in which the benzene ring has a lateral substituent in each of the above compounds. it can.

Among them, 4,4'-substituted biphenyl, 1- (4-substituted cyclohexyl) -4-substituted benzene, 4,4'-substituted bicyclohexane, 1- [2- (4- Substituted cyclohexyl)
Ethyl] -4-substituted benzene, 1- (4-substituted cyclohexyl) -2- (4-substituted cyclohexyl) ethane,
4,4 "-substituted terphenyl, 4- (4-substituted cyclohexyl) -4'-substituted biphenyl, 4- [2- (4-substituted cyclohexyl) ethyl] -4'-substituted biphenyl,
4- (4-substituted phenyl) -4'-substituted bicyclohexane, 4- [2- (4-substituted cyclohexyl) ethyl]-
4'-substituted biphenyl, 4- [2- (4-substituted cyclohexyl) ethyl] cyclohexyl-4'-substituted benzene, 4- [2- (4-substituted phenyl) ethyl] -4'-
Substituted bicyclohexane, 1- (4-substituted phenylethynyl) -4-substituted benzene, 1- (4-substituted phenylethynyl) -4- (4-substituted cyclohexyl) benzene and compounds in which the benzene ring is fluorine-substituted Is suitable.

[0068]

EXAMPLES Examples of the present invention are shown below to further explain the present invention. However, the invention is not limited to these examples.

The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and infrared absorption spectrum (IR). The measurement of the transition temperature was carried out using a polarizing microscope equipped with a hot stage and a differential scanning calorimeter (DSC). Further, "%" in the composition represents "% by weight". Reference Example 1 Synthesis of trans-4-propylcyclohexanecarbaldehyde

[0070]

[Chemical 21]

144 g of methoxymethyltriphenylphosphonium chloride was suspended in 350 ml of THF. This was ice-cooled, 55 g of potassium t-butoxide was slowly added, and the mixture was stirred at 0 ° C for 1 hr. 50 g of 4-propylcyclohexanone was dissolved in 300 ml of THF and added dropwise at the same temperature for 4 hours. After stirring for another 30 minutes, 200m of water
1 was added. The aqueous layer was separated and the organic layer was concentrated, 800 ml of hexane was added, and the insoluble material was filtered off. The precipitate was washed with hexane. The filtrate was collected, washed with a mixed solvent of methanol / water and then concentrated. The resulting oily crude product was treated with T
It was dissolved in 250 ml of HF, 250 ml of 10% hydrochloric acid was added, and the mixture was heated and stirred for 1 hour. After standing to cool, ethyl acetate 300m
After extracting with l and washing with water, the solvent was distilled off. The obtained oily substance was dissolved in 400 ml of ethanol, 40 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was stirred for 1 hour.
800 ml of water was added, and the mixture was extracted with the same amount of toluene. The organic layer was washed with 800 ml of water and then with 400 ml of saturated saline and then dried under reduced pressure to obtain 54 g of trans-4-propylcyclohexanecarbaldehyde as a colorless oil.
It crystallized on standing. Reference Example 2 Synthesis of trans-1-acetyl-4-propylcyclohexane

[0072]

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24 g of trans-4-propylcyclohexanecarbaldehyde obtained in Reference Example 1 was added to 100 ml of THF.
And cooled to 5 ° C. 200 ml of methylmagnesium bromide (0.95 mol THF solution) was added dropwise thereto over 30 minutes. After stirring at 5 ° C for 1 hour, the temperature was returned to room temperature, water was added, and the mixture was neutralized with dilute hydrochloric acid. It was extracted with ethyl acetate, and the organic layers were combined, washed with water and then with saturated saline. After dehydration over anhydrous sodium sulfate, the solvent was distilled off to obtain 23 g of 1- (trans-4-propylcyclohexyl) ethanol. This was dissolved in 100 ml of dichloromethane and added dropwise to a suspension of 50 g of pyridinium chlorochromate (PCC) in 200 ml of dichloromethane at room temperature. After further stirring for 3 hours, the insoluble matter was removed by decantation.
The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (dichloromethane) to obtain 16 g of trans-1-acetyl-4-propylcyclohexane. Reference Example 3 Synthesis of 2- (trans-4-propylcyclohexyl) propanol

[0074]

