JPH09143103A - 4-(2-cyclohexyl) ethyl biphenyl derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain a mixture composed of at least two kinds of the subject derivative bearing deuterium atom hard to develop crystal deposition and phase separation at low temperatures and useful as an electro-optical liquid crystal display material. SOLUTION: This compound, a 4-(2-cyclohexyl)ethyl biphenyl derivative, is expressed by formula I (R<1> is a 1-12C alkyl; X<1> -X<4> are each a hydrogen atom or deuterium atom; Y<1> -Y<5> are each a hydrogen atom or fluorine atom; (m) is an integer of 0 or 1; Z is a fluorine atom, chlorine atom R<2> , etc.; R<2> is a 1-12C alkyl or 3-12C alkenyl), e.g. d4 -3,4-difluoro-4'-[2-(trans-4-pentylcyclohexyl) ethyl]biphenyl. A mixture of the compound of formula I is obtained through a cyclohexanone derivative of formula II a intermediate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a mixture of 4- (2-cyclohexyl) ethylbiphenyl derivatives having deuterium atoms, which is useful as an electro-optical liquid crystal display material.

[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). ), Etc., and as the drive system, the conventional static drive has become more common and multiplex drive has become more common, and the simple matrix system and recently the active matrix system have been put into practical use.

Various characteristics are required as a liquid crystal material according to these display system and drive system. (1)
A wide temperature range and (2) low viscosity are important required characteristics common to all methods. Among these, (1) includes (1a) a high maximum temperature (T _NI ) of the nematic phase, and (1b) a low melting point, which hardly causes phase separation such as crystallization or precipitation.

Up to the present, no liquid crystal compound which alone satisfies such required properties has been known, and it is actually used as a mixture of various liquid crystal compounds. Although a wide variety of liquid crystal compounds have been developed so far, a compound having a 4- (2-cyclohexyl) ethylbiphenyl skeleton can be given as a relatively frequently used compound.

The compound having a 4- (2-cyclohexyl) ethylbiphenyl skeleton has a T _NI and a viscosity higher than those of other liquid crystal compounds having the same ring structure, for example, a compound having a corresponding 4-cyclohexylbiphenyl skeleton. It is almost the same level and has a feature that the compatibility with other liquid crystals is relatively excellent. However, it cannot be said that the low temperature characteristics, that is, the difficulty of causing precipitation or the like in the composition, is sufficiently satisfactory.

To lower the melting point of the liquid crystal material, it is effective to mix a large number of compounds and increase the number of components.
For example, in order to increase the number of components having the characteristics of 4- (2-cyclohexyl) ethylbiphenyl skeleton, a method of mixing homologues in which the number of carbon atoms of the terminal alkyl group is changed can be used. However, changes in the number of carbon atoms have a great influence on physical properties such as elastic constants, phase transition temperatures, and viscosity, and it is often not easy to prevent the precipitation of crystals at this low temperature.

Therefore, the same 4- (2-cyclohexyl)
A liquid crystal compound having an ethylbiphenyl skeleton, which has a low melting point without adversely affecting other properties or is hard to crystallize even at low temperature and has improved compatibility with other liquid crystal compounds, has been desired. .

[0008]

The problem to be solved by the present invention is to provide a liquid crystal compound having a 4- (2-cyclohexyl) ethylbiphenyl skeleton in which a cyclohexane ring is deuterated in order to meet the above object. Another object of the present invention is to provide a mixture, and further to provide a liquid crystal composition having a low viscosity and a wide liquid crystal temperature range, and in which precipitation, phase separation and the like hardly occur especially at low temperatures.

It has not been known that a hydrogen atom in a liquid crystal compound should be replaced with a deuterium atom (D), and several reports have already been made. 1) H. Gasparoux et al., Ann. Rev. Phys. Chem., 27, 175 (197
6) 2) GWGray et al., Mol.Cryst.Liq.Cryst., 41, 75 (1977) 3) AJ Leadbetter et al., J. Phys. [Paris] coll C3, 40,
125 (1979) 4) A. Kolbe et al., Z. Naturforsch., 23a, 1237 (1968) 5) JD Rowell et al., J. Chem. Phys., 43, 3442 (1965) 6) WD Philips et al., J. Chem. Phys ., 41, 2551 (1964) 7) AF Martins et al., Mol.Cryst.Liq.Cryst., 14, 75 (197
7) 8) ET Samulski et al., Phys. Rev. Lett., 29, 340 (1972) 9) H. Zimmermann, Liquid Crystals, 4, 591 (1989) In these reports, hydrogen in the carboxyl group of 4-alkoxybenzoic acid was reported. Atom (H) to deuterium atom (D)
In all the examples except that the hydrogen atom in the side chain is substituted, the hydrogen atom (H) of the cyclohexane ring is a heavy atom as in the compound of the general formula (I) of the present invention. An example in which a hydrogen atom (D) was substituted was not known.

[0010]

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

[0011]

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(Where R¹Is an alkane having 1 to 12 carbon atoms
Represents a kill group, X¹, X^Two, X^ThreeAnd X ^FourAre independent
Represents a hydrogen atom (H) or a deuterium atom (D), and Y
¹, Y^Two, Y^Three, Y^FourAnd Y^FiveAre each independently a hydrogen atom
Or represents a fluorine atom, and m represents an integer of 0 or 1.
Z is a fluorine atom, a chlorine atom, a hydrogen atom, a cyano group,
-R^Two, -OR^Two, -CF_Three, -OCF_Three, -OCF_TwoHmata
Is -OCH_TwoCF_ThreeAnd R^TwoHas 1 to 12 carbon atoms
An alkyl group or an alkenyl group having 3 to 12 carbon atoms
The cyclohexane ring is in the trans configuration. )so
Two or more compounds represented are (1) X¹~ X^Four
The number and / or substitution position of deuterium atoms (D) in
And (2) R to each other¹, M, Y¹, Y^Two, Y^Three,
Y^Four, Y^FiveAnd Z are the same,
Mixture of two or more compounds represented by general formula (I)
(Hereinafter, referred to as a mixture of general formula (I)).

