JPH07258639A - Phenylbicyclohexane derivative - Google Patents

Abstract

PURPOSE:To obtain a phenylbicyclohexane derivative which includes heavy hydrogen atoms, shows excellent compatibility to other liquid crystal compound and is useful as a material in liquid crystal displays in lowered temperature regions because the derivative causes no crystallization in a lowered temperature range for a long period of time. CONSTITUTION:Two or more kinds of compounds which are represented by the formula [R<1> is a 2-12C alkenyl, a (substituted) 1-7C alkyl; X<1>-X<3> are H, deuterium atom (D) where at least one X is D; Y<1>, Y<2> are H, F; Z is F, Cl, CN, R<2> (R<2> is a 1-12C alkyl, a 2-12C alkenyl), OR<2>, CF3, OCF3, OCF2H, OCH2CF3; the cyclohexane ring has the trans configurationl where the compounds differing in the number and/or the substitution positions of the deuterium atoms (D) in X<1>-X<3>, but being the same in R<1>, Y<1>, Y<2> and Z to one another are formulated to give the object derivative mixture which is useful as a constitution material for liquid crystal displays operating at low temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixture composed of a liquid crystal compound having a deuterium atom, which can improve the characteristics of an electro-optical liquid crystal display material. The present invention relates to a mixture of phenylbicyclohexane derivatives having excellent effects, and further relates to a mixture of cyclohexanone derivatives having a deuterium atom and a mixture of aldehyde derivatives, which are useful as intermediates for producing this mixture.

[0002]

2. Description of the Related Art Liquid crystal display devices have come to be used in watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, 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 system, the conventional static drive has become more common and multiplex drive has become popular.
An active matrix drive using an ansistor) or MIM (Metal-Insulator-Metal) has been put to practical use.

Liquid crystal compositions are required to have various characteristics according to these display systems and drive systems. (1) The liquid crystal phase has a wide temperature range from low temperature to high temperature, and can be driven in a wide temperature range. (2) Low threshold voltage, low voltage driving, and (3) low viscosity and high-speed response are common to all liquid crystal compositions regardless of display method or driving method. It is an important characteristic that is required.

Up to the present, no liquid crystal compound which alone satisfies such required properties is known, and at present, a liquid crystal composition having desired properties is obtained by mixing various liquid crystal compounds. .

Among these, in order to obtain a liquid crystal composition exhibiting a liquid crystal phase in a wide temperature range, a method of mixing various liquid crystal compounds having different temperature regions of the liquid crystal phase is used. When using such a technique, for example, a nematic phase of the liquid crystal composition - isotropic liquid phase transition temperature mixing ratio, the high T _NI point crystal compound when increasing (hereinafter, referred to as T _NI point.) Should be higher. However, such compounds are of a nematic phase lower limit temperature (hereinafter, referred to as T _CN point.) So is high, T _CN point inevitably resulting liquid crystal composition may cause increased, and crystallized at a low temperature deposition In many cases, it cannot be used as a practical liquid crystal composition.

From the above, when preparing a practical liquid crystal composition in which the temperature range of the nematic phase is wide from a low temperature region to a high temperature region, a liquid crystal compound having a low melting point and a nematic phase at room temperature are generally used. The temperature range of the liquid crystal phase is adjusted by empirically mixing 10 to 20 kinds of the liquid crystal compound shown and a compound having a high T _NI point.

However, at the same time as expanding the temperature range, it is necessary to optimize the electro-optical characteristics and the viscosity in accordance with the purpose of use, so that other liquid crystal compounds as constituent components of the liquid crystal composition are It cannot be used unless it satisfies various required properties to some extent, including compatibility with compounds. Therefore, of the many liquid crystal compounds, the selection range of compounds that can be used in preparing a practical liquid crystal composition is considerably limited.

For example, liquid crystal compositions for active matrix driving systems such as TFT and MIM, which are becoming the mainstream of liquid crystal display devices at present, are required to have the above-mentioned characteristics (1) to (3). In addition to the fourth characteristic, it is further required (4) to have a high voltage holding ratio. This is because if the voltage holding ratio of the liquid crystal composition is low, a flicker phenomenon occurs in which the luminance of the pixel that should have been driven changes.

In general, in order to increase the voltage holding ratio of a liquid crystal composition, it must be chemically stable against heat and light in the device and have a high specific resistance value. As a result of various investigations on liquid crystal compounds satisfying such required characteristics, among the compounds conventionally used for TN and STN, liquid crystal compounds having an ester group, a cyano group, a pyrimidine ring, a dioxane ring, or the like have a voltage holding property. It was found to be unsuitable for active matrix as it reduces the rate.

Also, in the active matrix drive system, the display system is the same as the conventional TN display system, and therefore it is essential that the dielectric anisotropy (Δε) of the liquid crystal composition is positive as a whole. However, among the conventionally used liquid crystal compounds having a positive Δε (hereinafter referred to as p-type liquid crystal compounds), those having a relatively large Δε also lower the voltage holding ratio. Was not suitable for active matrix driving.

[0011]

[Chemical 5]

(In the formula, R represents an alkyl group.) Therefore, at present, in order to make Δε of the liquid crystal composition a positive and appropriate value, a compound having a fluoro group or a chloro group as a functional group, for example, Such a p-type liquid crystal compound is used as a material for an active matrix.

[0013]

[Chemical 6]

[0014]

[Chemical 7]

(In the formula, R represents an alkyl group and R'represents an alkyl group, an alkenyl group or an alkoxyalkyl group.) However, these compounds are used to achieve the electro-optical characteristics required for active matrix driving. However, since many liquid crystal compounds used for the active matrix have a relatively high T _NI point, it is very difficult to prepare a liquid crystal composition having a sufficiently low T _CN point.

In order to solve this problem, several homologues having the same skeleton and different from each other in the range of 2 to 7 carbon atoms of the terminal alkyl group are added to the above fluoro compounds. Is used to lower the T _CN point of the liquid crystal composition. However, in this method, the T _CN point does not decrease so much, and the viscosity tends to increase as the number of carbon atoms of the terminal alkyl group increases, so that the response characteristic of the above (3) is deteriorated. I will end up.

As described above, no active liquid crystal composition satisfying all of the above-mentioned characteristics (1) to (4) has been obtained so far, and the liquid crystal composition for active matrix is (2). Priority is given to satisfying the characteristics of (4) to (4), and in the temperature range of (1), even if the T _CN point is not sufficiently low, it is unavoidable to use it. Many are easy to deposit.

In addition to the characteristics (1) to (3) described above, the liquid crystal composition used in the STN liquid crystal display device has a fourth characteristic (5) the elastic constant ratio of the liquid crystal composition ( K ₃₃ / K ₁₁ ) is large, and it is required to achieve high contrast. Further, since the STN display system is often applied to general-purpose devices such as laptop computers, the low threshold voltage of (2) is also an important required characteristic.

In order to lower the threshold voltage of the liquid crystal composition, it is necessary to increase the dielectric anisotropy Δε of the liquid crystal composition or decrease the elastic constant K according to the following formula.

[0020]

[Equation 1]

(In the formula, k represents a proportional constant, V _th represents a threshold voltage, and Δε represents a dielectric anisotropy.) Here, as a liquid crystal compound having a very large Δε, for example, the following formula is used. However, when a large amount of a compound having too large Δε is used, it often causes a problem such as an increase in current value, and when actually used as a liquid crystal display device, there is a problem in reliability. .