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Trans-1-acetyl-obtained in Reference Example 2
16 g of 4-propylcyclohexane was reacted with a Wittig reagent prepared from methoxymethyltriphenylphosphonium chloride in the same manner as in Reference Example 1 and then hydrolyzed to give 13 g of 2- (trans-4-propylcyclohexyl) propanal. Got 6g of this THF5
It was dissolved in 0 ml and added dropwise to lithium aluminum hydride suspended in 100 ml of THF. After stirring at room temperature for 30 minutes, excess hydride was decomposed and the precipitate was removed. T
After most of the HF was distilled off, toluene was added, washed with dilute hydrochloric acid and then with water, and the solvent was distilled off to obtain 6 g of an oily substance of 2- (trans-4-propylcyclohexyl) propanol. Reference Example 4 Synthesis of trans-1- (2-bromo-1-methyl) ethyl-4-propylcyclohexane

[0076]

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6 g of an oily product of 2- (trans-4-propylcyclohexyl) propanol obtained in Reference Example 3 was dissolved in 50 ml of hexane. This was ice-cooled to 0 ° C., and 2 ml of phosphorus tribromide was added dropwise. After stirring for 3 hours, methanol and then water were added to decompose excess phosphorus bromide. The aqueous layer was separated, the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water, and the solvent was distilled off after dehydration to obtain a crude product, which was distilled under reduced pressure (100 to 105 ° C / 2 mmHg). , Trans-1- (2-bromo-1-methyl) ethyl-4-propylcyclohexane was obtained as an oily substance (4.5 g). Reference Example 5 Synthesis of trans-1- (2-bromo-1-methyl) ethyl-4-pentylcyclohexane Trans-1- (2-bromo-1) was prepared from 4-pentylcyclohexanone in the same manner as in Reference Examples 1 to 4. -Methyl) ethyl-4-pentylcyclohexane was obtained. Example 1 Synthesis of 3,4-difluoro-1- [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene (Compound No. 1 in Table 1)

[0078]

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0.4 g of magnesium was suspended in 1 ml of THF. The trans-1- (2-
A solution of 2.5 g of bromo-1-methyl) ethyl-4-propylcyclohexane in 20 ml of THF was added dropwise at a rate at which gentle reflux was maintained, and the mixture was further stirred at room temperature for 1 hour to prepare a Grignard reaction agent. This is cooled to 0 ° C., 4-
(3,4-difluorophenyl) cyclohexanone 2.
A solution of 3 g of THF in 10 ml was added dropwise over 30 minutes. 0 ° C
After stirring for 1 hour at room temperature, the temperature was returned to room temperature, and water and then dilute hydrochloric acid were added to neutralize. The mixture was extracted with toluene, and the organic layers were combined and dehydrated with water and then saturated saline. The crude product obtained by distilling off the solvent was again dissolved in 25 ml of toluene, 0.5 g of p-toluenesulfonic acid dihydrate was added, and the mixture was heated and stirred under reflux for 3 hours. After allowing to cool to room temperature, it was washed with an aqueous sodium hydrogen carbonate solution, water, and then saturated saline. After dehydration with anhydrous sodium sulfate, the polar component was removed from the crude product obtained by distilling off the solvent using silica gel column chromatography (hexane). This was dissolved in 30 ml of ethyl acetate, 1.0 g of palladium carbon was added, and the mixture was stirred under a hydrogen atmosphere for 6 hours. The catalyst was filtered off, the solvent was distilled off, the residue was purified by silica gel column chromatography (hexane), and recrystallized from ethanol to give 3,4-difluoro-1- [trans-4- [2- (trans. 1.2 g of white crystals of -4-propylcyclohexyl) propyl] cyclohexyl] benzene were obtained.