Of these, in the general formula (I), R ¹ is a linear alkyl group having 1 to 7 carbon atoms, Z is a fluorine atom, a chlorine atom, a cyano group, or a direct alkyl group having 1 to 7 carbon atoms. chain alkyl group or an alkoxyl group, or -OCF _3,
Mixtures of the general formula (I) are preferred.

Among these, the general formula (I)
Y¹, Y^TwoAnd Y^ThreeAt least two of them are fluorine
Mixtures of compounds that are children, in general formula (I)
Y ¹, Y^TwoAnd Y^ThreeFrom a compound in which both are hydrogen atoms
Or in the general formula (I), Y¹,
Y^FourAnd at least one of Z is a fluorine atom
A mixture of compounds is more preferable. In the above case
In this case, m is preferably 1. Similarly,
In the case of d, it is preferable that m is 0.

Among such mixtures, the proportion of the number of deuterium atoms (D) in the mixture of two or more compounds represented by the general formula (I) is from X ¹ to the general formula (I). A mixture in the range of 30 to 95% is preferable, and a mixture in the range of 50 to 90% is more preferable, based on the total number of X ⁴ .

The mixture of the general formula (I) of the present invention can be prepared, for example, by the general formula (II)

[0017]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ and X ⁴
Represents the same meaning as in formula (I). It can be produced in exactly the same manner as in the case of the compound which is not substituted with the corresponding deuterium atom (D), using the mixture of cyclohexanone derivatives represented by the formula (4) as an intermediate. (Step A) Synthesis of Deuterium-Substituted Mixture of General Formula (II) A mixture of cyclohexanone derivatives of general formula (II) is
Corresponding general formula (II ′)

[0019]

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The cyclohexanone derivative of the formula (wherein R ¹ and m have the same meanings as in formula (I)) in a solvent such as dichloromethane in the presence of a base (D ₂
It can be easily obtained by reacting with O).
The reaction is preferably carried out at room temperature to the reflux temperature of the solvent, and the base is preferably a metal alcoholate or the like. Further, in order to accelerate the reaction, it is preferably carried out in the presence of a quaternary salt such as tetrabutylammonium bromide. The deuteration rate can be adjusted by the molar ratio of the heavy water used, but when a high value is required, the heavy water used can be replaced anew to continue the reaction. (Step B) Synthesis of Mixture of Cyclohexane Ethanal Derivative of General Formula (III) To a mixture of cyclohexanone derivative of General Formula (II),
General formula (IV)

[0021]

## STR00005 ## A Wittig reagent of CH ₃ OCH = PPh ₃ (IV) is reacted and then hydrolyzed with an acid to obtain a cyclohexanecarbaldehyde derivative. By repeating the same operation once more,
General formula (III)

[0022]

[Chemical 6]

(Wherein R ¹ , m, X ¹ , X ² , X ³ and X ⁴
Represents the same meaning as in formula (I). ), A mixture of deuterium-substituted cyclohexaneethanal derivatives is obtained. (Step C) Synthesis of Mixture of General Formula (I) (a) In General Formula (I), when Z represents other than a cyano group and a chlorine atom, a Grignard reagent or organolithium reaction prepared from bromobenzene or iodobenzene The agent is reacted with the mixture of the general formula (II), then dehydrated in the presence of an acid catalyst, and further catalytically reduced to give the general formula (V).

[0024]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ , X ⁴ ,
Y ⁴ and Y ⁵ have the above-mentioned meanings. A mixture of phenethylcyclohexane derivatives of 1) is obtained. General formula (VI) obtained by brominating (using bromine or the like) or iodating (using iodine / periodic acid or the like)

[0026]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ , X ⁴ ,
Y ⁴ and Y ⁵ have the same meanings as in formula (I), and W ¹ represents a bromine or iodine atom. And a mixture of halogenated benzene derivatives represented by the general formula (VI)
I)

[0028]

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(Wherein Y ¹ , Y ² and Y ³ have the above-mentioned meanings, W ² represents a bromine or iodine atom, and Z ′
Represents the meaning of Z in the general formula (I) excluding a cyano group and a chlorine atom. ), Which can be obtained by coupling a Grignard reagent or an organometallic reagent such as an organolithium reagent prepared from halogenated benzene in the presence of a catalyst. As the catalyst, nickel (II) -based, palladium (0) -based, palladium (II) -based or the like can be used.

When Z represents a cyano group in general formula (I), by using general formula (VIIh), which is a compound in which Z represents a hydrogen atom in general formula (VII), A compound of the general formula (Ih) in which Z represents a hydrogen atom

[0031]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ , X ⁴ ,
Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ have the same meanings as in formula (I). ) Is obtained, and (i) is brominated or iodinated as described above, and then copper cyanide is obtained.
Cyanation with (I) or (ii) Chloroformylation with oxalic acid chloride / aluminum chloride followed by amide formation with aqueous ammonia, followed by dehydration with thionyl chloride, etc.
i) It can be obtained by, for example, nitrating and then reducing it to give an aniline derivative, diazotizing it, and then decomposing it in the presence of copper (I) cyanide.

In the general formula (I), when Z represents a chlorine atom, the diazo compound of (iii) above is treated with copper chloride.
(I) It can be obtained by decomposing in the presence. When Z in the general formula (I) represents an alkenyloxy group, a similar reaction is carried out using a compound in the general formula (VII) in which Z is —OCH ₃ , followed by demethylation (hydrobromic acid, Trimethylsilyl iodide, boron tribromide and the like are used.) And in the general formula (I), Z is —OH.
A compound of the general formula (Ioh)

[0034]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ , X ⁴ ,
Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ have the same meanings as in formula (I). It can also be obtained by obtaining a mixture of) and alkenylating it by a conventional method.

When Z represents an alkenyl group in the general formula (I), the general formula (I
w)

[0037]

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(Wherein R ¹ , m, X ¹ , X ² , X ³ , X ⁴ ,
Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ have the same meanings as in formula (I), and W ³ represents a bromine atom or an iodine atom. ) In the presence of a copper (I) catalyst (or a catalyst of palladium (0), palladium (II), nickel (II), etc. in some cases) as a Grignard or organolithium reagent. It can also be obtained by reacting with an alkenyl halide, reacting with a alkenyl halide after forming a copper ate complex, or in particular in the case of a 1-alkenyl group, reacting with a corresponding aldehyde and then dehydrated.

