JP4973911B2 - Chroman derivative and liquid crystal composition containing the compound - Google Patents

Description

  The present invention relates to a trifluoronaphthalene-based liquid crystal compound useful as a component of a liquid crystal composition, a liquid crystal composition having a negative dielectric anisotropy and a large absolute value containing the compound, and a liquid crystal display device using the same .

  Liquid crystal display elements are currently widely used because of their excellent features such as low voltage operation and thin display. Conventional liquid crystal display device display methods include TN (twisted nematic), STN (super twisted nematic), or active matrix (TFT: thin film transistor) based on TN, which has a positive dielectric anisotropy value. The liquid crystal composition is used. However, one of the disadvantages of these display methods is a narrow viewing angle, and with the increasing demand for larger liquid crystal panels in recent years, the improvement has become a major issue.

  In recent years, display methods such as vertical alignment and IPS (in-plane switching) have been put to practical use as a solution. The vertical alignment method is a method in which the viewing angle is improved by utilizing the vertical alignment of liquid crystal molecules, and a liquid crystal composition having a negative dielectric anisotropy value is used. IPS is a method of improving viewing angle by switching liquid crystal molecules using a horizontal electric field in the horizontal direction with respect to a glass substrate, and a liquid crystal composition having a positive or negative dielectric anisotropy value is used. Is done. As described above, the vertical alignment method and the IPS, which are effective display methods for improving the viewing angle, require a liquid crystal compound and a liquid crystal composition having a negative dielectric anisotropy value. It has become. Conventionally, a compound having a 2,3-difluorophenylene group has been mainly used for a liquid crystal composition having a negative dielectric anisotropy (see Patent Document 1). However, a liquid crystal composition using this compound has a problem that the absolute value of dielectric anisotropy is not sufficiently large (see Patent Document 2).

  As a compound having a large absolute value of dielectric anisotropy, a liquid crystal compound having a 1,7,8-trifluoronaphthalene skeleton (see Patent Document 3) is disclosed. However, although this compound has a large absolute value of dielectric anisotropy, since it has a naphthalene skeleton, it has a large refractive index anisotropy and is difficult to apply to a liquid crystal composition having a small refractive index anisotropy. there were.

On the other hand, a compound having a chroman ring and a negative Δε has already been applied as a liquid crystal composition (see Patent Document 4). In general, in order to increase the absolute value of dielectric anisotropy, it is necessary to add a large amount of a compound having a large absolute value of Δε. However, such a compound does not necessarily have a good compatibility as a liquid crystal composition, and is limited in the amount of addition or cannot be said to have sufficient stability at low temperatures.
In view of the above, development of a liquid crystal compound having a large negative dielectric anisotropy and excellent compatibility with a liquid crystal composition has been demanded.

JP-T-2-503441 (Example of 8 pages) JP-A-10-176167 (Example of page 10) German Patent Application Publication No. 19522195 International Publication No. 2005/000995 Pamphlet

  To provide a compound having a negative dielectric anisotropy, a large absolute value and excellent compatibility with a liquid crystal composition, and a liquid crystal composition excellent in low-temperature stability using the compound. .

As a result of synthesizing various chroman derivatives and examining their physical properties, the present inventors have found that a difluorochroman derivative having a side chain as a linking group can solve the above-mentioned problems and have completed the present invention.
The present invention relates to the general formula (I)

(In the formula, R ^a is ^a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. a linear alkenyloxy group of 7, R ^b represents a linear alkyl group or linear alkenyl group having 2 to 7 carbon atoms of 1 to 7 carbon atoms, Z ^a and Z ^b are each Independently represents a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—, and X ^a and X ^b are each ^a hydrogen atom of X ^a X ^b represents a methyl group, or X ^a represents ^a methyl group, X ^b represents a hydrogen atom, and A ^a and A ^b are each independently a trans-1,4-cyclohexylene group or 1,4 A phenylene group, m and n each independently represents 0 or 1, at least one of m and n represents 0) and a dielectric constant comprising the compound as a constituent member anisotropy Negative nematic liquid crystal composition, a liquid crystal display element and further components of the liquid crystal composition.

  Since the liquid crystal composition of the present invention has a characteristic that the dielectric anisotropy is negative and has a large absolute value and is excellent in low-temperature stability of the composition, a display element using the liquid crystal composition is vertical. It is useful as a liquid crystal display element such as an alignment method and an in-plane switching (IPS) method. The trifluoronaphthalene derivative of the present invention has a negative dielectric anisotropy and a large absolute value, and is useful as a constituent member of a liquid crystal composition for a vertical alignment method, an IPS method, and the like.