The following compounds were obtained in the same manner. 3,4-Difluoro-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3,4-difluoro-1- [trans-4- [2- (trans-4- Butylcyclohexyl) propyl] cyclohexyl] benzene 3,4-difluoro-1- [trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene (Compound No. 2 in Table 1) 4 -Fluoro-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 4-fluoro-1- [trans-4- [2- (trans-4-propylcyclohexyl) propyl] Cyclohexyl] benzene (Compound No. 5 in Table 1) 4-Fluoro-1- [ Lance-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 4-fluoro-1- [trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3,4 , 5-trifluoro-1- [trans-4- [2
-(Trans-4-ethylcyclohexyl) propyl]
Cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene (Compound No. 3 in Table 1) 3,4,5-Trifluoro-1- [trans-4- [2
-(Trans-4-butylcyclohexyl) propyl]
Cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene (Compound No. 4 in Table 1) 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4-ethylcyclohexyl) propyl]
Cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4-butylcyclohexyl) propyl]
Cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro -4-Trifluoromethoxy-1- [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- (Trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3,5- Difluoro-4-trif Orometokishi-1
[Trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 4-methyl-1- [trans-4- [2- (trans-
4-Ethylcyclohexyl) propyl] cyclohexyl] benzene 4-methyl-1- [trans-4- [2- (trans-
4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-methyl-1- [trans-4- [2- (trans-
4-Butylcyclohexyl) propyl] cyclohexyl] benzene 4-methyl-1- [trans-4- [2- (trans-
4-pentylcyclohexyl) propyl] cyclohexyl] benzene 4-ethyl-1- [trans-4- [2- (trans-
4-ethylcyclohexyl) propyl] cyclohexyl] benzene 4-ethyl-1- [trans-4- [2- (trans-
4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-ethyl-1- [trans-4- [2- (trans-
4-Butylcyclohexyl) propyl] cyclohexyl] benzene 4-ethyl-1- [trans-4- [2- (trans-
4-Pentylcyclohexyl) propyl] cyclohexyl] benzene 4-propyl-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 4-propyl-1- [trans-4- [2 -(Trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-propyl-1- [trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 4-propyl-1- [trans- 4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 4-methoxy-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 4-methoxy-1 -[Trans-4- [ -(Trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-methoxy-1- [trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 4-methoxy-1- [trans- 4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 4-ethoxy-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 4-ethoxy-1 -[Trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 4-ethoxy-1- [trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 4 -Ethoxy-1- [ Lance-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 2,3-difluoro-4-methoxy-1- [trans -
4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 2,3-difluoro-4-methoxy-1- [trans-
4- [2- (trans-4-propylcyclohexyl)
Propyl] cyclohexyl] benzene 2,3-difluoro-4-methoxy-1- [trans-
4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 2,3-difluoro-4-methoxy-1- [trans-
4- [2- (trans-4-pentylcyclohexyl)
Propyl] cyclohexyl] benzene 2,3-difluoro-4-ethoxy-1- [trans-
4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 2,3-difluoro-4-ethoxy-1- [trans-
4- [2- (trans-4-propylcyclohexyl)
Propyl] cyclohexyl] benzene 2,3-difluoro-4-ethoxy-1- [trans-
4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 2,3-difluoro-4-ethoxy-1- [trans-
4- [2- (trans-4-pentylcyclohexyl)
Propyl] cyclohexyl] benzene [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene [trans- 4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene [trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans- 4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 3,5 -J Fluoro-1- [trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4-pentylcyclohexyl) propyl] ] Cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4- Propylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- ( Trans-4-pentylcyclohexyl) propyl] cyclo Hexyl] benzene (Example 2) 4-Cyano-1- [trans-4-
Synthesis of [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene

[0081]

[Chemical formula 26]

[Trans-4- [2-] obtained in Example 1
(Trans-4-propylcyclohexyl) propyl]
Cyclohexyl] benzene and anhydrous aluminum chloride were dissolved in dichloromethane. Oxalic acid chloride was added dropwise at 10 ° C under water cooling, and the mixture was further stirred at room temperature. It was poured into ice water and extracted with toluene. 20% aqueous ammonia was added to this, and it stirred at room temperature for 2 hours. The deposited precipitate is collected by filtration,
It was washed with methanol and dried under reduced pressure to obtain an amide compound. This was heated to reflux in thionyl chloride for 3 hours. Excessive thionyl chloride was distilled off under reduced pressure, toluene was added,
It was washed with water and then saturated saline. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography and recrystallized from ethanol to give 4-cyano-1- [trans-4- [2- (trans-4-propyl). White crystals of cyclohexyl) propyl] cyclohexyl] benzene were obtained.

The following compounds were obtained in the same manner. 4-cyano-1- [trans-4- [2- (trans-
4-Ethylcyclohexyl) propyl] cyclohexyl] benzene 4-cyano-1- [trans-4- [2- (trans-
4-Butylcyclohexyl) propyl] cyclohexyl] benzene 4-cyano-1- [trans-4- [2- (trans-
4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4-ethylcyclohexyl) propyl]
Cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4-butylcyclohexyl) propyl]
Cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] benzene (Example 3) trans-4- (3,4-difluoro) phenyl-trans-4 '-[2- (trans-4
Synthesis of -propylcyclohexyl) propyl] bicyclohexane In Example 1, instead of 4- (3,4-difluorophenyl) cyclohexanone, trans-4'-
(3,4-difluorophenyl) bicyclohexane-4
Similarly, trans-4- (3,4-difluoro) phenyl-trans-4 ′-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane was obtained using —one.