When Z in the general formula (I) represents --OCF ₂ H, the above general formula (Ioh) is used as a formic acid ester, which is converted into diethylaminosulfur trifluoride (DAS).
It can be obtained by reacting with a fluorinating agent such as T). (Step D) Synthesis of mixture of general formula (I) (b) Instead of the halogenated benzene derivative of general formula (VII) in step C, general formula (VIII)

[0040]

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From the halogenated biphenyl derivative of the formula (wherein Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Z'have the above meanings and W ³ represents a bromine or iodine atom), By directly reacting the Grignard reagent or the organolithium reagent prepared as described above with the mixture of the general formula (II),
Hereinafter, the mixture of the general formula (I) can be obtained in the same manner as in the step (C).

In the thus obtained general formula (I), X
An example of a mixture of compounds in which ^{1 to} X ⁴ are hydrogen atoms (H) or deuterium atoms (D) is shown in Table 1 below together with their phase transition temperatures.

[0043]

[Table 1]

(In the table, Cr represents a crystalline phase, SB represents a smectic B phase, N represents a nematic phase, and I represents an isotropic liquid phase. Also, () indicates a monotropic phase. The D conversion rate is X ¹ ~ in the mixture.
The ratio of the number of deuterium atoms (D) to the total number of X ⁴ is shown. This mixture of two or more compounds of the general formula (I) has a low melting point and does not precipitate crystals even in a low temperature region as compared with a corresponding single compound which is not deuterium-substituted but has the same skeleton. It has excellent characteristics. The present invention also provides a liquid crystal composition containing these mixtures.

As such an example, a host liquid crystal (M) which is currently widely used

[0046]

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(Wherein the cyclohexane ring represents the trans configuration and "%" represents "% by weight") 90% by weight and 10% by weight of the mixture of (No. 1) in Table 1 Liquid crystal (M-1), host liquid crystal (M) 90% by weight
And a mixed liquid crystal (M-11) consisting of 10% by weight of the mixture of (No. 11) in Table 1 was prepared. When these mixed liquid crystals (M-1) and mixed liquid crystals (M-11) were stored at 0 ° C., no crystal precipitation could be observed even after 2 weeks.

On the other hand, 90% by weight of host liquid crystal (M)
And (No. 1), but without deuterium substitution (R-1)

[0049]

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A mixed liquid crystal (M
R-1), 90% by weight of host liquid crystal (M) and (No. 1)
Corresponding to the mixture of 1) but without deuterium substitution (R-11)

[0051]

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A mixed liquid crystal (M
R-11) was prepared and stored at 0 ° C. in the same manner, and a minute amount of crystals was observed to deposit in one week. Next, a host liquid crystal (N) suitable for active matrix

[0053]

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(In the formula, the cyclohexane ring represents a trans configuration and "%" represents "% by weight") 85% by weight
And mixed liquid crystal (N-1) consisting of 15% by weight of the mixture of (No. 1) in Table 1, 90% by weight of host liquid crystal (N) and 10% by weight of the mixture of (No. 11) in Table 1. A mixed liquid crystal (N-11) was prepared and the mixed liquid crystal (N-1) and the mixed liquid crystal (N-11) were allowed to stand at 20 ° C., and crystal precipitation was observed even after standing for 2 weeks. could not.

On the other hand, the host liquid crystal (N) is 85% by weight.
And a mixed liquid crystal (NR-1) consisting of 15% by weight of a compound (R-1) not substituted with deuterium, a host liquid crystal (N) 9
0% by weight and a compound not substituted with deuterium (R-1
1) A mixed liquid crystal (NR-11) containing 10% by weight was prepared and stored in the same manner at 20 ° C.
In 1), precipitation of a trace amount of crystals was observed in 3 days and in (NR-1) in 1 week.

From the above, the mixture of two or more compounds represented by the general formula (I) according to the present invention has an excellent feature that crystals are not precipitated in the composition even in a low temperature region, and is practically used. It can be understood that it is extremely useful in preparing a typical liquid crystal material.

[0057]

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 in each mixture is
A known compound that is not deuterated is compared with a capillary gas chromatograph and a thin layer chromatograph to show the same retention time (or Rf value), and a nuclear magnetic resonance spectrum (NMR) and a mass spectrum (M
S), infrared absorption spectrum (IR), etc.
The D conversion rate of the mixture as a whole was measured by NMR. For the measurement, NMR of "JNM-GSX400" (400 MHz ¹ H, manufactured by JEOL Ltd.) was used.

It should be noted, previously noted the compounds name and structural formula "d ₄ -" in formula (I), of the substituents of X ¹ to X ^4, at least one deuterium atom (D) Is a mixture of the compounds (Reference Example 1) Synthesis of d _{4-4-propyl-cyclohexanone}

[0060]

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24 g of sodium methoxide was dissolved in 180 ml of heavy water (D conversion rate 99.8%). 185 g of 4-propylcyclohexanone and tetrabutylammonium bromide 1.2 dissolved in 200 ml of dichloromethane were added.
g was added and the mixture was heated with stirring at the reflux temperature of the solvent for 10 hours. After cooling, the organic layer was separated, and the aqueous layer was extracted with dichloromethane and then collected. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate.

[0062] 2-position and 6-position of the solvent was distilled off cyclohexanone ring to obtain a d _{4-4-propyl-cyclohexanone} 187g which is deuterated. When the D conversion rate was measured by NMR, it was about 82%.