In general formula (I), R ^a is preferably ^a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and a linear alkyl group having 1 to 5 carbon atoms. Alternatively, a straight-chain alkenyl group having 2 to 5 carbon atoms is more preferable. In the alkyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are more preferable. More preferred structure,

(The structural formula shall be connected to the ring at the right end.)
Particularly preferred are ethyl, propyl, butyl and pentyl groups.
R ^b is preferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and in the alkyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are more preferable, Of the alkenyl groups, the structures of formulas (a) to (e) are more preferred, with ethyl, propyl, butyl and pentyl groups being particularly preferred. In m and n, m is 1 or 0 and n is preferably 0, and m is 1 and n is more preferably 0. When m or n represents 1, Z ^a and Z ^b are preferably a single bond or —CH ₂ CH ₂ —, but at least one is preferably a single bond, more preferably a single bond. A ^a and A ^b are preferably trans-1,4-cyclohexylene groups.
The compound represented by the general formula (I) is specifically a compound represented by the following general formula (I-1) or general formula (I-2)

(Wherein, R ^a and R ^b each independently represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms) are particularly preferred. I-1) is more preferred.
The nematic liquid crystal composition having a negative dielectric anisotropy of the present invention contains one or more compounds represented by the general formula (I) as a constituent component, and the general formula (II)

(In the formula, R ^c represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and R ^d represents a linear alkyl group having 1 to 12 carbon atoms. Represents a linear alkenyl group having 2 to 12 carbon atoms, a linear alkoxyl group having 1 to 12 carbon atoms or a linear alkenyloxy group having 3 to 12 carbon atoms, p3 represents 0 or 1 , M ^b and M ^c each independently represents a single bond, —OCO—, —COO— or —CH ₂ CH ₂ —, and G ^c represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group. 1 type or 2 types or more are contained.

In the general formula (II), R ^c is preferably a linear alkyl group having 2 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. The chain alkyl group is more preferably an ethyl group, propyl group, butyl group or pentyl group, the 1-alkenyl group is more preferably a vinyl group or a trans-1-propenyl group, and the 3-alkenyl group is a 3-butenyl group. Or, a trans-3-pentenyl group is more preferable. R ^d is a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, a 3-alkenyl group having 4 to 5 carbon atoms, or a linear chain having 1 to 3 carbon atoms Alkoxyl groups are preferred. If the M ^b is present, at least one of M ^b and M ^c is a single bond.

  As the compound represented by the general formula (II), compounds represented by the following general formula (II-1) to general formula (II-14) are preferable, and the general formula (II-1), the general formula (II- 2), compounds represented by general formula (II-3), general formula (II-4), general formula (II-5) or general formula (II-6) are more preferred, and general formula (II-1) The compounds represented by general formula (II-3) or general formula (II-6) are particularly preferred.

Wherein R ¹ and R ² are each independently a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 3 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. R ³ represents a linear alkyl group having 1 to 5 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms, and R ⁴ represents a linear alkyl group having 1 to 3 carbon atoms. A group or a 3-alkenyl group having 4 to 5 carbon atoms, and R ⁵ represents a linear alkyl group having 1 to 3 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms.)
In the liquid crystal composition of the present invention, the compound represented by the general formula (I) is preferably contained in the composition in an amount of 1% by mass (hereinafter,% in the composition represents mass%) and 50% or less. % To 40% is more preferable, and 4 to 30% is more preferable. The content of the compound represented by the general formula (II) is preferably 10% to 70%, more preferably 20% to 50%.
In the liquid crystal composition of the present invention, the general formula (III)

(In the formula, R ^e represents a linear alkyl group having 1 to 7 carbon atoms, R ^f represents a linear alkyl group having 1 to 7 carbon atoms, and a linear alkoxyl group having 1 to 7 carbon atoms. Or a linear alkenyloxy group having 3 to 7 carbon atoms, p4 represents 0 or 1, M ^d and ^Me are each independently a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, -CH ₂ O-, -OCF _2- , -CF ₂ O-, -OCO- or -COO- represents G ^d substituted with a trans-1,4-cyclohexylene group or 1 to 2 fluorines It may contain one or more of 2,3-difluoro-1,4-phenylene derivatives represented by the following formula:

In the general formula (III), R ^e is preferably a linear alkyl group having 7 from 2 carbon atoms. R ^f is preferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxyl group having 1 to 5 carbon atoms, and a linear alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. The linear alkoxyl group is particularly preferable. M ^d is one single bond of M ^d and M ^e, the other is a single _{bond, -CH 2 CH 2 -, -} COO- or is preferably -CF ₂ O-in which.
The general formula (III) includes many compounds, but compounds represented by the following general formulas (III-1) to (III-7) are preferable.

In the above formula, R ⁶ represents a linear alkyl group having 1 to 7 carbon atoms, and R ⁷ is a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxyl group having 1 to 4 carbon atoms. Represents.
In the liquid crystal composition of the present invention, the general formula (IV) to the general formula (VIII)

(Wherein R ^g , R ⁱ , R ^k and R ^m each independently represents a linear alkyl group having 1 to 7 carbon atoms, and R ^h , R ^j and R ⁿ are each independently carbon. R ¹ represents a linear alkyl group having 1 to 7 atoms, a linear alkoxyl group having 1 to 7 carbon atoms, or a linear alkenyloxy group having 3 to 7 carbon atoms, and R ^l represents 1 to 7 carbon atoms. R ^o represents a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, or a linear alkenyl group having 2 to 7 carbon atoms Represents a linear alkenyloxy group having 3 to 7 carbon atoms, R ^p represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, X ^a And X ^b each independently represents a hydrogen atom or a fluorine atom, p5, p6, p7 and p8 each independently represents 0 or 1, and p9 and p10 each independently represents 0. , 1 or 2, and the sum of p9 and p10 is 1 or 2, and M ^f , M ^g , M ^h , M ⁱ , M ^j , M ^k , M ^l , M ^m and M ⁿ are each independently single _{bond, -CH 2 CH 2 -, -} OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - OCO- or represents -COO-, M ^o is a single bond or -CH ₂ CH _2- represents, and G ^e , G ^f , G ^g , G ^h , G ⁱ and G ^j are each independently substituted with a trans-1,4-cyclohexylene group or 1 to 2 fluorines. 1 or 4-phenylene group, and when there are a plurality of G ⁱ , G ^j , M ⁿ and ^Mo , they may be the same or different.) Or you may contain 2 or more types.