In the same manner, the following compound was obtained. Trans-4- (3,4-difluoro) phenyl-trans-4 '-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans-4- (3,4-difluoro) phenyl-trans-4' -[2- (trans-4-Butylcyclohexyl) propyl] bicyclohexane trans-4- (3,4-difluoro) phenyl-trans-4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans -4- (3,4,5-Trifluoro) phenyl-trans-4 '-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans-4- (3,4,5-trifluoro) phenyl -Trans-4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexyl Sun trans-4- (3,4,5-trifluoro) phenyl-trans-4 '-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (3,4,5-trifluoro) ) Phenyl-trans-4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-fluoro) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-fluoro) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-fluoro) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-fluoro) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4-phenyl-trans-4'-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans-4-phenyl- Trans-4 ′-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4-phenyl-trans-4 ′-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- Phenyl-trans-4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-trifluoromethoxy) phenyl-trans-4'-[2- (trans-4-ethylcyclohexyl) ) Propyl] bicyclohexane trans- -(4-Trifluoromethoxy) phenyl-trans-4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-trifluoromethoxy) phenyl-trans-4'-[2 -(Trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (4-trifluoromethoxy) phenyl-trans-4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (3-Fluoro-4-trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-
4-ethylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-
4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-
4-Butylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-
4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans- 4- (3,5-difluoro-4-trifluoromethoxy) phenyl-trans-4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-) Trifluoromethoxy) phenyl-trans-4 ′-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-trifluoromethoxy) phenyl-trans-4′- [2- (trans-4-pentylcyclohexyl) pro Le] bicyclohexane trans-4- (3,5-difluoro-4-methoxy)
Phenyl-trans-4 '-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-methoxy)
Phenyl-trans-4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-methoxy)
Phenyl-trans-4 '-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-methoxy)
Phenyl-trans-4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-methoxy) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-methoxy) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-methoxy) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-methoxy) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-ethoxy) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-ethoxy) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-ethoxy) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-ethoxy) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-methyl) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-methyl) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-methyl) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-methyl) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (4-ethyl) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-ethyl) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (4-ethyl) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-ethyl) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro) phenyl-trans-4'-[2- (trans-4-ethylcyclohexyl) propyl] bi Cyclohexane trans-4- (3,5-difluoro) phenyl-trans-4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro) phenyl-trans-4 '-[2- (Trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro) phenyl-trans-4'-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane Trans-4- (3-fluoro) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (3-fluoro) phenyl-trans-
4 '-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (3-fluoro) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane (Example 4) trans-4- (4-cyanophenyl) -trans-4'-[2- (trans-4-propylcyclohexyl) Synthesis of propyl] bicyclohexane trans-4-phenyl-trans-obtained in Example 3
From 4 ′-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane in the same manner as in Example 2, trans-4- (4-cyanophenyl) -trans-4 ′-[2- (trans-4 -Propylcyclohexyl) propyl] bicyclohexane was obtained.

The following compounds were obtained in the same manner. Trans-4- (4-cyano) phenyl-trans-
4 '-[2- (trans-4-ethylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-cyano) phenyl-trans-
4 '-[2- (trans-4-butylcyclohexyl)
Propyl] bicyclohexane trans-4- (4-cyano) phenyl-trans-
4 '-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-cyano) phenyl-trans-4'-[2- (trans-4-ethylcyclohexyl) propyl ] Bicyclohexane trans-4- (3-fluoro-4-cyano) phenyl-trans-4 ′-[2- (trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-cyano ) Phenyl-trans-4 '-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane trans-4- (3-fluoro-4-cyano) phenyl-trans-4'-[2- (trans-4 -Pentylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro- 4-Cyano) phenyl-trans-4 '-[2- (trans-4-ethylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-cyano) phenyl-trans-4'-[2 -(Trans-4-propylcyclohexyl) propyl] bicyclohexane trans-4- (3,5-difluoro-4-cyano) phenyl-trans-4 '-[2- (trans-4-butylcyclohexyl) propyl] bicyclohexane Trans-4- (3,5-difluoro-4-cyano) phenyl-trans-4 ′-[2- (trans-4-pentylcyclohexyl) propyl] bicyclohexane (Example 5) 3,4-difluoro-1- [Trans-4- [2- (trans-4'-propylbicyclohexane-trans-4-yl) pro Synthesis of pill] cyclohexyl] benzene In Example 1, trans-1- (2-bromo-1-
Methyl) ethyl-4-propylcyclohexane was replaced with trans-4- (2-bromo-1-methyl) ethyl-trans-4′-propylbicyclohexane in the same manner except that 3,4-difluoro-hexane was used. 1- [trans-4- [2- (trans-4′-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene was obtained.