Similarly, the following deuterium-substituted cyclohexanone derivative was obtained. d _{4-4-pentylcyclohexanone} (D ratio of about 85
%) D _{4-4-ethyl-cyclohexanone} (D ratio of about 85%) d ₄ - trans-4'-propyl-bi cyclohexane -4
- one (D ratio of about 80%) (Reference Example 2) d ₄ - Synthesis of trans-4-propyl cyclohexane carbaldehyde

[0064]

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250 g of methoxymethyltriphenylphosphonium chloride was added to 1.0 l of tetrahydrofuran (THF).
And was cooled to 5 ° C or lower with ice. 87 g of potassium t-butoxide was added thereto, taking care not to exceed an internal temperature of 10 ° C, over about 30 minutes, and stirred at 5 to 10 ° C for 1 hour to prepare a Wittig reaction agent. A solution of 80 g of d ₄ -trans-4-propylcyclohexanone in 160 ml of THF was slowly added dropwise thereto, and after completion, the mixture was further stirred at 5 to 10 ° C. for 1 hour. 0.6 l of water was added, and the water layer was 400 ml of hexane.
It was extracted with and added to the organic layer. The solvent was distilled off under reduced pressure to obtain about 7
The concentration was stopped when 0 ml of the solvent remained, 1.2 l of hexane was added, and the precipitated crystals (triphenylphosphine oxide) were filtered off. The filtrate was added to methanol / water (2 /
1) The mixture was washed twice with 800 ml of the mixed solvent and further washed once with saturated saline. The solvent is distilled off and the enol ether body 9 is obtained.
5 g were obtained.

This was mixed with 400 ml of THF and 5% of 10% hydrochloric acid.
It was dissolved in 0 ml and stirred at room temperature for 4 hours. Hexane 10
0 ml and 300 ml of water were added, and the water layer was hexane 300.
The mixture was extracted with ml, added to the organic layer, washed with saturated brine, and dried over anhydrous magnesium sulfate. After separation by filtration, the solvent was distilled off to obtain about 90 g of crude crystals of cyclohexanecarbaldehyde. (Cis / trans = 2/8) This whole amount was dissolved in a mixed solvent of 400 ml of methanol and 100 ml of ethanol, and 10 ml of 20% sodium hydroxide aqueous solution was added,
Stir at room temperature for 1.5 hours. 500 ml of water was added, neutralized with a small amount of 10% hydrochloric acid, and extracted with 2500 ml of hexane three times. After washing the hexane layer with saturated brine, the solvent was distilled off d ₄ - the trans-4-propyl cyclohexane carbaldehyde 90 g.

Similarly, the following cyclohexanecarbaldehyde derivative was obtained. d ₄ - trans-4-pentylcyclohexanecarboxylate carbaldehyde d ₄ - trans-4-ethylcyclohexane carbaldehyde d ₄ - trans-4'-propyl-bi cyclohexane - trans-4-carbaldehyde (Example 3) d ₄ - trans - Synthesis of 4-propylcyclohexaneethanal

[0068]

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D ₄ -trans- _4- obtained in Reference Example 2
The trans-4-propyl cyclohexane ethanal 85 g - d ₄ by propyl cyclohexanecarbaldehyde 90g from Reference Example 2 and the same operation (except for isomerization with sodium hydroxide solution.).

Similarly, the following cyclohexaneethanal derivative was obtained. d ₄ - trans-4-pentylcyclohexanecarboxylate ethanal d ₄ - trans-4-ethylcyclohexane ethanal d ₄ - trans-4'-propyl-bi cyclohexane -4
- ethanal (Reference Example 4) d _{4-2-(trans-4-propyl-cyclohexyl)} Synthesis of ethylbenzene

[0071]

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To 16 g of magnesium in 50 ml of THF, a solution of 94 g of bromobenzene in 250 ml of THF was added dropwise over 3 hours at a rate at which gentle reflux was maintained, and the mixture was further stirred for 1 hour. Cool to 10 ° C or below and d ₄ -transformer-4
-Propyl cyclohexane ethanal 81 g THF2
A 50 ml solution was added dropwise at an internal temperature of 20 ° C. or lower in about 1 hour.
After the completion, the mixture was further stirred for 1 hour at room temperature, and diluted hydrochloric acid was added until it became weakly acidic. After separating the organic layer, the aqueous layer was extracted twice with 50 ml of ethyl acetate, the organic layers were combined, washed with water and then saturated saline, and dehydrated and dried with a small amount of anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 105 g of alcohol. The total amount was dissolved in 300 ml of toluene, 5 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 3 hours while removing azeotropic water out of the system. The mixture was cooled to room temperature and washed with an aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with 50 ml of toluene and the toluene layers were combined. After washing with water, drying with a small amount of anhydrous sodium sulfate and distilling off the solvent, d ₄ -2
84 g of a crude product of-(trans-4-propylcyclohexyl) ethenylbenzene was obtained. This was purified by silica gel column chromatography (hexane) to obtain 66 g of a purified product. The whole amount was dissolved in 100 ml of ethyl acetate, 1.0 g of 5% palladium carbon was added, and the mixture was stirred in an autoclave at a hydrogen pressure of 4 atm at room temperature for 4 hours. The catalyst was filtered through Celite, the solvent was distilled off d _4-2-(trans -
65 g of a crude product of 4-propylcyclohexyl) ethylbenzene was obtained. This was recrystallized from ethanol at a low temperature of 0 ° C. or lower to obtain 50 g of a purified product.

Similarly, the following 2- (cyclohexyl)
An ethylbenzene derivative was obtained. d _{4-2-(trans-4-pentylcyclohexyl)}
Ethylbenzene d _{4-2-(trans-4-ethyl-cyclohexyl)} ethylbenzene d ₄ - trans-4'-propyl - trans-4- (2
- phenylethyl) bicyclohexane d _{4-3-fluoro-1-} [2- (trans-4-propyl cyclohexyl) ethyl] benzene d _{4-3,5-difluoro-1-} [2- (trans-4
- pentylcyclohexyl) ethyl] benzene d _{4-2-fluoro-4-} [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl (Example 5) d _4-1-[2- (trans-4-propylcyclohexyl ) Synthesis of ethyl] -4-iodobenzene

[0074]

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50 g of the mixture of d ₄ 2- (trans-4-propylcyclohexyl) ethylbenzene obtained in Reference Example 4 was dissolved in 230 ml of acetic acid, and 33 g of iodine, 24 g of periodic acid dihydrate, 55 ml of sulfuric acid and water. 45 ml and 25 ml of 1,2-dichloroethane were added. After heating under reflux for 1 hour, pour into 400 ml of water and add 200 m of toluene.
Extracted twice with l. The toluene layer was washed with a 10% sodium sulfite aqueous solution, water and saturated saline, and dehydrated and dried over anhydrous sodium sulfate. The crude crystal obtained by distilling off the solvent was recrystallized twice from ethanol to obtain 28 g of d ₄ -1- [2- (trans-4-propylcyclohexyl) ethyl] -4-iodobenzene.