In the general formulas (IV) to (VIII), R ^g , R ⁱ , R ^k , R ^m and R ^p are preferably linear alkyl groups having 2 to 7 carbon atoms. R ^h , R ^j , R ⁿ and R ^o are preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkoxyl group. R ^l is preferably a linear alkyl group having 1 to 3 carbon atoms. M ^f and M ^g , M ^h and M ⁱ , M ^j and M ^k , M ^l and M ^m are each independently a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, — OCF ₂ —, —CF ₂ O— or —COO— is represented, and one is preferably a single bond and the other is preferably a single bond, —CH ₂ CH ₂ — or —COO—. M ⁿ is preferably a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —CF ₂ O—.

In the liquid crystal composition of the present invention thus obtained, the nematic phase upper limit temperature (T _NI ) is 70 ° C. or higher, more preferably 75 ° C. or higher, and the nematic phase lower limit temperature (T _{> N 2} ) is −20 ° C. or lower.

In the present invention, production examples of the compound represented by the general formula (I-1) are given below. Of course, the gist and scope of the present invention are not limited by these production examples.
(Production method 1) Synthesis of a compound in which X ^a represents ^a methyl group and X ^b represents a hydrogen atom A ketone derivative represented by the general formula (IX)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表す。)に、一般式（X）

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I)), and in general formula (X)

(式中、R^qはアルキル基を表す。)で表されるホスホン酸エステル及び水素化ナトリウム等の強塩基から調製される，ホルナー-エモンズ試薬を反応させることにより一般式(XI)

(Wherein R ^q represents an alkyl group) and a holonic-Emmons reagent prepared from a strong base such as sodium hydride and a phosphonic acid ester represented by the general formula (XI)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、R^qはアルキル基を表す。)で表されるα,β-不飽和エステル誘導体を得た後、二重結合をパラジウム／炭素等の金属触媒存在下に水素により還元し一般式（XII）

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I) and R ^q represents an alkyl group), an α, β-unsaturated ester derivative represented by After that, the double bond is reduced with hydrogen in the presence of a metal catalyst such as palladium / carbon to form a general formula (XII)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、R^qはアルキル基を表す。)で表されるエステルを得た後、水素化アルミニウムリチウム、水素化ビス(2-メトキシエトキシ)アルミニウムナトリウムなどの還元剤を作用させて還元することにより、一般式(XIII)

(Wherein R ^a , A ^a , Z ^a and m represent the same meaning as in general formula (I), R ^q represents an alkyl group), and after obtaining an ester represented by lithium aluminum hydride By reducing by acting a reducing agent such as sodium bis (2-methoxyethoxy) aluminum hydride, general formula (XIII)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表す。)で表されるアルコールを得る。これに、ピリジン、トリエチルアミン、4-(N,N-ジメチルアミノ)ピリジン、ジアザビシクロオクタンなどの塩基存在下、塩化ベンゼンスルホニル、塩化p-トルエンスルホニル、塩化メタンスルホニル又は塩化トリフルオロメタンスルホニルなどを作用させるか、あるいは硫酸酸性下、臭化水素酸、ヨウ化水素酸を作用させるか、あるいは塩化チオニル、臭化チオニルを作用させるか、あるいは三塩化リン、五塩化リン、三臭化リンを作用させるか、あるいはトリフェニルホスフィン存在下、四塩化炭素、四臭化炭素を作用させるなどして、一般式(XIV)

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I)). Benzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, or trifluoromethanesulfonyl chloride acts on this in the presence of a base such as pyridine, triethylamine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane, etc. Or hydrobromic acid or hydroiodic acid in sulfuric acid, thionyl chloride or thionyl bromide, or phosphorus trichloride, phosphorus pentachloride or phosphorus tribromide Or by reacting carbon tetrachloride, carbon tetrabromide in the presence of triphenylphosphine, etc.

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、Xは塩素、臭素、ヨウ素、ベンゼンスルホニル基、p-トルエンスルホニル基、メタンスルホニル基又はトリフルオロメタンスルホニル基などの脱離基を表す。)で表される化合物を得る。得られた一般式(XIV)と一般式(XV)

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I), X is chlorine, bromine, iodine, benzenesulfonyl group, p-toluenesulfonyl group, methanesulfonyl group or trifluoro group) Represents a leaving group such as a lomethanesulfonyl group). Obtained general formula (XIV) and general formula (XV)

(式中、R^b、A^b、Z^b及びｎは一般式(I)におけると同じ意味を表す。)で表される化合物をを金属ナトリウム、金属カリウム、金属セシウム、あるいはその炭酸塩、水酸化物、水素化物などの存在下、反応させることにより、一般式(I)で表される化合物を得ることができる。
（製法２） X^aが水素原子を表しX^bがメチル基を表す化合物の合成
一般式（XVI）