[0022]

[Chemical 8]

(In the formula, R represents an alkyl group.) The liquid crystal composition having a small elastic constant has a matrix liquid crystal composed of a p-type liquid crystal compound, a high T _NI point, and a relatively small elastic constant. Tri-ring liquid crystal compound or tri-ring system p of liquid crystal compound having negative Δε (hereinafter referred to as n-type liquid crystal compound)
Formed liquid crystal compounds are prepared by a method of mixing.

As the p-type liquid crystal compound having a large elastic constant ratio K ₃₃ / K ₁₁ , for example, a compound of the following formula is used.

[0025]

[Chemical 9]

(In the formula, R'represents an alkyl group, an alkenyl group or an alkoxyalkyl group, and X represents a hydrogen atom or a fluorine atom.) Therefore, in order to satisfy the threshold voltage characteristic and the contrast characteristic in STN, When such a p-type liquid crystal compound is mixed with the above-mentioned tricyclic p-type or n-type liquid crystal compound, there is a problem that crystals tend to precipitate in a low temperature region. Therefore, as in the case of the active matrix, many kinds of homologues having the same skeleton and different carbon atoms of R ′ are added, or when R ′ is an alkenyl group, the position of the double bond is Are added to reduce the T _CN point of the resulting liquid crystal composition.

However, in such a method, due to the difference in the number of carbon atoms or the position of the double bond,
The value of the elastic constant ratio K ₃₃ / K ₁₁ of the compound also differs greatly, eventually, the elasticity of the liquid crystal composition obtained constant ratio K ₃₃ / K ₁₁
In many cases, and the contrast is often reduced. In addition, the method of adding a homologue has a problem in that the T _CN point can be lowered only in addition to increasing viscosity and slowing the response speed. It is very difficult to design the composition of a product.

At present, although a liquid crystal composition for STN having a low threshold voltage of about 1.2 V is prepared, the elastic constant ratio K ₃₃ / K ₁₁ is as described above. Since it is not large enough, it can be driven at a low voltage and S with high contrast.
No TN liquid crystal display device has been manufactured so far.

As described above, as the liquid crystal composition having a wide temperature range of the liquid crystal phase of the above (1),
Although it is required that the liquid crystal composition has a high T _NI point as well as a low T _CN point, in reality, even if the temperature is higher than the T _CN point, crystals will not be formed if stored in a low temperature region for a long period of time. Since a large number of materials are deposited, a highly reliable liquid crystal display device does not have crystals deposited in the liquid crystal composition for a long period of time even in a low temperature region, and there is no display defect due to environmental temperature change on the entire display screen. Required.

At the T _CN point of the liquid crystal composition, a mixed composition composed of individual liquid crystal simple substances often exhibits a supercooling phenomenon. Therefore, at the T _CN point, the liquid crystal composition is solidified with liquid nitrogen or the like. Crystallization is performed by cooling to a glass state at a sufficiently low temperature (for example, −70 ° C.), and then the transition temperature from the solid to the nematic phase is measured while gradually increasing the temperature, and this is taken as the T _CN point.

However, in the case of a practical liquid crystal composition having 10 to 20 kinds of components, since it is not a eutectic mixture,
Even if the crystal is stored at a temperature higher than the lower limit temperature of the nematic phase based on the above-described measurement, crystals are often precipitated, which eventually narrows the drivable temperature range.

For example, it is not uncommon for crystals to precipitate at room temperature even though the T _CN point is -70 ° C. In addition, as described above, it is required that a nematic phase is stably shown in a wide temperature range from -40 ° C to 110 ° C for in-vehicle use or aircraft use, but -55 ° C.
At present, no liquid crystal composition has been obtained in which crystals do not precipitate even when stored at low temperature. Therefore, even a liquid crystal composition that is actually widely used for in-vehicle use is, for example, -25 ° C.
When stored in, some crystals may precipitate in about one week.

From such an example, the T _{CN of the} liquid crystal composition is also
Even if the point is very low, it does not mean that the crystal does not precipitate at a higher temperature. Therefore, what satisfies the characteristics of (1) above is not that the T _CN point is low, but that the crystal does not grow even in the low temperature region. No precipitation is required for high reliability.

As described above, the liquid crystal composition is prepared by mixing various liquid crystal compounds so as to be adapted to the display system and the driving system. However, the liquid crystal compounds currently used alone can improve the characteristics. Is limited. In particular,
A general-purpose liquid crystal composition is often designed with a focus on satisfying electro-optical characteristics. However, among such general-purpose liquid crystal compositions, particularly TF
In the liquid crystal composition for the active matrix driving system such as T and MIM and the liquid crystal composition for the STN liquid crystal display device, the temperature range of the liquid crystal phase of (1) is wide, and the crystal is formed in the low temperature region. Almost no material has high reliability in practice because it does not precipitate.

A general-purpose liquid crystal composition which substantially satisfies the above-mentioned characteristics (2) to (5) has different temperatures depending on the purpose of use, but crystals are deposited for about one month even if stored at a relatively low temperature. If not, it is recognized as a highly reliable practical liquid crystal.

However, when such a liquid crystal composition is used, the ambient temperature at which the liquid crystal display device using the composition is used is naturally limited. As is clear from the above, it is a highly reliable liquid crystal composition in which crystals do not precipitate even at a lower temperature and sufficiently satisfies the electro-optical characteristics required for various display systems and drive systems. Despite the desire for liquid crystal compositions, such liquid crystal compositions have not yet been obtained.

[0037]

The problem to be solved by the present invention is to show the effect that the problem of crystal precipitation in a low temperature region can be remarkably improved by adding it to a liquid crystal material, and the threshold voltage etc. Another object of the present invention is to provide a liquid crystal material which does not deteriorate the electro-optical characteristics of the above.

[0038]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems. However, there is a limit to the improvement of the characteristics as described above only with the liquid crystal compounds which are currently widely used. . Therefore, the present inventors considered that it is necessary to develop a liquid crystal material that has not been used in general-purpose liquid crystal compositions at all.

Therefore, the present inventors have paid attention to various documents, and among them, regarding the liquid crystal compound having a deuterium atom (D), there have already been reports of several examples as shown below. 1) H. Gasparoux et al., Ann.ReV.Phys.Chem., 27, 175 (1976) 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, 85 (197
1) 8) ET Samulski et al., Phys. Rev. Lett., 29, 340 (1972) 9) H. Zimmermann et al., Liquid Crystals., 4, 591 (1989)

However, in these reports, 4
-Example of replacing hydrogen atom (H) in carboxyl group of alkoxyalkoxybenzoic acid with deuterium atom (D) (Reference (1))
In all the examples except the above, the hydrogen atom (H) in the terminal group was replaced with a deuterium atom (D), or the hydrogen atom (H) bonded to the benzene ring was replaced with a deuterium atom (D). . Moreover, these documents do not describe even an example in which the compound is added to a liquid crystal composition.

Therefore, the present inventors have not reported a hydrogen atom (H) bonded to a saturated hydrocarbon ring, which has not been reported so far.
Was attempted to be replaced by a deuterium atom (D), but it was revealed that the liquid crystal material obtained thereby had excellent properties that could not be predicted at all from the aforementioned literature. .

That is, the present invention has the general formula (I) in order to solve the above problems.