[0076] Similarly d _{4-3-fluoro-1-} [2
-(Trans-4-propylcyclohexyl) ethyl]
It was obtained d ₄ -1- [2- (trans-4-propyl cyclohexyl) ethyl] -3-fluoro-4-iodobenzene benzene. (Reference Example 6) d _{4-3,5-difluoro-1-} [2-
(Trans-4-propylcyclohexyl) ethyl]-
Synthesis of 4-iodobenzene

[0077]

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111 g of a mixture of d ₄ -3,5-difluoro-1- [2- (trans-4-propylcyclohexyl) ethyl] benzene obtained in Reference Example 4 was dissolved in 400 ml of tetrahydrofuran (THF) to obtain -45. Cooled to ° C. 255 ml of n-butyllithium (1.66M hexane solution) was added dropwise thereto at a temperature of -40 ° C or lower for 2 hours, and the mixture was further stirred at the same temperature for 1 hour. 118g of iodine T
470 ml of HF solution was added dropwise at -40 ° C or lower for 1 hour,
Further, the mixture was stirred at the same temperature for 1 hour. 25 ml of water was added, the temperature was returned to room temperature, 10% aqueous sodium hydrogen sulfite solution was added, and the mixture was extracted twice with 500 ml of hexane. Combine the organic layers 1
The extract was washed with 0% aqueous sodium hydrogen sulfite solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent d _4-3,5-oil was distilled off difluoro-1- [2-
(Trans-4-propylcyclohexyl) ethyl]-
155 g of 4-iodobenzene was obtained.

Similarly, d ₄ -3,5-difluoro-
1- [2- (trans-4-pentylcyclohexyl)
Ethyl] -4-iodobenzene was obtained. (Example 1) d _{4-3,4-difluoro-4} '- [2
-(Trans-4-pentylcyclohexyl) ethyl]
Synthesis of biphenyl (mixture of No. 3 in Table 1)

[0080]

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0.55 g of magnesium was suspended in 6 ml of THF, and a solution of 4.62 g of 1-bromo-3,4-difluorobenzene in 15 ml of THF was added dropwise thereto in about 30 minutes at a rate at which gentle reflux was continued to give a Grignard reactant. Prepared. After further stirring for 1 hour, unreacted insoluble matter such as magnesium was filtered off. Separately, d ₄ -1 obtained in Reference Example 5
-[2- (trans-4-propylcyclohexyl) ethyl] -4-iodobenzene 6.39 g in THF 15 m
It was dissolved in 1 and 0.21 g of tetrakis (triphenylphosphine) palladium (0) was added, followed by cooling with water. The total amount of the Grignard reactant was added dropwise to this over 3 hours. After stirring for a further 1 hour, water was added and the mixture was neutralized with 10% hydrochloric acid and extracted with toluene. The organic layer was washed with water and then with saturated saline, and dehydrated and dried over anhydrous sodium sulfate. The crude crystals 7.3g obtained by distilling off the solvent was purified by silica gel column chromatography (hexane), d _{4-3,4-difluoro-4} was recrystallized further from ethanol '- [2- (trans 5.55 g of -4-pentylcyclohexyl) ethyl] biphenyl was obtained. The phase transition temperatures are summarized in Table 1.