(Wherein R ^b , A ^b , Z ^b and n represent the same meaning as in general formula (I)), a compound represented by metal sodium, metal potassium, metal cesium, or a carbonate thereof, water By reacting in the presence of an oxide, hydride or the like, a compound represented by the general formula (I) can be obtained.
(Production Method 2) Synthesis of a compound in which X ^a represents ^a hydrogen atom and X ^b represents a methyl group General formula (XVI)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表す。)で表されるケトン誘導体に塩化メトキシメチルトリフェニルホスホニウムから調製したイリドを作用させた後、加水分解することにより、一般式(XVII)

(Wherein R ^a , A ^a , Z ^a and m have the same meanings as in general formula (I)), and an ylide prepared from methoxymethyltriphenylphosphonium chloride is allowed to act on the ketone derivative represented by By hydrolyzing, general formula (XVII)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表す。)で表されるアルデヒドを得る。一般式（XVII）に一般式（X）で表されるホスホン酸エステル及び水素化ナトリウム等の強塩基から調製される，ホルナー-エモンズ試薬を反応させることにより一般式(XVIII)

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I)). By reacting the general formula (XVII) with a Horner-Emmons reagent prepared from a phosphonate represented by the general formula (X) and a strong base such as sodium hydride, the general formula (XVIII)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、R^qはアルキル基を表す。)で表されるα,β-不飽和エステル誘導体を得た後、、二重結合をパラジウム／炭素等の金属触媒存在下に水素により還元し一般式（XIX）

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I) and R ^q represents an alkyl group), an α, β-unsaturated ester derivative represented by After that, the double bond is reduced with hydrogen in the presence of a metal catalyst such as palladium / carbon to form a general formula (XIX)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、R^qはアルキル基を表す。)で表されるエステルを得た後、水素化アルミニウムリチウム、水素化ビス(2-メトキシエトキシ)アルミニウムナトリウムなどの還元剤を作用させて還元することにより、一般式(XX)

(Wherein R ^a , A ^a , Z ^a and m represent the same meaning as in general formula (I), R ^q represents an alkyl group), and after obtaining an ester represented by lithium aluminum hydride By reducing by acting a reducing agent such as sodium bis (2-methoxyethoxy) aluminum hydride, general formula (XX)

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表す。)で表されるアルコールを得る。これに、ピリジン、トリエチルアミン、4-(N,N-ジメチルアミノ)ピリジン、ジアザビシクロオクタンなどの塩基存在下、塩化ベンゼンスルホニル、塩化p-トルエンスルホニル、塩化メタンスルホニル又は塩化トリフルオロメタンスルホニルなどを作用させるか、あるいは硫酸酸性下、臭化水素酸、ヨウ化水素酸を作用させるか、あるいは塩化チオニル、臭化チオニルを作用させるか、あるいは三塩化リン、五塩化リン、三臭化リンを作用させるか、あるいはトリフェニルホスフィン存在下、四塩化炭素、四臭化炭素を作用させるなどして、一般式(XXI)

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I)). Benzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, or trifluoromethanesulfonyl chloride acts on this in the presence of a base such as pyridine, triethylamine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane, etc. Or hydrobromic acid or hydroiodic acid in sulfuric acid, thionyl chloride or thionyl bromide, or phosphorus trichloride, phosphorus pentachloride or phosphorus tribromide Or by reacting carbon tetrachloride, carbon tetrabromide in the presence of triphenylphosphine, etc.

(式中、R^a、A^a、Z^a及びｍは一般式(I)におけると同じ意味を表し、Xは塩素、臭素、ヨウ素、ベンゼンスルホニル基、p-トルエンスルホニル基、メタンスルホニル基又はトリフルオロメタンスルホニル基などの脱離基を表す。)で表される化合物を得る。得られた一般式(XXI)と一般式(XV)で表される化合物をを金属ナトリウム、金属カリウム、金属セシウム、あるいはその炭酸塩、水酸化物、水素化物などの存在下、反応させることにより、一般式(I)で表される化合物を得ることができる。

(Wherein R ^a , A ^a , Z ^a and m have the same meaning as in general formula (I), X is chlorine, bromine, iodine, benzenesulfonyl group, p-toluenesulfonyl group, methanesulfonyl group or trifluoro group) Represents a leaving group such as a lomethanesulfonyl group). By reacting the compounds represented by the general formula (XXI) and the general formula (XV) in the presence of metal sodium, metal potassium, metal cesium, or a carbonate, hydroxide, hydride thereof, etc. A compound represented by the general formula (I) can be obtained.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
The following abbreviations are used in compound descriptions.
Me: methyl group
Et: ethyl group
Pr: Propyl group
Bu: Butyl group
Pen: pentyl group
SBMEA: Bis (2-methoxyethoxy) aluminum sodium hydride
Ms: Methanesulfonyl group
Py: pyridine The following symbols are used in the description of the phase transition temperature.
C crystal phase
N nematic phase
S unknown smectic phase
I isotropic liquid phase
Example 1 Synthesis of 7,8-difluoro-2-pentyl-6- (3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butoxy) chroman (I-1)