[0043]

[Chemical 10]

(In the formula, R ¹ represents an alkenyl group having 2 to 12 carbon atoms or an alkyl group having 1 to 7 carbon atoms substituted by an alkoxyl group having 1 to 7 carbon atoms,
A linear alkenyl group having 2 to 7 carbon atoms is preferable. X
¹ , X ² and X ³ each independently represent a hydrogen atom (H) or a deuterium atom (D), but at least one is a deuterium atom (D). Y ¹ and Y ² each independently represent a hydrogen atom or a fluorine atom. Z represents a fluorine atom, a chlorine atom, a cyano ^{group, -R 2, -OR 2, -CF} 3, -OCF 3,
-OCF represents ₂ H or -OCH ^₂ CF _3, R ₂ represents an alkyl group or an alkenyl group having 2 to 12 carbon atoms having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a cyano group, a carbon atom Number 1 to 7 straight-chain alkoxyl group or -O
CF ₃ is preferred. Two or more compounds represented by the formula (1) are different from each other in (1) the number and / or substitution position of deuterium atoms (D) in X ^{1 to} X ³ , and (2) R ¹ , Y ¹ , and Y ² are mutually different. And Z are the same,
There is provided a mixture of two or more compounds represented by the general formula (I) (hereinafter referred to as a mixture of the general formula (I)).

Of these, in the general formula (I), R ¹ is a linear alkenyl group having 2 to 7 carbon atoms or a linear alkoxyalkyl group, Z is a fluorine atom, a chlorine atom,
Cyano group, a linear alkyl group having 1 to 7 carbon atoms, a mixture of alkoxyl group, the general formula is a -OCF ₃ or -OCH ₂ CF ₃ (I) are preferred.

Among these, the general formula (I)
And R¹Is a linear alkenyl group having 2 to 7 carbon atoms.
R, Y¹And Y²Are both hydrogen atoms, and Z is -OCF.₃
Wherein R is R in the general formula (I)¹Is carbon
An alkoxyl group having 2 to 7 children, and Y¹, Y²And of Z
A mixture in which at least two of them are fluorine atoms, or
In the general formula (I) is R¹Has 2 to 7 carbon atoms
A linear alkenyl group, Y¹, Y²And less of Z
Mixtures of at least two of which are fluorine atoms are preferred, especially
(A) In the general formula (I), Y¹And Z are both
A prime atom, Y²A mixture in which is a hydrogen atom, or
(B) In the general formula (I), Y¹, Y ²And Z are both
Mixtures of fluorine atoms are preferred.

As mentioned above, the characteristics of the mixture of the general formula (I) of the present invention are that X ¹ , X ² and X in the general formula (I) are characterized.
³ each independently represent a hydrogen atom (H) or a deuterium atom (D), and at least one of them is a deuterium atom (D), and is composed of two or more compounds, and two or more thereof. In the compound of (1), X ^{1 to} X ³ are mutually present.
The number and / or substitution position of deuterium atoms (D) in the above are different, and (2) R ¹ , Y ¹ , Y ² and Z are mutually the same. That is, when R ¹ , Y ¹ , Y ² and Z are fixed in the general formula (I), X ^{1 to} X
Due to differences in the number and / or substitution position of deuterium atoms (D) in ^3, the compounds of general formula (I) will be approximately ten compounds Including stereoisomers can exist.

However, as will be described later, it is not industrially advantageous to selectively produce each of these 10 compounds in the production process, because the production process becomes complicated. Therefore, there is no problem as a liquid crystal material when it is used as a liquid crystal material in the state of a mixture composed of several kinds of compounds of 10 kinds of homologues depending on the number of deuterium atoms (D) and / or the difference in substitution position.

On the contrary, when it is used as a mixture, excellent properties such that crystal precipitation in the low temperature region is hard to occur and the compatibility with other liquid crystal compounds is improved are obtained, rather, it is represented by the general formula (I). It is preferred to use one compound alone.

Among such mixtures of the present invention, the ratio of the number of deuterium atoms (D) in the mixture of two or more compounds represented by the general formula (I) is the same as in the general formula (I). 30 to 95 for the total number of X ^{1 to} X ³
% Mixtures are preferred, 40-90% range is particularly preferred and 60-85% range is most preferred.

The mixtures of general formula (I) according to the invention are
For example, it can be produced via the following intermediates. First, bicyclohexane 4,4′-dione monoethylene acetal is reacted with heavy water (D ₂ O) in the presence of a base in a solvent such as dichloromethane to give a compound of the general formula (IVd)

[0052]

[Chemical 11]

(In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom (H) or a deuterium atom (D), at least one of which is a deuterium atom (D). Represents.)
A mixture of two or more compounds represented by
A mixture of general formula (IVd)) can be obtained. The reaction is suitably carried out at room temperature to the reflux temperature of the solvent, and a metal alcoholate or the like is preferable as the base. Further, in order to accelerate the reaction, it is preferably carried out in the presence of a quaternary salt such as tetrabutylammonium bromide.

[0054]

[Chemical 12]

(In the formula, X ¹ , X ² , X ³ , Y ¹ and Y ² have the same meanings as in formula (I), and Z ′ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, cyano. Group, -R
_{^{2, -OR 2, -CF 3,}} -OCF 3, -OCF 2 H, -O
CH ₂ CF _3, represents a hydrogen atom, -OH or -OCH ₂ Ph, R ² represents an alkyl group or an alkenyl group having 2 to 12 carbon atoms having 1 to 12 carbon atoms, the cyclohexane ring is in trans configuration , M is MgBr, MgCl,
Represents MgI or Li. ) By reacting the mixture of the general formula (IVd) with the organometallic reagent of the general formula (V), and then dehydrating with an acid to give a cyclohexene derivative, hydrogenating this, and further deacetalizing with an acid, Two or more compounds represented by the general formula (III) are (1) different from each other in the number and / or substitution position of deuterium atoms (D) in X ^{1 to} X ³ , and (2) Y ¹ and Y are mutually different. ^A mixture of two or more 4- (4-phenylcyclohexyl) cyclohexanone derivatives in which ² and Z are the same (hereinafter referred to as the mixture of general formula (III)) can be obtained.

However, in the general formula (III), when Z'is a mixture of chlorine atom, bromine atom, iodine atom or cyano group, in general formula (V), Z'is a hydrogen atom. (Vh)

[0057]

[Chemical 13]

(Wherein Y ¹ and Y ² have the same meanings as in the general formula (I), and M has the same meaning as described above), and Z ′ in the general formula (III) is used. Is a hydrogen atom in the general formula (IIIh)

[0059]

[Chemical 14]

(Wherein Y ¹ , Y ² , X ¹ , X ² and X ³ have the same meanings as in formula (I)), a nitration followed by reduction is obtained. , The general formula (II
In formula (III), Z ′ in I) is —NH _2.

[0061]

[Chemical 15]

A compound of the formula (Y ¹ , Y ² , X ¹ , X ^2, X ³ and X ³ has the same meaning as in formula (I)), followed by diazo decomposition. You can

In the general formula (III), Z'is --OH.
Is a general formula (IIIo)

[0064]

[Chemical 16]

When a mixture of the formulas (wherein Y ¹ , Y ² , X ¹ , X ² and X ³ have the same meanings as in formula (I)) is obtained, in formula (V), Z'is -OCH
General formula (Vm) which is ₃

[0066]

[Chemical 17]

(Wherein Y ¹ and Y ² have the same meanings as in the general formula (I), and M has the same meaning as described above).
In the general formula (IIIm), wherein Z ′ is —OCH _3.

[0068]

[Chemical 18]

A compound of the formula (Y ¹ , Y ² , X ¹ , X ² and X ³ has the same meaning as in formula (I)) is obtained and demethylated to obtain a mixture. be able to. (Hydrobromic acid, trimethylsilyl iodide, boron tribromide, aluminum chloride, etc. can be used.) Alternatively, the mixture of the general formula (IIIo) can be used as the general formula (V).
In the general formula (Vb), Z ′ is —OCH ₂ Ph.