The following compounds were obtained in the same manner. 3,4-Difluoro-1- [trans-4- [2- (trans-4′-ethylbicyclohexane-trans-4
-Yl) propyl] cyclohexyl] benzene 3,4-difluoro-1- [trans-4- [2- (trans-4'-butylbicyclohexane-trans-4
-Yl) propyl] cyclohexyl] benzene 3,4-difluoro-1- [trans-4- [2- (trans-4'-pentylbicyclohexane-trans-
4-yl) propyl] cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4'-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4'-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4'-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,4,5-trifluoro-1- [trans-4- [2
-(Trans-4'-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-fluoro-1- [trans-4- [2- (trans-4'-ethylbicyclohexane-trans-4- Il) propyl] cyclohexyl] benzene 4-fluoro-1- [trans-4- [2- (trans-4′-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-fluoro-1- [trans -4- [2- (trans-4'-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-fluoro-1- [trans-4- [2- (trans-4'-pentylbicyclohexane] -Trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4 -Trifluoromethoxy-1-
[Trans-4- [2- (trans-4′-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4′-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4′-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-trifluoromethoxy-1-
[Trans-4- [2- (trans-4′-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- ( Trans-4′-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- (trans-4′-propylbicyclohexane- Trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- [2- (trans-4′-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl ] Benzene 3-fluoro-4-trifluoromethoxy-1- [trans-4- 2- (trans-4'-pentylbicyclohexyl cyclohexane - trans-4-yl) propyl] cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4'-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4'-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4'-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 4-trifluoromethoxy-1- [trans-4- [2
-(Trans-4'-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4'-ethylbicyclohexane-trans- Four
-Yl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4'-propylbicyclohexane-trans-
4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4′-butylbicyclohexane-trans-4
-Yl) propyl] cyclohexyl] benzene 3,5-difluoro-1- [trans-4- [2- (trans-4'-pentylbicyclohexane-trans-
4-yl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4′-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-1- [Trans-4- [2- (trans-4′-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4′-butyl) Bicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-1- [trans-4- [2- (trans-4′-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 1 -[Trans-4- [2- (trans-4'-ethylbicyclohexane-trans- 4-yl) propyl] cyclohexyl] benzene 1- [trans-4- [2- (trans-4'-propylbicyclohexane-trans-4-yl) propyl]
Cyclohexyl] benzene 1- [trans-4- [2- (trans-4'-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 1- [trans-4- [2- (trans-4'- Pentylbicyclohexane-trans-4-yl) propyl]
Cyclohexyl] benzene (Example 6) 4-cyano-1- [trans-4-
[2- (trans-4'-propylbicyclohexane-
Trans-4-yl) propyl] cyclohexyl] benzene From 1- [trans-4- [2- (trans-4′-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene obtained in Example 5, In the same manner as in Example 2, 4-cyano-1- [trans-4-
[2- (trans-4'-propylbicyclohexane-
Trans-4-yl) propyl] cyclohexyl] benzene was obtained.

In the same manner, the following compound was obtained. 4-cyano-1- [trans-4- [2- (trans-
4'-ethylbicyclohexane-trans-4-yl)
Propyl] cyclohexyl] benzene 4-cyano-1- [trans-4- [2- (trans-
4'-butylbicyclohexane-trans-4-yl)
Propyl] cyclohexyl] benzene 4-cyano-1- [trans-4- [2- (trans-
4'-Pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4'-ethylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4'-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4'-butylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3-fluoro-4-cyano-1- [trans-4- [2
-(Trans-4'-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4'-ethylbicyclohexane-
Trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4'-propylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4'-butylbicyclohexane-
Trans-4-yl) propyl] cyclohexyl] benzene 3,5-difluoro-4-cyano-1- [trans-4
-[2- (trans-4'-pentylbicyclohexane-trans-4-yl) propyl] cyclohexyl] benzene (Example 7) 3,4,5-trifluoro-4'-
Synthesis of [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl

[0088]