(1-1) Synthesis of ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2-butenoate (2) Sodium hydride (60% mineral oil dispersion, 17.6 g, 0.440 mol) While the toluene (200 ml) suspension solution was vigorously stirred while cooling to 10 ° C. or lower, ethyl phosphonoacetate (99.6 g, 0.440 mol) was added dropwise while maintaining the temperature. While maintaining the temperature at 10 ° C. or lower, a toluene (200 ml) solution of 1- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) ethanone (1) (100.0 g, 0.399 mol) was added dropwise. After heating to reflux for 2 hours, water was added dropwise to stop the reaction. The organic layer was extracted with toluene (3 times), and the collected organic layer was washed with 3 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine in this order, and the solution was purified as it was through a column (silica gel, toluene). Further distillation under reduced pressure (160-210 ° C., 1.0 KPa) gave a slightly yellow liquid of ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2-butenoate (2).
Yield 129.3 g (Yield 92.0%)

(1-2) Synthesis of ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butanoate (3)
(The following is carried out in an autoclave.) 5% palladium-carbon in a mixed solution of the compound (2) obtained in (1-1) (129.3 g, 0.368 mol) in ethanol / ethyl acetate (200 ml / 200 ml). (50% water content, 12.6 g) was added, and the mixture was stirred at room temperature for 6 hours under hydrogen pressure (0.5 MPa). After the catalyst was filtered off using powdered cellulose, the filtrate was concentrated under reduced pressure to obtain a slightly yellow liquid of ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butanoate (3).
Yield 133.3 g (Yield quantitative)

(1-3) Synthesis of 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butanol (4)
While a solution of the compound (3) obtained in (1-2) (133.3 g, 0.368 mol) in toluene (400 ml) was vigorously stirred at room temperature, 70% bis (2-methoxyethoxy) aluminum hydride was added. Sodium acid toluene solution (SBMEA, 120.0 g, 0.416 mol) was added dropwise. After stirring at room temperature for 1 hour, the reaction was stopped by adding dropwise to water. 3 M hydrochloric acid was added until the precipitated solid was dissolved, followed by extraction with ethyl acetate (3 times). The collected organic layer was washed with a saturated aqueous sodium bicarbonate solution and then with saturated brine, and dried over anhydrous sodium sulfate. did. The solvent was distilled off to obtain a pale yellow liquid of 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butanol (4).
Yield 108.0 g (Yield quantitative)

(1-4) Synthesis of 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl (5) methanesulfonate
Methanesulfonyl chloride (31.0 ml, 0.401 mol) was added dropwise to a solution of compound (4) obtained in (1-3) (108.0 g, 0.368 mol) in dichloromethane (300 ml) under water cooling. While maintaining the temperature, pyridine (35.5 ml, 0.439 mol) was added dropwise. Subsequently, 4-dimethylaminopyridine (5.4 g, 0.044 mol) was added, and stirring was continued at room temperature for 8 hours. Water was added to the reaction solution to stop the reaction, and then the organic layer was separated and extracted from the aqueous layer with dichloromethane (twice). The collected organic layer was washed with 3M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting liquid was purified using a column (alumina, toluene) and further recrystallized (hexane) to give 3- (trans-4- (trans-4-propylcyclohexyl) methanesulfonate. A white solid of) cyclohexyl) butyl (5) was obtained.
Yield 103.0 g (Yield 75.4%)

(1-5) Synthesis of 7,8-difluoro-2-pentyl-6- (3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butoxy) chroman (I-1)
(Hereafter, in a nitrogen atmosphere.) 7,8-Difluoro-2-pentylchroman-6-ol (6) (14.3 g, 0.056 mol) in DMF (300 ml) was added to tripotassium phosphate (23.7 g, 0.112 mol), and then added 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butyl methane (5) (20.0 g, 0.056 mol) obtained in (1-4). added. After heating to reflux for 2 hours, the mixture was cooled to room temperature, and water was added dropwise to stop the reaction. Extracted with toluene (3 times), and the collected organic layer was washed with 3 M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order, and the solution was used as it was with a column (silica gel + alumina, toluene). And recrystallized (acetone) to give 7,8-difluoro-2-pentyl-6- (3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) butoxy) chroman (I-1 ) White powder was obtained. Yield 25.2 g (Yield 87.1%)
1H-NMR (400MHz, CDCl3) d (ppm) 0.77-2.02 (m, 43H, CH + CH2 + CH3), 0.85 (t, J = 7.2Hz, 3H, CH3), 2.60-2.80 (m, 2H, CH2 ), 3.88-3.99 (m, 3H, CH2O + CHO), 6.38 (dm, J = 6.4Hz, 1H, ArH), purity 99.9% (GC),
Phase transition temperature (° C) C 91.5 (S 55 N 76.5) I
Example 2 Synthesis of 7,8-difluoro-2-pentyl-6- (2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propoxy) chroman (I-2)

(2-1) Synthesis of trans-4- (trans-4-propylcyclohexyl) cyclohexylacetaldehyde (8)
(Hereafter, this is carried out under a nitrogen atmosphere.) While stirring a solution of methoxymethyltriphenylphosphonium chloride (7) (370 g, 1.079 mol) in tetrahydrofuran (THF, 740 ml) vigorously under ice-cooling, the internal temperature While maintaining the above, a solution of potassium t-butoxy (121 g, 1.078 mol) in THF (600 ml) was added dropwise. After maintaining vigorous stirring for 30 minutes while maintaining the internal temperature, a THF (400 ml) solution of 4- (trans-4-propylcyclohexyl) cyclocyclohexanone (1, 200 g, 0.899 mol) was added dropwise while maintaining the internal temperature. Added. Stirring vigorously for 1 hour while maintaining the internal temperature, water was added dropwise to stop the reaction, hexane and methanol were added, the organic layer was separated, and the aqueous layer was extracted with hexane (twice). ). The collected organic layer was washed with a 50% aqueous methanol solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off, and purification using a column (silica gel, hexane) gave a pale yellow liquid (224.7 g).