[0070]

[Chemical 19]

It can also be obtained by using a mixture of the formula (Y ¹ and Y ² have the same meanings as in the general formula (I), and M has the same meaning as described above).

In the general formula (III), Z'is -OR.
^When a mixture of ² is obtained, the mixture of the general formula (IIIo) is added to the compound of the general formula (a) in the presence of a base.

[0073]

[Chemical 20] R²-W (a) (In the formula, R²Means the above meaning, W is chlorine atom, odor
Elemental atom, iodine atom or p-toluenesulfonyloxy group
Represents a leaving group such as. ) By reacting with a compound of
Can be obtained. In particular, R²Is an alkenyl group
This method is desirable. In addition, in the general formula (III)
Z'is -OCH ₂CF₃For a mixture of
You can

In the general formula (III), Z'is --OC.
In order to obtain a mixture which is F ₂ H, the general formula (III
It can be obtained by converting the mixture of o) into a formate ester and then reacting it with a fluorinating agent such as diethylaminosulfur trifluoride (DAST).

The general formula (III) thus obtained is
A mixture of cyclohexanone derivatives of the general formula (VI
a)

[0076]

Embedded image The step of reacting with a Wittig reagent of CH ₃ OCH = PPh ₃ (VIa) and then acid-treating is repeated (m + 1) times to give a compound of the general formula (II)

[0077]

[Chemical formula 22]

(Wherein Y ¹ , Y ² , X ¹ , X ² and X ³ have the same meanings as in the general formula (I), Z ′ has the same meaning as in the general formula (V), and m Represents an integer of 0 to 10, and the cyclohexane ring has a trans configuration.
(1) The number and / or substitution position of deuterium atoms (D) in X ^{1 to} X ³ are different from each other, and (2) m is mutually,
A mixture of two or more compounds having the same Y ¹ , Y ² and Z (hereinafter referred to as the mixture of the general formula (II)) is obtained. Alternatively, instead of reacting the compound of the general formula (VIa) three times, the compound of the general formula (VIb)

[0079]

[Chemical formula 23]

The Wittig reactant of (1) may be reacted. The mixture of the general formula (II) thus obtained is added with the general formula (VIc)

Embedded image _{^{R 4 CH = PPh 3 (VIc}} ) ( wherein, R ⁴ is a hydrogen atom or a carbon atoms (. Representing a 12-m) an alkyl group) by reacting a Wittig reagent of the general Formula (Ia)

[0081]

[Chemical 25]

(Wherein Y ¹ , Y ² , X ¹ , X ² , X ³ and Z
Represents the same meaning as in formula (I), and m and R
⁴ has the same meaning as described above, and the cyclohexane ring has a trans configuration. ) Can be obtained.

In the obtained mixture of the general formula (Ia), the terminal alkenyl group is usually a cis isomer when R ⁴ is other than a hydrogen atom, but this is isomerized to the trans isomer by benzenesulfinic acid or the like. It is possible.

General formula (VII) obtained by reducing the mixture of general formula (II) with lithium aluminum hydride, sodium borohydride or the like.

[0085]

[Chemical formula 26]

(Wherein Y ¹ , Y ² , X ¹ , X ² , X ³ and Z
Represents the same meaning as in formula (I), and m and R
⁴ has the same meaning as described above, and the cyclohexane ring has a trans configuration. ) An alcohol derivative represented by
General formula

[0087]

Embedded image By reacting with a compound represented by R ⁵ —W (wherein R ⁵ represents an alkyl group having 1 to 7 carbon atoms, and W has the same meaning as described above) in the presence of a base. , The general formula (I
b)

[0088]

[Chemical 28]

(Wherein Y ¹ , Y ² , X ¹ , X ² , X ³ and Z
Represents the same meaning as in formula (I), and m and R
⁵ has the same meaning as described above, and the cyclohexane ring has a trans configuration. ), That is, a mixture in which R ¹ is an alkoxylalkyl group in the general formula (I) can be obtained.

[0090]

[Chemical 29]

(In the formula, R ¹ , Y ¹ , Y ² , Z, X ¹ , X ² and X ³ have the above-mentioned meanings.) General formula (I) of the present invention
In the case of obtaining a mixture of Z, which is a chlorine atom, a fluorine atom, etc., the mixture represented by the general formula (Ih) in which Z is a hydrogen atom in the general formula (I) is nitrated and then reduced to give the general formula It can also be obtained by using an aniline derivative of (In) and subjecting it to diazo decomposition.

Further, in the general formula (I), when a mixture of Z is a cyano group is obtained, a corresponding derivative in which Z is a bromine atom or an iodine atom is reacted with Cu ₂ (CN) ₂ , or After acetylating the mixture represented by the general formula (Ih), the compound is oxidized with hypochlorite or hypobromite to give a benzoic acid derivative, which is converted to an acid chloride with a chlorinating agent such as thionyl chloride. It can also be obtained by reacting to give an amide derivative and then dehydrating.

In the general formula (I), when a mixture of Z such as R ² is obtained, a corresponding derivative in which Z is a bromine atom or an iodine atom is used as a Grignard reagent or an organometallic reagent such as a phenyllithium derivative. After that, it can also be obtained by reacting with the compound of the above-mentioned general formula (a) in the presence of a copper-based catalyst or the like.

In the general formula (I), Z is -OR ² ,-.
In order to obtain a mixture which is OCF ₂ H or -OCH ₂ CF ₃ is represented by the general formula Z is -OCH ₃ (Im)

[0095]

[Chemical 30]

(Wherein R ¹ , Y ¹ , Y ² , X ¹ , X ² and X ³
Represents the same meaning as in formula (I). Or a compound of the general formula (Ij) in which Z is —OCH ₂ Ph.

[0097]

[Chemical 31]

(Wherein R ¹ , Y ¹ , Y ² , X ¹ , X ² and X ³
Represents the same meaning as in formula (I). It can also be obtained in the same manner as in the case of the mixture of the general formula (III).

The general formula (I
The deuterium-substituted mixtures of I), (III) and (IVd) are also novel and the present invention also provides these mixtures.
In the mixture of the general formula (IVd), X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom (H) or a deuterium atom (D) as described above. As is clear from the method, in the general formula (III), ^one of X ^{1 to} X ⁴ in the general formula (IVd) is lost during dehydration, and hydrogenation results in a hydrogen atom (H). Will be replaced by. At this time, since there is no distinction between X ^{1 to} X ^4, it may be considered that X ⁴ is eliminated and replaced with a hydrogen atom (H) for convenience. In addition, the general formula (IV
In the step from d) to the mixture of general formula (II),
It is not considered that the deuterium atom (D) is replaced with the hydrogen atom (H).

Further, among such a mixture of the general formula (I) of the present invention, in two or more compounds represented by the general formula (I), deuterium atoms (D) with respect to the total number of X ^{1 to} X ⁴ are included. A mixture having a number ratio of 30 to 95% is preferable because it can exhibit a more excellent effect, but each of the formula (II), (III) or (IVd) is preferable. Also in the mixture, in the two or more compounds represented by each general formula, X ^{1 to} X ³ or X ¹ to
The ratio of the number of deuterium atoms (D) to the total number of X ⁴ is 3
Mixtures in the range of 0-95% are preferred, especially 40-
The range of 90% is preferable, and the range of 60 to 85% is the most preferable.

Typical examples of the thus obtained mixture of two or more compounds represented by the general formula (I) are shown in Table 1 below together with their phase transition temperatures.