The following compounds were obtained in the same manner. d _{4-3,4-difluoro-4} '- [2- (trans -
Ethyl cyclohexyl) ethyl 4-] biphenyl d _{4-3,4-difluoro-4} '- [2- (trans -
4-propyl cyclohexyl) ethyl] biphenyl d _{4-3,5-difluoro-4} '- [2- (trans -
Ethyl cyclohexyl) ethyl 4-] biphenyl d _{4-3,5-difluoro-4} '- [2- (trans -
4-propyl cyclohexyl) ethyl] biphenyl d _{4-3,5-difluoro-4} '- [2- (trans -
4-pentylcyclohexyl) biphenyl d ₄ -3,4,5-trifluoro -4 '- No.1 mixture of [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl (Table 1 in) d ₄ - 3,4,5-trifluoro-4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -3,4,5-trifluoro-4' - [2- (trans-4-pentyl cyclohexyl) ethyl] biphenyl d ₄ 4-fluoro-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-fluoro-4' - [2- (trans-4-propyl-cyclohexyl) ethyl] biphenyl d ₄ 4-fluoro-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (mixture No.4 in table 1) d _4-3-fluoro-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-3-fluoro-4'} - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -3-fluoro-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ 4- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4- [2- ( trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 4- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -3,4,5-trifluoro-4 '- [2- (trans - 4'-ethyl-bi cyclohexane-yl) ethyl] biphenyl d ₄ -3,4,5-trifluoro-4 '- [2- (trans-4'-propyl Bicyclohexane-4-yl) ethyl] biphenyl (mixture No.2 in Table 1) d ₄ -4-trifluoromethoxy-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-trifluoromethoxy-4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 4-trifluoromethoxy-4' - [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d _4-4-methyl-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-methyl-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 4-methyl-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ 4-ethyl-4' - [2 (Trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-ethyl-4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 4-ethyl-4' - [2- (trans 4-pentylcyclohexyl) ethyl] biphenyl d ₄ 4-propyl-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-propyl-4' - [2- (trans-4 -Propylcyclohexyl) ethyl] biphenyl (No. Mixture of 5) d ₄ -4-propyl-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ 4-methoxy-4' - [2- (trans-4-ethyl-cyclohexyl) ethyl ] biphenyl d ₄ 4-methoxy-4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 4-methoxy-4' - [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d _{4-2,3-difluoro-4-ethoxy-4} '- [2
- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2,3-difluoro-4-ethoxy-4} '- [2
-(Trans-4-propylcyclohexyl) ethyl]
Biphenyl d _{4-2,3-difluoro-4-ethoxy-4} '- [2
-(Trans-4-pentylcyclohexyl) ethyl]
Biphenyl d ₄ -2 ', 4-difluoro-4' - [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 4-difluoro-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ', 4-difluoro-4' - [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2 ', 3- difluoro-4' - [2- (trans 4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3- difluoro-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3- difluoro-4' - [ 2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2 ', 3,4-trifluoro-4' - [2- (trans-4-ethylcyclohexyl) e Le] biphenyl d ₄ -2 ', 3,4-trifluoro-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3,4-trifluoro-4' - [ 2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2 ', 3,5-trifluoro-4' - [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3 , 5-trifluoro-4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2', 3,5-trifluoro-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2 ', 3,4,5-tetrafluoro-4' - [2
- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3,4,5-tetrafluoro-4' - [2
-(Trans-4-propylcyclohexyl) ethyl]
Biphenyl (No.6 mixture in Table 1) d ₄ -2 ', 3,4,5- tetrafluoro-4' - [2
-(Trans-4-pentylcyclohexyl) ethyl]
Biphenyl d _{4-2'-fluoro-4-trifluoromethoxy} -
4 '-[2- (trans-4-ethylcyclohexyl)
Ethyl] biphenyl d _{4-2'-fluoro-4-trifluoromethoxy} -
4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl (No.8 mixture in Table 1) d _{4-2'-fluoro-4-trifluoromethoxy} -
4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2', 3- difluoro-4-trifluoromethoxy-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3- difluoro-4-trifluoromethoxy-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ', 3- difluoro-4-trifluoromethyl-methoxy-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2', 3,5-trifluoro-4-trifluoromethoxy-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl ] biphenyl d ₄ -2 ', 3,5-trifluoro-4-trifluoromethoxy-4' - [2- (trans-4-propylcyclohexyl ) Ethyl] biphenyl d ₄ -2 ', 3,5-trifluoro-4-trifluoromethoxy-4' - [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d _{4-2'-fluoro-4-} methyl-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2'-fluoro-4-methyl-4'} - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ 2'-fluoro-4-methyl-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (example _{2) d 4 -2', 6} ', 4- trifluoro -
Synthesis of 4 '-[2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (No. 12 in Table 1)
Compound of 0.6) Magnesium (0.6 g) is suspended in THF (5 ml), and 1-bromo-4-fluorobenzene (3.8 g) in THF (25 ml) is suspended.
The solution was added dropwise at a rate followed by gentle reflux. After the dropping was completed, the mixture was further stirred for 1 hour at room temperature. It was filtered off excess magnesium, which d _{4-3,5-difluoro} obtained in Reference Example 6 1- [2- (trans-4-pentylcyclohexyl) ethyl] -4-iodobenzene 5.3g and Dichloro [1,2-bis (diphenylphosphino) ethane] nickel (II) 0.1 g in THF 35 ml solution 30
Dropped in minutes. After completion of the dropping, the mixture was heated under reflux for 6 hours and allowed to cool to room temperature. 50 ml of 10% hydrochloric acid was added, and hexane 10 was added.
It was extracted with 0 ml and washed successively with water and saturated saline. The extract was dried over anhydrous sodium sulfate, the solvent was distilled off, the residue was purified by silica gel column chromatography (hexane), recrystallized from ethanol and d ₄ -2 ', 6', 4-trifluoro-4 '-[. 5.5 g of white crystals of 2- (trans-4-pentylcyclohexyl) ethyl] biphenyl
I got The phase transition temperatures are summarized in Table 1.

The following compounds were obtained in the same manner. _{d 4 -2 ', 6',} 4- trifluoro-4 '- [2-
(Trans-4-ethyl-cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 4- trifluoro-4 '- [2-
(Trans-4-propyl cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,4- tetrafluoro-4'
[2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,4- tetrafluoro-4'
[2- (trans-4-propyl cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,4- tetrafluoro-4'
[2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (a mixture of No.11 in Table _{1) d 4 -2 ', 6'} , 3,4,5- pentafluoro-4 '
- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,4,5- pentafluoro-4 '
- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,4,5- pentafluoro-4 '
- (a mixture of No.10 in Table 1) [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2 ', 6'-difluoro-4-trifluoromethoxy-4' - [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2 ', 6'-difluoro-4-trifluoromethoxy-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ' , 6'-difluoro-4-trifluoromethoxy-4 '- (a mixture of No.13 in table 1) [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ -2', 6 ', 3-trifluoromethyl-4-trifluoromethoxy-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl _{d 4 -2', 6 ',} 3- trifluoro-4-triflate Ruorometokishi -4 '- [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl _{d 4 -2', 6 ',} 3- trifluoro-4-trifluoromethoxy-4' - [2- (trans-4- pentylcyclohexyl) ethyl] biphenyl _{d 4 -2 ', 6',} 3,5- tetrafluoro-4-trifluoromethoxy-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ -2' , 6 ', 3,5-tetrafluoro-4-trifluoromethyl-methoxy-4' - [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d ₄ -2 ', 6', 3,5-tetrafluoro - 4-trifluoromethoxy-4 '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (example 3) d _{4-2-fluoro-4'-propyl} -
4- [2- (trans-4-propylcyclohexyl)
Synthesis d _{4-2-fluoro-4-} [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl 3.24g ethyl] biphenyl (mixture No.9 in Table 1) was dissolved in dichloromethane 10 ml. To this, 1.93 g of anhydrous aluminum chloride was added and ice-cooled. A solution of 1.45 g of propanoic acid chloride in 5 ml of dichloromethane was added dropwise thereto while being careful not to let the internal temperature exceed 10 ° C.
Stirred for hours. It was poured into ice water, extracted with hexane, and washed with water. D _4-2-fluoro obtained by distilling off the solvent -
3.5 g of a crude product of 4′-propanoyl-4- [2- (trans-4-propylcyclohexyl) ethyl] biphenyl was suspended in 30 ml of diethylene glycol. While adding 3.0 ml of hydrazine dihydrate and 3.0 g of potassium hydroxide to remove distilled water out of the system, 90
The mixture was heated and stirred at -100 ° C for 2 hours and then at 140-150 ° C for 2 hours. After allowing to cool, the mixture was poured into water, neutralized with diluted hydrochloric acid, extracted with hexane, and washed with water and then saturated saline. The solvent crude product obtained was distilled off and purified by column chromatography (hexane) and then recrystallized from ethanol, d _{4-2-fluoro-4'-propyl-4-}
2.0 g of white crystals of [2- (trans-4-propylcyclohexyl) ethyl] biphenyl were obtained.