  While the obtained liquid THF (300 ml) solution was vigorously stirred at room temperature, 3 M hydrochloric acid (300 ml) was added, and the mixture was heated to reflux for 2 hours. After cooling to room temperature, the organic layer was separated and the aqueous layer was extracted with hexane (twice). The collected organic layer was washed with water, a saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a pale yellow liquid (211.8 g).

While vigorously stirring the obtained liquid methanol (400 ml) solution under ice-cooling, 10% aqueous sodium hydroxide solution (40 ml) was added dropwise while maintaining the internal temperature. While stirring, stirring was continued for 1 hour. While maintaining the internal temperature, water was added dropwise to stop the reaction, ethyl acetate was added, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (twice). The collected organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off and recrystallization (methanol) gave trans-4- (trans-4-propylcyclohexyl) cyclohexylacetaldehyde (8) as a white solid.
Yield 210 g (Yield 95.8%)

(2-2) Synthesis of ethyl 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) acrylate (9) Sodium hydride (60% mineral oil dispersion, 8.4 g, 0.210 mol) While stirring a toluene (120 ml) suspension solution at a temperature of 10 ° C or lower, while maintaining the temperature, triethyl 2-phosphonopropionate (50.0 g, 0.210 mol) was added dropwise. added. While maintaining the temperature below 10 ° C, a solution of trans-4- (trans-4-propylcyclohexyl) cyclohexylacetaldehyde (8) (46.1 g, 0.189 mol) obtained in (2-1) was added dropwise. It was. After heating to reflux for 2 hours, water was added dropwise to stop the reaction. The organic layer was extracted with toluene (3 times), and the collected organic layer was washed with 3 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine in this order, and the solution was purified as it was through a column (silica gel, toluene). A yellow liquid of ethyl 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) acrylate (9) was obtained.
Yield 68.0 g (Yield quantitative)

(2-3) Synthesis of ethyl 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propanoate (10)
(The following is carried out in an autoclave.) 5% palladium-carbon in a mixed solution of the compound (3) obtained in (2-2) (68.0 g, 0.189 mol) in ethanol / ethyl acetate (300 ml / 300 ml). (50% water content, 8.0 g) was added, and the mixture was stirred at room temperature for 6 hours under hydrogen pressure (0.5 MPa). After filtering the catalyst using powdered cellulose, the filtrate was concentrated under reduced pressure to obtain a yellow liquid of ethyl 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propanoate (10). It was.
Yield 55.4 g (Yield 90.0%)

(2-4) 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propanol (11)
While a solution of the compound (10) (55.4 g, 0.170 mol) obtained in (2-3) in toluene (150 ml) was vigorously stirred at room temperature, 70% bis (2-methoxyethoxy) aluminum hydride was added. Sodium acid toluene solution (SMEBA, 60.0 g, 0.208 mol) was added dropwise. After stirring at room temperature for 1 hour, the reaction was stopped by adding dropwise to water. 3 M hydrochloric acid was added until the precipitated solid was dissolved, followed by extraction with ethyl acetate (3 times). The collected organic layer was washed with a saturated aqueous sodium bicarbonate solution and then with saturated brine, and dried over anhydrous sodium sulfate. did. The solvent was distilled off to obtain a yellow liquid of 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propanol (11).
Yield 49.4 g (Yield quantitative)

(2-5) 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propyl methanesulfonate (12)
Methanesulfonyl chloride (15.5 ml, 0.200 mol) was added dropwise to a solution of the compound (11) obtained in (2-4) (49.4 g, 0.170 mol) in dichloromethane (250 ml) under water cooling. While maintaining the temperature, pyridine (20.0 ml, 0.247 mol) was added dropwise. Subsequently, 4-dimethylaminopyridine (2.6 g, 0.021 mol) was added, and stirring was continued at room temperature for 8 hours. Water was added to the reaction solution to stop the reaction, and then the organic layer was separated and extracted from the aqueous layer with dichloromethane (twice). The collected organic layer was washed with 3M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting liquid was purified using a column (alumina, toluene), and further recrystallized (hexane) to give 2-methyl-3- (trans-4- (trans-4- (trans- A white solid of 4-propylcyclohexyl) cyclohexyl) propyl (12) was obtained.
Yield 50.5 g (Yield 77.1%)