[0102]

[Table 1]

(In the table, Cr represents a crystalline phase, Sm represents a smectic phase, N represents a nematic phase, and I represents an isotropic liquid phase. In addition, () indicates a monotropic phase. The transition temperature represents a transition temperature between the phases on the left and right sides of the numeral, for example, C44 N represents a transition temperature between the crystalline phase and the nematic phase of 44 ° C. Further, D-formation The ratio indicates the ratio of the number of deuterium atoms (D) to the total number of X ^{1 to} X ⁴ in the mixture.) This mixture of two or more compounds of the general formula (I) is deuterium. Compared with a single compound which is not substituted but has the same skeleton, it has an excellent feature that crystals are not precipitated even in a low temperature region.

As such an example, a matrix liquid crystal (A) which is widely used at present is used.

[0105]

[Chemical 32]

(Wherein, the cyclohexane ring represents the trans configuration and "%" represents "% by weight"), and 85% by weight of the base liquid crystal (A) and (No. 1) in Table 1.

[0107]

[Chemical 33]

A mixed liquid crystal (M) consisting of 15% by weight of the mixture of was prepared and stored at -20 ° C.
No precipitation of crystals was observed even after a lapse of months. On the other hand, the same base liquid crystal (A) 85% by weight, and (No. 1)
Of the formula (R-1) having a structure similar to that of but having no deuterium substitution.

[0109]

[Chemical 34]

A mixed liquid crystal (M
R) was prepared and stored in the same manner at −20 ° C.,
Crystallization was observed after 10 days. From this,
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 useful for preparing a practical liquid crystal material. It can be understood that it is extremely useful.

[0111]

EXAMPLES The present invention will be further described below by showing Examples of 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" (manufactured by JEOL Ltd., 400 MHz ¹ H) was used.

[0113] Incidentally, noted before the compound names and structural formulas "d ₃ -" in the formula (I), of the substituents of X ¹ to X ^3, at least one deuterium atom (D) Is a mixture of the compounds Also, "d ₄
- "in formula (II), the substituents of X ¹ to X ^4, indicating that a mixture of at least one is made of compounds which are deuterium atoms (D).

Example 1 Bicyclohexane-4,
Deuteration of 4'-dione monoethylene acetal

[0115]

[Chemical 35]

54.0 g of sodium methoxide was dissolved in 100 ml of heavy water (D conversion rate: 99.8%). Bicyclohexane-4,4'-dione monoethylene acetal 100.2 dissolved in 100 ml of dichloromethane was added thereto.
g, and then tetrabutylammonium bromide 2.0 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 reaction product of the aqueous layer was extracted with dichloromethane and then collected. The organic layer was combined with this, washed with water, and dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off, d ₄ - was obtained bicyclohexane-4,4'-dione monoethylene acetal 100.5 g. When the D conversion rate was measured by NMR, it was about 86%.

Example 2 d ₃ -4- [trans-4
Synthesis of-(3,4-difluorophenyl) cyclohexyl] cyclohexanone

[0118]

[Chemical 36]

Magnesium 11.0 in 50 ml THF
1 g dissolved in 300 ml of THF under a nitrogen atmosphere 1-
Bromo-3,4-difluorobenzene (81.2 g) was added dropwise at a rate at which the solvent continued to gently reflux. After completion of dropping, the mixture was further stirred for 1 hour to prepare a Grignard reaction agent. This was ice-cooled to 10 ° C. or lower, and d ₄ -bicyclohexane-4,4′-dione monoethylene acetal 9 obtained in Example 1 was used.
A solution of 1.4 g of THF in 270 ml was added dropwise with care so that the internal temperature did not exceed 20 ° C. After stirring at room temperature for 1 hour, water and then dilute hydrochloric acid were added for neutralization. The reaction product was extracted with ethyl acetate, and the organic layer was washed with water and saturated saline. After dehydration over anhydrous sodium sulfate and drying, the solvent was distilled off.

The total amount of the obtained residue is 500 ml of toluene.
Was dissolved in water, 5.2 g of potassium hydrogensulfate was added, and the mixture was heated under reflux for 3 hours while removing distilled water with stirring. After adding 5 ml of ethylene glycol and heating and stirring for 1 hour, the mixture was allowed to cool to room temperature. The extract was washed with water, a saturated aqueous solution of sodium hydrogencarbonate, water and then saturated saline, and dehydrated and dried over anhydrous sodium sulfate. Crude crystals obtained by distilling off the solvent 14
0 g was recrystallized from ethanol for purification, and d ₃ -3,4
-Difluoro-1- [4- [4- (1,3-dioxolan-2-yl) cyclohexyl] cyclohexene-1-
Ill] benzene was obtained (95.6 g). The whole amount was added to the autoclave and dissolved in 500 ml of ethyl acetate. To this, 9.6 g of palladium carbon was added, and the hydrogen pressure was 3 Kg /
The mixture was stirred at cm ² for 3 hours at room temperature. The catalyst was removed by celite filtration, and the solvent was distilled off under reduced pressure, d _3-3,4-
Difluoro-1- [trans-4- [4- (1,3-dioxolan-2-yl) cyclohexyl] cyclohexyl] benzene and d _{3-3,4-difluoro-1-} [cis-4- [4- (1 , 3-Dioxolan-2-yl) cyclohexyl] cyclohexyl] benzene 56/44
96 g of a mixture was obtained. This is dimethylformamide (D
MF) dissolved in 280 ml and potassium t-butoxide 1
5.9g was added and it was made to react at 80 degreeC for 3 hours. The mixture was returned to room temperature, neutralized with diluted hydrochloric acid, and the reaction product was extracted twice with toluene. The toluene layer was washed with water and then with saturated saline, dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Which was recrystallized from ethanol, d ₃ -3,
4-difluoro-1- [trans-4- [4- (1,3
85.3 g of -dioxolan-2-yl) cyclohexyl] cyclohexyl] benzene were obtained. Dissolve the whole amount in 400 ml of toluene and 200 ml of formic acid,
Stir for hours. After allowing to cool, water was added, the organic layer was separated, and washed with saturated aqueous sodium hydrogen carbonate solution, water, and then saturated brine. The solvent was recrystallized from ethanol to crude crystals obtained by distilling off the, d ₃ -4- [trans-4- (3,4
76.3 g of -difluorophenyl) cyclohexyl] cyclohexanone were obtained.

Example 3 d ₃ -4- [trans-4]
Synthesis of-(3,4,5-trifluorophenyl) cyclohexyl] cyclohexanone

[0122]

[Chemical 37]

In Example 2, 1-bromo-3,4-
1-Bromo-3,4,5 instead of difluorobenzene
- except for using trifluorobenzene in the same manner as in Example 2 to obtain a d ₃ -4- [trans-4- (3,4,5-trifluorophenyl) cyclohexyl] cyclohexanone.