Embedded image

[Trans-4- [2- (trans-4-
Propyl cyclohexyl) propyl] cyclohexyl]
32.6 g of benzene is dissolved in 120 ml of dichloromethane, 0.3 g of iron powder and 0.2 g of iodine are added, and -15 ° C is added.
And cooled. Bromine (19 g) was dissolved in dichloromethane (50 ml) and added dropwise with care so that the internal temperature did not exceed 0 ° C.
The mixture was stirred at -10 ° C for 5 hours and then at room temperature for 2 hours, and water and then an aqueous sodium hydrogen sulfite solution were added. The insoluble material was filtered off, extracted with hexane, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1), and recrystallized from ethanol to give 4-bromo- [trans-4- [2- 12 g of (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene was obtained. Next, 4.0 g of this was dissolved in 20 ml of THF,
Tetrakis (triphenylphosphine) palladium (0)
0.2 g was added. 1-bromo-
A Grignard reactant prepared from 2.2 g of 3,4,5-trifluorobenzene was added dropwise at room temperature, and the mixture was heated under reflux for 4 hours, neutralized by adding water and then dilute hydrochloric acid, and extracted with toluene. After washing with water, the solvent was distilled off, the residue was purified by silica gel column chromatography, and recrystallized from ethanol to give 3,4,5-trifluoro-4 '.
2.6 g of crystals of-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl were obtained.

The following compounds were obtained in the same manner. 3,4,5-Trifluoro-4 '-[trans-4-
[2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,5-trifluoro-4 '-[trans-4-
[2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,5-trifluoro-4 '-[trans-4-
[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4-difluoro-4 ′-[trans-4- [2-
(Trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4-difluoro-4 ′-[trans-4- [2-
(Trans-4-propylcyclohexyl) propyl]
Cyclohexyl] biphenyl 3,4-difluoro-4 ′-[trans-4- [2-
(Trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4-difluoro-4 ′-[trans-4- [2-
(Trans-4-pentylcyclohexyl) propyl]
Cyclohexyl] biphenyl 4-fluoro-4 ′-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 4-fluoro-4 ′-[trans-4- [2- (trans-4 -Propylcyclohexyl) propyl] cyclohexyl] biphenyl 4-fluoro-4 '-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 4-fluoro-4'-[trans-4- [ 2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 3,4-trifluoro-4 ′-[trans-4-
[2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 3,4-trifluoro-4 ′-[trans-4-
[2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ', 3,4-trifluoro-4'-[trans-4-
[2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ', 3,4-trifluoro-4'-[trans-4-
[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 4-difluoro-4 ′-[trans-4- [2-
(Trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 4-difluoro-4 ′-[trans-4- [2-
(Trans-4-propylcyclohexyl) propyl]
Cyclohexyl] biphenyl 2 ', 4-difluoro-4'-[trans-4- [2-
(Trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 4-difluoro-4 ′-[trans-4- [2-
(Trans-4-pentylcyclohexyl) propyl]
Cyclohexyl] biphenyl 2 ′, 3,4,5-tetrafluoro-4 ′-[trans-4- [2- (trans-4-ethylcyclohexyl)
Propyl] cyclohexyl] biphenyl 2 ', 3,4,5-tetrafluoro-4'-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ', 3,4,5- Tetrafluoro-4 '-[trans-4- [2- (trans-4-butylcyclohexyl)
Propyl] cyclohexyl] biphenyl 2 ', 3,4,5-tetrafluoro-4'-[trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 4-trifluoromethoxy-4'- [Trans-4-
[2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 4-trifluoromethoxy-4 ′-[trans-4-
[2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 4-trifluoromethoxy-4 '-[trans-4-
[2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 4-trifluoromethoxy-4 '-[trans-4-
[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 3-fluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3-Fluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 3-fluoro-4-trifluoromethoxy-4 ′-[trans- 4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3-fluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl ] Biphenyl 3,5-diflu B-4-trifluoromethoxy-4 '
-[Trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5-difluoro-4-trifluoromethoxy-4 '
-[Trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5-difluoro-4-trifluoromethoxy-4 '
-[Trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5-difluoro-4-trifluoromethoxy-4 '
-[Trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2'-fluoro-4-trifluoromethoxy-4'-
[Trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2'-fluoro-4-trifluoromethoxy-4'-
[Trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 2'-fluoro-4-trifluoromethoxy-4'-
[Trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2'-fluoro-4-trifluoromethoxy-4'-
[Trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 3-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 3-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 3-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 3-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 3,5-trifluoro-4-trifluoromethoxy-4 '-[trans-4- [2 -(Trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ', 3,5-trifluoro-4-trifluoromethoxy-4'-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] ] Cyclohexyl] biphenyl 2 ′, 3,5-trifluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ′, 3,5 -Trifluoro-4-trifluoromethoxy-4 '-[trans-4- [2- (trans-4-pen Tylcyclohexyl) propyl] cyclohexyl] biphenyl (Example 8) 3,4,5,2 ', 6'-pentafluoro-4'-[trans-4- [2- (trans-4-
Propyl cyclohexyl) propyl] cyclohexyl]
Biphenyl synthesis