(2-6) 7,8-Difluoro-2-pentyl-6- (2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propoxy) chroman (I-2)
(The following is performed in a nitrogen atmosphere.) To a solution of 7,8-difluoro-2-pentylchroman-6-ol (16) (7.1 g, 0.028 mol) in DMF (100 ml) was added anhydrous tripotassium phosphate (11.8 g, 0.056 mol), and then 2-methyl-3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propyl methanesulfonate (12) (10.0 g, obtained in (2-4). 0.028 mol) was added. After heating to reflux for 2 hours, the mixture was cooled to room temperature, and water was added dropwise to stop the reaction. The mixture was extracted with a toluene / hexane mixed solution (3 times), and the collected organic layer was washed with 3 M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. Purification using toluene / hexane = 1/1) and recrystallization (acetone) gave 7,8-difluoro-2-pentyl-6- (2-methyl-3- (trans-4- (trans- A white powder of 4-propylcyclohexyl) cyclohexyl) propoxy) chroman (I-2) was obtained. Yield 11.8 g (Yield 82.1%)
1H-NMR (400MHz, CDCl3) d (ppm) 0.77-1.17 (m, 16H, CH + CH2), 0.87 (t, J = 7.3Hz, 3H, CH3), 0.99 (d, J = 6.6Hz, 3H, CH3), 1.23-1.83 (m, 22H, CH + CH2), 1.96-2.07 (m, 2H, CH2), 2.64-2.81 (m, 2H, CH2), 3.65 (dd, J1 = 8.9Hz, J2 = 7.2 Hz, 1H, CH2O), 3.78 (dd, J1 = 8.9Hz, J2 = 5.5Hz, 1H, CH2O), 3.94-4.00 (m, 1H, CHO), 6.38 (dm, J = 7.8Hz, 1H, ArH) , Purity 99.9% (GC),
Phase transition temperature (° C) C 66.5 (N 56.5) I
(Example 3) Preparation of liquid crystal composition (1)
Host liquid crystal composition comprising the following composition (H)

を調製した。ここで(H)の物性値は以下の通りである。

Was prepared. Here, the physical properties of (H) are as follows.

Nematic phase upper limit temperature (T _NI ): 103.2 ℃
Dielectric anisotropy (Δε): 0.04
Refractive index anisotropy (Δn): 0.098
A liquid crystal composition (M-1) comprising 80% of the base liquid crystal (H) and 20% of the formula (I-1) obtained in Example 1 was prepared. The physical properties of this composition are as follows.

Nematic phase upper limit temperature (T _NI ): 97.4 ℃
Dielectric anisotropy (Δε): −1.08
Refractive index anisotropy (Δn): 0.095
In the liquid crystal composition (M-1) containing the compound (IA) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). This shows that the compound (IA) of the present invention has a negative dielectric anisotropy and an extremely large absolute value.

  Further, when the voltage holding ratio of the liquid crystal composition (M-1) was measured at 80 ° C., the voltage holding ratio of the host liquid crystal composition (H) was as high as 98% or more. This shows that the compound (I-A) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.

(Example 4) Preparation of liquid crystal composition (2)
A liquid crystal composition (M-2) comprising 80% of the base liquid crystal (H) prepared in Example 3 and 20% of the formula (I-2) obtained in Example 2 was prepared. The physical properties of this composition are as follows.
Nematic phase upper limit temperature (T _NI ): 92.1 ℃
Dielectric anisotropy (Δε): −1.01
Refractive index anisotropy (Δn): 0.093
In the liquid crystal composition (M-2) containing the compound (I-2) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). . This shows that the compound (I-2) of the present invention has a negative dielectric anisotropy and an extremely large absolute value.
Further, when the voltage holding ratio of the liquid crystal composition (M-2) was measured at 80 ° C., the voltage holding ratio of the host liquid crystal composition (H) was as high as 98% or more. This shows that the compound (I-2) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.

(Comparative Example 1) Preparation of liquid crystal composition (3)
80% of the base liquid crystal (H) prepared in Example 3 and the following compound similar to the compound of the present invention (R-1)

A liquid crystal composition (M-R1) comprising 20% was prepared. This composition was unstable in that crystals precipitated at room temperature. Since 20% of the compound of Comparative Example cannot be added, a liquid crystal composition (M-R2) comprising 90% of the base liquid crystal (H) and 10% of (R-1) was prepared.
The physical properties of this composition are as follows.

Nematic phase upper limit temperature (T _NI ): 105.0 ℃
Dielectric anisotropy (Δε): −0.53
Refractive index anisotropy (Δn): 0.098
Although the liquid crystal composition (M-R2) containing the compound (R-1) of the comparative example has a higher nematic phase upper limit temperature than the liquid crystal compositions described in Examples 3 and 4, the absolute value of Δε is about half. It became a low value.
From the above, it is clear that the compound of the present invention has both high compatibility with the liquid crystal composition and a large absolute value of Δε.
(Example 5) Preparation of liquid crystal composition (4)
A liquid crystal composition (M-3) having the following composition was prepared.

The physical properties of (MF) were as follows.
Nematic phase upper limit temperature (T _NI ): 82.0 ℃
Dielectric anisotropy (Δε): −3.20
Refractive index anisotropy (Δn): 0.092
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.

(Example 6) Preparation of liquid crystal composition (5)
A liquid crystal composition (M-4) having the following composition was prepared.

The physical properties of this (MG) were as follows.
Nematic phase upper limit temperature (T _NI ): 80.1 ℃
Dielectric anisotropy (Δε): −3.16
Refractive index anisotropy (Δn): 0.091
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.