Example 4 d ₃ -4- [trans-4
Synthesis of-(4-trifluoromethoxyphenyl) cyclohexyl] cyclohexanone

[0125]

[Chemical 38]

In Example 2, 1-bromo-3,4-
Instead of difluorobenzene, 1-bromo-4-except for using trifluoromethoxy benzene in the same manner as in Example 2, d ₃ -4- [trans-4- (4-trifluoromethoxyphenyl) cyclohexyl] cyclohexanone Got

Example 5 d ₃ -trans-4′-
Synthesis of (3,4-difluorophenyl) bicyclohexane-trans-4-carbaldehyde

[0128]

[Chemical Formula 39]

15.2 g of methoxymethyltriphenylphosphonium chloride was added to 15 ml of THF and 45 ml of toluene.
And was cooled with ice. Add t-butoxy potassium 5.
A Wittig reaction agent was prepared by adding 5 g in two batches so that the internal temperature did not exceed 5 ° C. After stirring for 1 hour, d ₃ -4- [trans-4- obtained in EXAMPLE 2 (3,4
Dissolve 11.5 g of difluorophenyl) cyclohexyl] cyclohexanone in 25 ml of toluene to give an internal temperature of 1
It was added dropwise at 0 ° C or lower. After stirring for another hour, 50m of water
1 was added and neutralized with a small amount of dilute hydrochloric acid. The organic layer was concentrated under reduced pressure, 50 ml of hexane was added, and the precipitated crystals were separated by filtration. The filtrate was washed with a water / methanol mixed solvent and the solvent was distilled off to obtain 14.2 g of an intermediate enol ether compound.
Got The whole amount was dissolved in 30 ml of THF, the same amount of dilute hydrochloric acid was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction product was extracted with ethyl acetate, dehydrated and the solvent was distilled off. It was dissolved in 50 ml of ethanol, a 20% aqueous solution of sodium hydroxide was added dropwise, and the mixture was stirred for 2 hours. 30 ml of water was added, the reaction product was extracted with toluene, and the organic layer was washed with water.
The solvent was distilled off under reduced pressure, and d ₃ -trans-4′-
11.0 g of (3,4-difluorophenyl) bicyclohexane-trans-4-carbaldehyde was obtained.

Example 6 d ₃ -trans-4′-
Synthesis of (3,4,5-trifluorophenyl) bicyclohexane-trans-4-carbaldehyde

[0131]

[Chemical 40]

D _3- [trans-4- (3,4,5-trifluorophenyl) cyclohexyl] cyclohexanone obtained in Example 3 was used in the same manner as in Example 5 except that d _3- Trans-4 ′-(3,4,5-trifluorophenyl) bicyclohexane-trans-4-
Got Carbal Dehide.

Example 7 d ₃ -trans-4′-
Synthesis of (4-trifluoromethoxyphenyl) bicyclohexane-trans-4-carbaldehyde

[0134]

[Chemical 41]

[0135] except for using the d ₄ 4- [trans-4- (4-trifluoromethoxyphenyl) cyclohexyl] cyclohexanone obtained in Example 4 in the same manner as in Example 5, d ₃ - trans-4 '-(4-Trifluoromethoxyphenyl) bicyclohexane-trans-4-
Got Carbal Dehide.

Example 8 d ₃ -trans-4′-
Synthesis of (3,4,5-trifluorophenyl) bicyclohexane-trans-4-propanal

[0137]

[Chemical 42]

11.1 g of 3- (1,3-dioxolan-2-yl) propyltriphenylphosphonium bromide was suspended in 40 ml of toluene and 20 ml of THF. This was ice-cooled to 5 ° C or lower, and 2.8 g of potassium t-butoxide was added at an internal temperature of 5 ° C or lower to prepare a Wittig reaction agent. D ₃ -4- obtained in Example 3 to [trans-4-
5.2 g of (3,4,5-trifluorophenyl) cyclohexyl] cyclohexanone was dissolved in 10 ml of toluene, and the solution was added dropwise so that the internal temperature did not exceed 10 ° C. and reacted for 1 hour. 30 ml of water was added and neutralized with a small amount of dilute hydrochloric acid. The organic layer was concentrated under reduced pressure, 30 ml of hexane was added, and the precipitated crystals were separated by filtration. The filtrate was washed with a water / methanol mixed solvent and the solvent was distilled off to obtain 8.8 g of a crude product.
Was purified by silica gel column chromatography (hexane / ethyl acetate = 4/1), and recrystallized from ethanol to give an intermediate d ₃ -3- [4- [trans-4- (3,4. 5.5 g of 5,5-trifluorophenyl) cyclohexyl] cyclohexylidene] propanal ethylene acetal were obtained. Toluene 80m
1 and triethylamine (6 ml), palladium carbon (1.1 g) was added, and the mixture was reacted under a hydrogen pressure of 3 atm for 4 hours.
The catalyst was filtered off, washed with diluted hydrochloric acid and then with water, and the solvent was distilled off under reduced pressure to obtain 5.3 g of crude crystals (cyclohexane ring is a mixture of trans / cis of about 8/2). Recrystallized from a toluene / ethanol mixed solvent to give d ₃ -trans-4 ′-(3,4,5-trifluorophenyl)
Bicyclohexane-trans-4-propanal ethylene acetal (3.9 g) was obtained. Toluene 25
This was dissolved in ml, 7 ml of formic acid was added, and the mixture was stirred for 4 hours at room temperature. Water was added, the organic layer was separated, washed with an aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous sodium sulfate. The solvent was distilled off, d ₃ - trans-4 '- (3,
3.4 g of 4,5-trifluorophenyl) bicyclohexane-trans-4-propanal was obtained.

Example 9 d ₃ -trans-4′-
Synthesis of (3,4-difluorophenyl) bicyclohexane-trans-4-propanal

[0140]

[Chemical 43]

[0141] except for using the d ₃ -4- [trans-4- (3,4-difluorophenyl) cyclohexyl] cyclohexanone obtained in Example 2 in the same manner as in Example 8, d ₃ - trans-4 '-(3,4,5-Trifluorophenyl) bicyclohexane-trans-4-propanal was obtained.

[0142] (Example 10) d ₃ - trans-4'
Synthesis of (4-trifluoromethoxyphenyl) bicyclohexane-trans-4-propanal

[0143]

[Chemical 44]

[0144] except for using the d ₃ -4- [trans-4- (trifluoromethoxy) cyclohexyl] cyclohexanone obtained in Example 4 in the same manner as in Example 8, d ₃ - trans-4' (4-Trifluoromethoxyphenyl) bicyclohexane-trans-4-propanal was obtained.

[0145] (Example 11) d ₃ - trans-4'
Ethenyl-trans-4- (3,4-difluorophenyl) bicyclohexane (mixture of No. 1 in Table 1)
Synthesis of

[0146]

[Chemical formula 45]

Methyltriphenylphosphonium iodide 1
3.3 g was suspended in 50 ml of toluene and 14 ml of THF, and ice-cooled to 5 ° C or lower. 4.0 g of potassium t-butoxide was added, and the mixture was stirred for 1 hour to prepare a Wittig reaction agent. In addition to this, d ₃ -trans-obtained in Example 5
A solution of 7.5 g of 4 '-(3,4-difluorophenyl) bicyclohexane-trans-4-carbaldehyde in 20 ml of toluene was added dropwise at an internal temperature of 10 ° C or lower, and the mixture was further stirred at the same temperature for 1 hour. After adding 50 ml of water and neutralizing with dilute hydrochloric acid, the organic layer was separated and concentrated under reduced pressure. The obtained residue was dissolved in 50 ml of hexane and the insoluble material was filtered off. The filtrate was washed with a water / methanol mixed solvent, the solvent was distilled off, and 11 g of the crude product obtained was purified by silica gel column chromatography (hexane) to give d ₃ -trans-4′-ethenyl-. 6.7 g of white crystals of trans-4- (3,4-difluorophenyl) bicyclohexane were obtained. The phase transition temperature and the like are summarized in Table 1.

Example 12 d ₃ -trans-4′-
Synthesis of (3-butenyl) -trans-4- (3,4-difluorophenyl) bicyclohexane (mixture of No. 2 in Table 1)

[0149]

[Chemical formula 46]

D ₃ -trans-4 ′ obtained in Example 9
-(3,4-Difluorophenyl) bicyclohexane-
Example 11 except that trans-4-propanal was used
In the same manner as in d ₃ -trans-4 ′-(3-butenyl) -trans-4- (3,4-difluorophenyl)
Bicyclohexane was obtained.