In the same manner, the following compound was obtained. d _{4-2-fluoro-4'-propyl-4-} [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-propyl-4-} [2- (trans-4- propyl cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-propyl-4-} [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-ethyl-4-} [2 - (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-ethyl-4-} [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-} ethyl-4- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-butyl-4-} [2- (trans-4 - ethyl cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-butyl-4-} [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl d _{4-2-fluoro-4'-butyl-4-} [ 2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (example 4) d ₄ -4-cyano-4 '- [2- synthesis d ₄ 4 of (trans-4-propyl cyclohexyl) ethyl] biphenyl [ 4.0 g of 2- (trans-4-propylcyclohexyl) ethyl] biphenyl was dissolved in 20 ml of dichloromethane, 3.6 g of anhydrous aluminum chloride was added, and the mixture was ice-cooled. 2.9 g of oxalic acid dichloride dissolved in 5 ml of dichloromethane was added dropwise with care so that the internal temperature did not exceed 10 ° C. After stirring for 1 hour under ice cooling, the mixture was poured into diluted hydrochloric acid and ice and extracted with dichloromethane. This dichloromethane solution was added dropwise to 50 ml of 29% ammonia water at 10 ° C or lower under ice cooling. After stirring for 1 hour at 5 to 10 ° C, the precipitated crystals were collected by filtration, dried under reduced pressure and d ₄ -4 '-[2-
4.5 g of crude crystals of (trans-4-propylcyclohexyl) ethyl] biphenyl-4-carboxylic acid amide were obtained.

The total amount was suspended in 20 ml of toluene, 10 ml of thionyl chloride was added, and the mixture was heated with stirring under reflux for 1 hour. After allowing to cool, water was added and the mixture was stirred, and the organic layer was separated. The aqueous layer was extracted with toluene, the organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (toluene) and recrystallized from ethanol to give d ₄
2.2 g of -4-cyano-4 '-[2- (trans-4-propylcyclohexyl) ethyl] biphenyl was obtained.

The following compounds were obtained in the same manner. d _4-4-cyano-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-cyano-4' - [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl d ₄ 2'-fluoro-4-cyano-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2'-fluoro-4-cyano-4'} - [2- (trans-4- propyl cyclohexyl) ethyl] biphenyl d _{4-2'-fluoro-4-cyano-4} '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (example 5) d _{4-2'-fluoro-4-} Chloro-
Synthesis of 4 '-[2- (trans-4-propylcyclohexyl) ethyl] biphenyl (mixture of No. 7 in Table 1)

[0087]

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3.1 g of d ₄ 2-fluoro-4- [2- (trans-4-propylcyclohexyl) ethyl] biphenyl was added to 15 ml of acetic acid and 10 ml of concentrated nitric acid, and 8
The mixture was heated and stirred at 0 to 90 ° C for 1 hour. Cooled to room temperature, poured into water, d _{4-2-fluoro-4'-nitro-4-obtained} The precipitated crystals were collected by filtration total amount of [2- (trans-4-propyl cyclohexyl) ethyl] biphenyl Is dissolved in 15 ml of ethanol and palladium carbon (5%)
0.5 g and 15% hydrochloric acid 1 ml were added, and the mixture was stirred under a hydrogen atmosphere for 3 hours. The catalyst was filtered off, poured into an aqueous sodium hydrogen carbonate solution, extracted with toluene, and washed with water and saturated brine. Purification by silica gel column chromatography (dichloromethane) d _{4-2'-fluoro-4-amino-4} '- to give the 2- (trans-4-propyl cyclohexyl) ethyl] biphenyl 1.3 g. This is 3
The mixture was cooled to 0 ° C. in 5 ml of 5% hydrochloric acid, and a 1 ml aqueous solution of 0.3 g of sodium nitrite was slowly added to diazotize. This was slowly added dropwise to a solution of separately prepared 0.5 g of copper (I) chloride in 3 ml of 35% hydrochloric acid. It was poured into water, extracted with dichloromethane, washed with water and then with saturated saline, and dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by column chromatography (hexane) and recrystallized from ethanol to give d ₄ -2'-fluoro-4-chloro-.
0.7 g of crystals of 4 '-[2- (trans-4-propylcyclohexyl) ethyl] biphenyl were obtained.

The following compounds were obtained in the same manner. d _{4-2'-fluoro-4-chloro-4} '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d _{4-2'-fluoro-4-chloro-4'} - [2- (trans - 4-pentylcyclohexyl) ethyl] biphenyl d ₄ 4-chloro-4 '- [2- (trans-4-ethyl-cyclohexyl) ethyl] biphenyl d ₄ 4-chloro-4' - [2- (trans-4- propyl cyclohexyl) ethyl] d ₄ 4-chloro-4-biphenyl '- [2- (trans-4-pentylcyclohexyl) ethyl] biphenyl (example 6) nematic having a composition of preparation (1) the following liquid crystal composition Host liquid crystal (M)

[0090]

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(In the formula, the cyclohexane ring represents a trans configuration.) Shows a nematic (N) phase at 54.5 ° C. or lower. A mixed liquid crystal (M-1) comprising 90% by weight of this host liquid crystal (M) and 10% by weight of the mixture of (No. 1) in Table 1 obtained in Example 1 was prepared. This mixed liquid crystal (M-
The upper limit temperature (T _NI ) of the N phase in 1) was 52.0 ° C.