The liquid crystal composition, display element, and compound of the present invention are useful as constituent members of a liquid crystal display element such as a vertical alignment method and IPS.

Claims (11)

Formula (I)

(In the formula, R ^a is ^a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. a linear alkenyloxy group of 7, R ^b represents a linear alkyl group or linear alkenyl group having 2 to 7 carbon atoms of 1 to 7 carbon atoms, Z ^a and Z ^b are each Independently represents a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—, and X ^a and X ^b are each ^a hydrogen atom of X ^a X ^b represents a methyl group, or X ^a represents ^a methyl group, X ^b represents a hydrogen atom, and A ^a and A ^b are each independently a trans-1,4-cyclohexylene group or 1,4 -Represents a phenylene group, and m and n each independently represents 0 or 1, but at least one of m and n represents 0). The compound according to claim 1, wherein in the general formula (I), m represents 1 and n represents 0. The compound according to claim 1 or 2, wherein in the general formula (I), R ^a and R ^b represent a linear alkyl group having 1 to 5 carbon atoms. Formula (I)

(In the formula, R ^a is ^a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. a linear alkenyloxy group of 7, R ^b represents a linear alkyl group or linear alkenyl group having 2 to 7 carbon atoms of 1 to 7 carbon atoms, Z ^a and Z ^b are each Independently represents a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—, and X ^a and X ^b are each ^a hydrogen atom of X ^a or represents a X ^b methyl group represents, X ^a represents X ^b hydrogen atom a methyl group, a ^a and a ^b are each independently trans-1,4-cyclohexylene group or 1,4-phenylene And m and n each independently represents 0 or 1, but at least one of m and n represents 0), containing one or more compounds represented by the general formula (II )

(In the formula, R ^c represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and R ^d represents a linear alkyl group having 1 to 12 carbon atoms. Represents a linear alkenyl group having 2 to 12 carbon atoms, a linear alkoxyl group having 1 to 12 carbon atoms or a linear alkenyloxy group having 3 to 12 carbon atoms, p3 represents 0 or 1 , M ^b and M ^c each independently represents a single bond, —OCO—, —COO— or —CH ₂ CH ₂ —, and G ^c represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group. A nematic liquid crystal composition having a negative dielectric anisotropy, which contains one or more compounds represented by: Formula (III)

(In the formula, R ^e represents a linear alkyl group having 1 to 7 carbon atoms, R ^f represents a linear alkyl group having 1 to 7 carbon atoms, and a linear alkoxyl group having 1 to 7 carbon atoms. Or a linear alkenyloxy group having 3 to 7 carbon atoms, p4 represents 0 or 1, M ^d and ^Me are each independently a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, -CH ₂ O-, -OCF _2- , -CF ₂ O-, -OCO- or -COO- represents G ^d substituted with a trans-1,4-cyclohexylene group or 1 to 2 fluorines The liquid crystal composition according to claim 4, which contains one or more compounds represented by the formula: General formula (IV), general formula (V), general formula (VI), general formula (VII) and general formula (VIII)

(Wherein R ^g , R ⁱ , R ^k and R ^m each independently represents a linear alkyl group having 1 to 7 carbon atoms, and R ^h , R ^j and R ⁿ are each independently carbon. R ¹ represents a linear alkyl group having 1 to 7 atoms, a linear alkoxyl group having 1 to 7 carbon atoms, or a linear alkenyloxy group having 3 to 7 carbon atoms, and R ^l represents 1 to 7 carbon atoms. R ^o represents a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, or a linear alkenyl group having 2 to 7 carbon atoms Represents a linear alkenyloxy group having 3 to 7 carbon atoms, R ^p represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, X ^a And X ^b each independently represents a hydrogen atom or a fluorine atom, p5, p6, p7 and p8 each independently represents 0 or 1, and p9 and p10 each independently represents 0. , 1 or 2, and the sum of p9 and p10 is 1 or 2, and M ^f , M ^g , M ^h , M ⁱ , M ^j , M ^k , M ^l , M ^m and M ⁿ are each independently single _{bond, -CH 2 CH 2 -, -} OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - OCO- or represents -COO-, M ^o is a single bond or -CH ₂ CH _2- represents, and G ^e , G ^f , G ^g , G ^h , G ⁱ and G ^j are each independently substituted with a trans-1,4-cyclohexylene group or 1 to 2 fluorines. And when there are a plurality of G ⁱ , G ^j , M ⁿ and ^Mo , they may be the same or different.) The liquid crystal composition according to claim 4 or 5, which comprises one or more compounds selected from the group consisting of more than one compound. Contains two or more compounds represented by general formula (III), represented by general formula (IV), general formula (V), general formula (VI), general formula (VII) and general formula (VIII) The liquid crystal composition according to claim 6, comprising two or more selected from the group of compounds. The nematic phase upper limit temperature is 70 ° C or higher, the nematic phase lower limit temperature is -20 ° C or lower, and the content of the compound represented by the general formula (I) is in the range of 1 to 50% by mass. 8. The liquid crystal composition according to any one of 7 above. The liquid crystal display device using the liquid crystal composition according to any one of claims 4 to 8. The liquid crystal display element according to claim 9, which is driven in an active matrix. The liquid crystal display element according to claim 10, which is displayed in a vertical alignment mode.