[0151] (Example 13) d ₃ - trans-4'
(3-Methoxypropyl) -trans-4- (3,4-
Difluorophenyl) bicyclohexane (N in Table 1
o. Synthesis of 3)

[0152]

[Chemical 47]

0.5 g of lithium aluminum hydride was added to T
It was suspended in 50 ml of HF. This Example 9 obtained in d ₃ - trans-4 '- (3,4-difluorophenyl) bicyclohexane - and the THF30ml solution of trans-4-propanal 5.0g was slowly added dropwise at room temperature. After completion of dropping, ethyl acetate was added to decompose excess hydride, and then dilute hydrochloric acid was added to precipitate an inorganic substance. The precipitate was decanted, washed with toluene, and the organic layers were combined and dried over anhydrous magnesium sulfate. And the solvent was distilled off under reduced pressure, d _{3-3-[trans-4-} [trans-4-
4.8 g of (3,4-difluorophenyl) cyclohexyl] cyclohexyl] propanol were obtained. The whole amount was dissolved in 20 ml of THF, and this was added dropwise to 0.5 g of sodium hydride suspended in 30 ml of THF. After stirring at room temperature for 2 hours, 5.0 g of methyl iodide was added dropwise,
The mixture was further stirred under heating under reflux for 24 hours. After cooling, water was added to decompose excess hydride and then neutralized with dilute hydrochloric acid. After adding toluene and separating the aqueous layer, most of the THF was distilled off, followed by washing with water and dehydration drying with anhydrous sodium sulfate. The crude product obtained by distilling off the solvent under reduced pressure was purified using silica gel column chromatography (hexane / ethyl acetate = 5/1) to separate unreacted alcohol, and d ₃ -trans-4 was used. '-(3-Methoxypropyl) -trans-4- (3,4-difluorophenyl)
2.3 g of bicyclohexane was obtained. The phase transition temperatures are summarized in Table 1.

[0154] (Example 14) d ₃ - trans-4'
Synthesis of ethenyl-trans-4- (3,4,5-trifluorophenyl) bicyclohexane (mixture of No. 4 in Table 1)

[0155]

[Chemical 48]

D ₃ -trans-4 ′ obtained in Example 6
- (3,4,5-trifluorophenyl) bicyclohexane - except for using trans-4-carbaldehyde in the same manner as in Example 11, d ₃ - trans-4'-ethenyl - trans-4- (3 , 4,5-Trifluorophenyl) bicyclohexane was obtained. The phase transition temperatures are summarized in Table 1.

[0157] (Example 15) d ₃ - trans-4'
(3-butenyl) -trans-4- (3,4,5-trifluorophenyl) bicyclohexane (N in Table 1
o. (Mixture of 5)

[0158]

[Chemical 49]

D ₃ -trans-4 ′ obtained in Example 8
- (3,4,5-trifluorophenyl) bicyclohexane - except for using trans-4-propanal in the same manner as in Example 11, d ₃ - trans-4 '- (3-butenyl) - trans - 4- (3,4,5-Trifluorophenyl) bicyclohexane was obtained. Phase transition temperature is first
It is summarized in the table.

[0160] (Example 16) d ₃ - trans-4'
Synthesis of ethenyl-trans-4- (4-trifluoromethoxyphenyl) bicyclohexane (mixture of No. 6 in Table 1)

[0161]

[Chemical 50]

D ₃ -trans-4 ′ obtained in Example 7
- (4-trifluoromethoxyphenyl) bicyclohexane - except for using trans-4-carbaldehyde in the same manner as in Example 11, d ₃ - trans-4'-ethenyl - trans-4- (3,4, 5-Trifluorophenyl) bicyclohexane was obtained. The phase transition temperatures are summarized in Table 1.

Example 17 d ₃ -trans-4′-
(3-butenyl) -trans-4- (4-trifluoromethoxyphenyl) bicyclohexane (N in Table 1
o. (Mixture of 7)

[0164]

[Chemical 51]

D ₃ -trans-obtained in Example 10
D ₃ -trans-4 ′-(3 was prepared in the same manner as in Example 11 except that 4 ′-(4-trifluoromethoxyphenyl) bicyclohexane-trans-4-propanal was used.
-Butenyl) -trans-4- (3,4,5-trifluorophenyl) bicyclohexane was obtained. The phase transition temperatures are summarized in Table 1.

Example 18 Preparation of Liquid Crystal Composition

[0167]

[Chemical 52]

(Wherein, the cyclohexane ring represents a trans configuration, and "%" represents "% by weight"). A matrix liquid crystal (A) was prepared, and a nematic (N) phase was obtained at 54.5 ° C or lower. showed that.

85% by weight of this host liquid crystal (A) and obtained in Example 11

[0170]

[Chemical 53]

A mixed liquid crystal (M) consisting of 15% by weight of the mixture of was prepared. The maximum temperature of the N phase of this mixed liquid crystal (M) was 62.2 ° C. When this mixed liquid crystal was stored at -20 ° C, no precipitation of crystals was observed even after 1 month.

Comparative Example The same host liquid crystal (A) 85 as the above
% By weight and undeuterated formula (R-1)

[0173]

[Chemical 54]

A mixed liquid crystal (M
R) was prepared. The maximum temperature of the N phase of this mixed liquid crystal is 6
It was 2.3 ° C. Next, when this mixed liquid crystal was stored at −20 ° C., precipitation of crystals was observed after 10 days.

From this, it can be said that the mixture of the general formula (I) of the present invention, when added to a general-purpose host liquid crystal, does not precipitate crystals in the low temperature region as compared with the corresponding compound not deuterium-substituted. It is clear that it has excellent effects. Therefore, a liquid crystal composition having a wider driving temperature range can be easily obtained.

[0176]

INDUSTRIAL APPLICABILITY As shown in the examples, the mixture of the deuterium-substituted compounds represented by the general formula (I) of the present invention can be easily produced industrially from commercially available compounds. It is also possible to have excellent compatibility with other liquid crystal compounds. Therefore, when added to a liquid crystal material that is currently widely used, the T _NI point is not significantly lowered, and the electro-optical characteristics are not reduced,
An excellent effect that crystals are not precipitated even in a low temperature region of 20 ° C. can be obtained. Therefore, it is extremely useful as a constituent material of liquid crystal display devices used in a low temperature region, particularly TN, STN, and active matrix display devices.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 43/21 43/225 C 7419-4H 47/24 47/277 47/457 47/47 49 / 697 49/753 C 9049-4H 255/50 255/54 255/56 C07D 317/72 C09K 19/30 9279-4H 19/52 9279-4H G02F 1/13 500 // C07M 5:00

Claims (31)