Further, a mixture 10 of 90% by weight of the host liquid crystal (M) and (No. 11) in Table 1 obtained in Example 2 was used.
A mixed liquid crystal (M-11) consisting of wt% was prepared. The T _NI of this mixed liquid crystal (M-11) was 55.2 ° C.

When these mixed liquid crystals were stored at 0 ° C., no crystal precipitation could be observed even after 2 weeks. (Comparative Example 1) 90% by weight of host liquid crystal (M) and (No.
1) corresponding to the mixture but not deuterium substituted (R
-1)

[0094]

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A mixed liquid crystal (M
R-1) was prepared. T of this mixed liquid crystal (MR-1)
_NI was 52.2 ° C. In addition, the host liquid crystal (M) 9
It corresponds to a mixture of 0% by weight and (No. 11), but is not deuterated (R-11).

[0096]

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A mixed liquid crystal (M
R-11) was prepared. The T _{NI of} this mixed liquid crystal is 67.
1 ° C. These mixed liquid crystals were prepared in the same manner as in Example 6,
When stored at 0 ° C., a minute amount of crystals was found to deposit in one week. (Example 7) Preparation of liquid crystal composition (2) Host liquid crystal (N) having the following composition

[0098]

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(In the formula, the cyclohexane ring represents the trans configuration) and showed a nematic phase up to 116.7 ° C. A mixed liquid crystal (N) composed of 85% by weight of this host liquid crystal (N) and 15% by weight of a mixture of (No. 1) in Table 1.
-1) was prepared. The T _{NI of} this mixed liquid crystal is 104.3.
° C. Further, a mixed liquid crystal (N-11) was prepared which was composed of 90% by weight of the host liquid crystal (N) and 10% by weight of the mixture of (No. 11) in Table 1. The T _{NI of} this composition was 111.3 ° C. When these mixed liquid crystals were allowed to stand at 20 ° C., crystal precipitation could not be observed even after standing for 2 weeks. (Comparative Example 2) 85% by weight of host liquid crystal (N) and (R-
1) A mixed liquid crystal (NR-1) consisting of 15% by weight was prepared. The T _{NI of} this mixed liquid crystal was 104.5 ° C. When this mixed liquid crystal was stored at 20 ° C. in the same manner as in Example 7, a minute amount of crystals was observed to deposit in one week.

A mixed liquid crystal (NR-1) composed of 90% by weight of the host liquid crystal (N) and 10% by weight of (R-11).
1) was prepared. The T _{NI of} this mixed liquid crystal is 111.4 ° C.
Met. Further, this mixed liquid crystal was used in the same manner as in Example 7
When stored at 0 ° C., a minute amount of crystals was found to be deposited in 3 days.

Therefore, the liquid crystal composition obtained by adding the deuterium-substituted liquid crystal mixture of the present invention to the conventionally used host liquid crystal is the same as the composition to which the corresponding non-deuterium-substituted compound is added. By comparison, it can be seen that crystals hardly precipitate even at low temperatures, although T _NI hardly changes.

[0102]

INDUSTRIAL APPLICABILITY The mixture of 4- (2-cyclohexyl) ethylbiphenyl derivatives in which the cyclohexane ring is deuterium-substituted, provided by the present invention, is industrially produced from easily available compounds as shown in Examples. Can also be easily manufactured.

Further, the obtained mixture of 4- (2-cyclohexyl) ethylbiphenyl derivatives has a low melting point, and the liquid crystal composition containing it has the characteristic that crystals are hard to precipitate even at low temperatures. Is extremely useful as

Claims (10)

[Claims] 1. A compound of the general formula (I)(Where R¹Represents an alkyl group having 1 to 12 carbon atoms
Then X¹, X^Two, X^ThreeAnd X ^FourAre each independently a hydrogen atom
(H) or a deuterium atom (D), Y¹, Y^Two,
Y^Three, Y^FourAnd Y^FiveAre each independently a hydrogen atom or
Represents an elementary atom, m represents an integer of 0 or 1, and Z represents a flux.
Fluorine atom, chlorine atom, hydrogen atom, cyano group, -R^Two, −
OR^Two, -CF_Three, -OCF_Three, -OCF_TwoH or -OCH
_TwoCF_ThreeAnd R^TwoIs alkyl having 1 to 12 carbon atoms
A group or an alkenyl group having 3 to 12 carbon atoms,
The hexane ring is in the trans configuration. )
Two or more compounds are (1) mutually X¹~ X^FourHeavy in
The number of hydrogen atoms (D) and / or the substitution position is different, and
(2) R¹, M, Y¹, Y^Two, Y^Three, Y^Four, Y^FiveAnd Z
Are represented by the above general formula (I),
Mixtures of two or more of the compounds mentioned. 2. In the general formula (I), R ¹ is a linear alkyl group having 1 to 7 carbon atoms, Z is a fluorine atom,
The mixture according to claim 1, which is a chlorine atom, a cyano group, a linear alkyl group having 1 to 7 carbon atoms or an alkoxyl group, or -OCF ₃ . 3. In the general formula (I), Y ¹ , Y ² and Y
Mixture of claim 2, wherein at least two are fluorine atoms of ^3. 4. In the general formula (I), Y ¹ , Y ² and Y
The mixture according to claim 2, wherein ³ are both hydrogen atoms. 5. In the general formula (I), Y ¹ , Y ⁴ and Z
The mixture according to claim 2, wherein at least one of them is a fluorine atom. 6. The mixture according to claim 3, wherein m is 1 in the general formula (I). 7. The mixture according to claim 3, 4 or 5, wherein m is 0 in the general formula (I). 8. The ratio of the number of deuterium atoms (D) to the total number of X ¹ , X ² , X ³ and X ^{4 in} a mixture composed of two or more compounds represented by general formula (I). 30-95
8. The mixture according to claim 1, which is in the range of%. 9. The ratio of the number of deuterium atoms (D) to the total number of X ¹ , X ² , X ³ and X ^{4 in} a mixture of two or more compounds represented by general formula (I). 50-90
8. The mixture according to claim 1, which is in the range of%. 10. A liquid crystal composition comprising a mixture of the general formula (I) according to any one of claims 1 to 9.