[0091]

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3,5-difluoro-1- [trans-4
3.6 g of [[2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] benzene in THF
It was dissolved in 15 ml and cooled to -50 ° C. To this, n-butyllithium (1.6 M, n-hexane solution) 7.2 m
1 was slowly added dropwise, and the mixture was further stirred at the same temperature for 30 minutes. To this, triisopropyl borate 5.0 g THF2
The 0 ml solution was added dropwise over 30 minutes, the temperature was raised to 0 ° C. over 1 hour, and the mixture was further stirred at 0 ° C. for 2 hours. 10% hydrochloric acid 30m
1 was added, and the mixture was stirred at 5 to 10 ° C for 1 hr. Return to room temperature,
It was extracted with toluene, washed with a saturated aqueous solution of sodium hydrogen carbonate and then with water, and dehydrated with anhydrous sodium sulfate. 4.0 g of white crystals of 2,6-difluoro-4- [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] phenyl borate obtained by distilling off the solvent were obtained.

This whole amount and 2.6 g of 1-bromo-3,4,5-trifluorobenzene were dissolved in 15 ml of benzene and 10 ml of ethanol, and a sodium carbonate aqueous solution (2
N) 15 ml was added. 0.2 g of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated under reflux for 8 hours. After cooling to room temperature, hexane was added, the aqueous layer was separated, and the aqueous layer was further extracted with hexane to combine the organic layers. After the solvent was distilled off, the residue was purified by column chromatography (hexane) and recrystallized three times from ethanol to give 3,4,5,2 ', 6'-pentafluoro-4'-.
1.8 g of white crystals of [trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl were obtained.

The following compounds were obtained in the same manner. 3,4,5,2 ', 6'-Pentafluoro-4'-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,5,2 ', 6' -Pentafluoro-4 '-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,5,2', 6'-pentafluoro-4 '-[trans-4 -[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,2 ', 6'-tetrafluoro-4'-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] ] Cyclohexyl] biphenyl 3,4,2 ′, 6′-tetrafluoro-4 ′-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] sik Lohexyl] biphenyl 3,4,2 ', 6'-tetrafluoro-4'-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,4,2 ', 6'- Tetrafluoro-4 '-[trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 4,2', 6'-trifluoro-4 '-[trans-4
-[2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 4,2 ', 6'-trifluoro-4'-[trans-4
-[2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 4,2 ', 6'-trifluoro-4'-[trans-4
-[2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 4,2 ', 6'-trifluoro-4'-[trans-4
-[2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 2 ', 6'-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 6'-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 6'-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 2', 6'-difluoro-4-trifluoromethoxy-
4 '-[trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl 3,2', 6'-trifluoro-4-trifluoromethoxy-4 '-[trans-4- [ 2- (trans-4-
Ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,2 ′, 6′-trifluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-
Propyl cyclohexyl) propyl] cyclohexyl]
Biphenyl 3,2 ', 6'-trifluoro-4-trifluoromethoxy-4'-[trans-4- [2- (trans-4-
Butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,2 ′, 6′-trifluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-
Pentylcyclohexyl) propyl] cyclohexyl]
Biphenyl 3,5,2 ′, 6′-tetrafluoro-4-trifluoromethoxy-4 ′-[trans-4- [2- (trans-4-ethylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5,2 ′ , 6'-Tetrafluoro-4-trifluoromethoxy-4 '-[trans-4- [2- (trans-4-propylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5,2', 6'-tetrafluoro- 4-Trifluoromethoxy-4 '-[trans-4- [2- (trans-4-butylcyclohexyl) propyl] cyclohexyl] biphenyl 3,5,2', 6'-tetrafluoro-4-trifluoromethoxy-4 '-[Trans-4- [2- (trans-4-pentylcyclohexyl) propyl] cyclohexyl] biphenyl (Example ) Host liquid crystal is suitable as a particularly active matrix drive Preparation of liquid crystal composition (H)

[0095]

[Chemical 29]

Was prepared. This host liquid crystal (H) is 11
It shows a nematic phase below 6.7 ℃ and its melting point is 11 ℃.
Met. Further, the threshold voltage (V _th ) of the TN cell having a cell thickness of 6 μm produced using this was 2.14V.