[Claims] 1. A compound represented by the general formula (I):(In the formula, R¹Is an alkenyl group having 2 to 12 carbon atoms or
Charcoal substituted with an alkoxyl group having 1 to 7 carbon atoms
Represents an alkyl group having 1 to 7 elementary atoms, X¹, X²And X
³Are each independently a hydrogen atom (H) or a deuterium atom.
(D), at least one of which is a deuterium atom (D)
Represents Y¹And Y²Are each independently a hydrogen atom or
Represents a fluorine atom, Z is a fluorine atom, a chlorine atom, a shear
Group, -R², -OR², -CF₃, -OCF₃, -OCF
₂H or -OCH₂CF₃And R ²Is 1 to 1 carbon atoms
12 alkyl groups or alkenyl having 2 to 12 carbon atoms
Represents a group and the cyclohexane ring is in the trans configuration.
It ) Two or more compounds represented by
X¹~ X³Number and / or substitution of deuterium atoms (D) in
The position is different, and (2) R is mutually¹, Y¹, Y²And 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 alkenyl group having 2 to 7 carbon atoms or a linear alkoxyalkyl group, and Z is a fluorine atom, a chlorine atom, a cyano group or a carbon atom. linear alkyl group or alkoxyl group having 1 to 7, the mixture of claim 1, wherein it is -OCF ₃ or -OCH ₂ CF _3. 3. In the general formula (I), R ¹ is a linear alkenyl group having 2 to 7 carbon atoms, and Y ¹ , Y ² and Z
The mixture according to claim 2, wherein at least two of them are fluorine atoms. 4. The mixture according to claim 3, wherein in the general formula (I), Y ¹ and Z are both fluorine atoms, and Y ² is a hydrogen atom. 5. In the general formula (I), Y ¹ , Y ² and Z
The mixture according to claim 3, wherein both are fluorine atoms. 6. In the general formula (I), R ¹ is a linear alkenyl group having 2 to 7 carbon atoms, Y ¹ and Y ² are both hydrogen atoms, and Z is —OCF _3. Item 2. A mixture according to item 2. 7. The formula (I), wherein R ¹ is an alkoxyalkyl group having 2 to 7 carbon atoms, and at least two of Y ¹ , Y ² and Z are fluorine atoms. blend. 8. The mixture according to claim 7, wherein in the general formula (I), Y ¹ and Z are both fluorine atoms, and Y ² is a hydrogen atom. 9. The ratio of the number of deuterium atoms (D) to the total number of X ¹ , X ² and X ³ in two or more compounds represented by general formula (I) is in the range of 30 to 95%. 9. The mixture according to claim 1, characterized in that 10. The ratio of the number of deuterium atoms (D) to the total number of X ¹ , X ² and X ³ in two or more compounds represented by general formula (I) is in the range of 40 to 90%. 9. The mixture according to claim 1, characterized in that 11. The ratio of the number of deuterium atoms (D) to the total number of X ¹ , X ² and X ³ in two or more compounds represented by formula (I) is in the range of 60 to 85%. 9. The mixture according to claim 1, characterized in that 12. A compound represented by the general formula (II): (In the formula, m represents an integer of 0 to 10, and X ¹ , X ² and X
Each ³ independently represents a hydrogen atom (H) or a deuterium atom (D), but at least one is a deuterium atom (D).
And Y ¹ and Y ² each independently represent a hydrogen atom or a fluorine atom, and Z ′ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, —R ² , —OR ² , or —CF.
_{3, -OCF 3, -OCF 2 H} , -OCH 2 CF 3, represents a hydrogen atom, -OH or -OCH ^₂ Ph, R ₂ is a 2-12 carbon alkyl group or a carbon atom having 1 to 12 carbon atoms Represents an alkenyl group, the cyclohexane ring being in the trans configuration. Two or more compounds represented by the formula (1) are different from each other in the number and / or substitution position of deuterium atoms (D) in X ^{1 to} X ³ , and (2) m, Y ¹ , Y ² and Z
A mixture of two or more compounds represented by the general formula (II). 13. In the general formula (II), at least two of Y ¹ , Y ² and Z are fluorine atoms, and m is 0.
The mixture according to claim 12, which is an integer of ˜2. 14. In the general formula (II), Y ¹ and Z
14. The mixture according to claim 13, wherein both are fluorine atoms, Y ² is a hydrogen atom, and m is 0 or an integer of 2. 15. The mixture according to claim 13, wherein in the general formula (II), Y ¹ , Y ² and Z are all fluorine atoms, and m is an integer of 0 or 2. 16. In the general formula (II), Y ¹ and Y ²
Are both hydrogen atoms, Z is —OCF ₃ , and m is 0.
The mixture according to claim 12, which is an integer of ˜2. 17. The ratio of the number of deuterium atoms (D) in a mixture composed of two or more compounds represented by the general formula (II) is such that the total number of X ¹ , X ² and X ^{3 in} the general formula (II). The mixture according to claims 12 to 16, which is in the range of 30 to 95%. 18. The ratio of the number of deuterium atoms (D) in a mixture composed of two or more compounds represented by general formula (II) is the total number of X ¹ , X ² and X ³ in general formula (II). The mixture according to claims 12 to 16, which is in the range of 40 to 90%. 19. The ratio of the number of deuterium atoms (D) in a mixture of two or more compounds represented by general formula (II) is the total number of X ¹ , X ² and X ³ in general formula (II). The mixture according to claims 12 to 16, which is in the range of 60 to 85%. 20. The general formula (III): (In the formula, X ¹ , X ² and X ³ each independently represent a hydrogen atom (H) or a deuterium atom (D);
Represents a deuterium atom (D), Y ¹ and Y ² each independently represent a hydrogen atom or a fluorine atom, and Z ′ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group,
_{^{R 2, -OR 2, -CF 3}} , -OCF 3, -OCF 2 H, -
OCH ₂ CF _3, represents a hydrogen atom, -OH or -OCH ₂ Ph, R ² represents an alkyl group or an alkenyl group having 2 to 12 carbon atoms having 1 to 12 carbon atoms, the cyclohexane ring is the trans configuration . ) Two or more compounds represented by the formula (1) are different from each other in the number and / or substitution position of deuterium atoms (D) in X ^{1 to} X ³ , and (2) Y ¹ , Y ² and Z are mutually different. A mixture of two or more compounds represented by the general formula (III), which are the same. 21. In the general formula (III), Y ¹ , Y ²
21. The mixture according to claim 20, wherein at least two of Z and Z are fluorine atoms. 22. The mixture according to claim 21, wherein in the general formula (III), Y ¹ and Z are both fluorine atoms, and Y ² is a hydrogen atom. 23. In the general formula (III), Y ¹ , Y ²
22. The mixture according to claim 21, wherein both and Z are fluorine atoms. 24. The mixture according to claim 20, wherein in the general formula (III), Y ¹ and Y ² are both hydrogen atoms, and Z is —OCF ₃ . 25. The proportion of the number of deuterium atoms (D) in the mixture of two or more compounds represented by the general formula (III) is such that X ¹ , X ² and X in the general formula (III).
It is in the range of 30 to 95% with respect to the total number of ^3.
The mixture according to 0 to 24. 26. The proportion of the number of deuterium atoms (D) in the mixture composed of two or more compounds represented by the general formula (III) is X ¹ , X ² and X in the general formula (III).
It is in the range of 40 to 90% with respect to the total number of ^3.
The mixture according to 0 to 24. 27. The proportion of the number of deuterium atoms (D) in the mixture composed of two or more compounds represented by the general formula (III) is X ¹ , X ² and X in the general formula (III).
It is in the range of 60 to 85% with respect to the total number of ^3.
The mixture according to 0 to 24. 28. A compound represented by the general formula (IVd): (In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom (H) or a deuterium atom (D), but at least one represents a deuterium atom (D).) 2 represented by
A mixture of one or more compounds. 29. The proportion of the number of deuterium atoms (D) in the mixture of two or more compounds represented by the general formula (IVd) is X ¹ , X ² , X ³ in the general formula (IVd).
And the total number of X ⁴ is in the range of 30 to 95%. 30. The proportion of the number of deuterium atoms (D) in a mixture composed of two or more compounds represented by general formula (IVd) is X ¹ , X ² , X ³ in general formula (IVd).
And the total number of X ⁴ is in the range of 40 to 90%. 31. The proportion of the number of deuterium atoms (D) in a mixture composed of two or more compounds represented by general formula (IVd) is X ¹ , X ² , X ³ in general formula (IVd).
And the total number of X ⁴ is in the range of 60-85%.