70% by weight of this host liquid crystal (H) and the first
A mixed liquid crystal (M-3) consisting of 30% by weight of the compound (No. 3) in the table was prepared. The upper limit temperature (T _NI ) of the N phase and its threshold voltage measured in the same manner are as follows.

Upper limit temperature of N phase (T _NI ) 102.0 ° C. Threshold voltage (V _th ) 1.86 V Therefore, although T _NI is slightly lowered, the threshold voltage (V _th ) is significantly increased. It can be seen that it has been reduced.

Next, when this (M-4) was stored at -20 ° C, precipitation of crystals and phase separation could not be observed even after 1 week. In addition, (M-3) is solidified at -60 ° C,
The melting temperature was measured and found to be -10 ° C. (Comparative Example 1) 70% by weight of host liquid crystal (H) and (No.
Formula (R-2) having a structure similar to the compound of 3), but having a skeleton containing no methyl branch.

[0100]

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A comparative composition (MR-2) was prepared consisting of 30% by weight of the compound of. The T _NI and its threshold voltage measured in the same manner are as follows. Upper limit temperature of N phase (T _NI ) 105.0 ° C. Threshold voltage (V _th ) 1.84 V Therefore, although T _NI is slightly higher than (M-3), the threshold voltage Were about the same.

However, this (MR-3) is -20
When left at 0 ° C., partial precipitation of crystals was observed within one week. Further, it was solidified at −60 ° C. and its melting temperature was measured, and it was 0 ° C., which was considerably higher than that of (M-3).

As described above, the compound of the general formula (I) of the present invention has excellent compatibility with other liquid crystal compounds and compositions, as compared with the corresponding compound having a skeleton containing no methyl branch. It can be seen that it is easy to obtain a liquid crystal composition in which crystal precipitation or phase separation does not easily occur even at low temperatures.

[0104]

INDUSTRIAL APPLICABILITY The 1,2-dicyclohexylpropane derivative provided by the present invention can be industrially easily produced from a commercially available compound as shown in Examples. The liquid crystal composition containing the obtained 1,2-dicyclohexylpropane derivative has almost the same electro-optical characteristics as compared with the liquid crystal composition containing the compound having a corresponding dicyclohexylethane skeleton, and also has a crystal It is extremely useful as a practical liquid crystal because it has a characteristic of being difficult to precipitate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09K 19/30 9279-4H C09K 19/30 G02F 1/13 500 G02F 1/13 500

Claims (7)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, n represents an integer of 1 or 2, and X ¹ , X ² and X ³ each independently represent a hydrogen atom or a fluorine atom, Y
It is _{-CH 2 CH 2 -, - COO} -, - OCO -, - CH 2
_{O -, - OCH 2 -,} 1,4- cyclohexylene group, 1
Pieces or two fluorine atoms by represents may also be 1,4-phenylene group or a single bond substituted, Z is a hydrogen atom, a fluorine atom, a chlorine atom, -CN, -R ^2, -OR ^2,
_{-OCN, -CF 3, -OCF 3,} -OCF 2 H or -O
CH ₂ CF ₃ is represented, R ² is an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, and the cyclohexane ring is in the trans configuration. Where Y
Represents a 1,4-cyclohexylene group, a 1,4-phenylene group optionally substituted by 1 or 2 fluorine atoms, n represents 1. ). 2. Y is a 1,4-cyclohexylene group, optionally substituted by one or two fluorine atoms, 1,
A compound of general formula (I) according to claim 1, characterized in that it represents a 4-phenylene group or a single bond. 3. Z is a fluorine atom, a chlorine atom, or —CF_Three,
-OCF_Three, -OCF _TwoH or -OCH_TwoCF_ThreeTo represent
A compound of general formula (I) according to claim 2, characterized in that 4. The compound according to claim 3, wherein Z is a fluorine atom. 5. The compound according to claim 4, wherein R ¹ is a linear alkyl group having 1 to 7 carbon atoms. 6. The compound according to claim 5, wherein n is 1 and Y is a single bond. 7. A liquid crystal composition containing a compound represented by the general formula (I) according to claim 1, 2, 3, 4, 5 or 6.