JPH1180049A - Liquid crystalline compound with negative dielectric constant anisotropy value, liquid crystal composition comprising the compound, and liquid crystal display element using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new crystalline compound comprising a specific spiro ring in its molecule, capable of providing a negative dielectric constant anisotropy value large in absolute value, proper refractive index anisotropy, small elastic constant, lower viscosity, good compatibility, and chemical/physical stability, and useful for liquid crystalline elements. SOLUTION: This compound is shown by formula I [R<1> and Y<1> are each a 1-30C alkyl, etc,; A<1> to A<5> are each e.g. a group of formula II (W<1> to W<4> are each H, a halogen, etc., noted that the whole of them are not H simultaneously, and when one of them is other than H, additional other one connected to the same carbon atom is also other than H); and (a<1> ) to (a<5> ) are each 0 or 1], e.g. 1,1-difluoro-2- 2-[trans-4-(2,3- difluoro-4-ethoxy phenyl) cyclohexyl]ethyl}-7-n-propylspiro[3.5] nonane. This example compound is obtained by reacting a compound of formula III with that of formula IV to thereby obtain a compound of formula V, subjecting it to dehydration and hydrogen addition in this order, and turning it into an oxo-compound and followed by difluorination.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention mainly relates to a liquid crystal display device, for example, a vertical alignment system, an IPS (in-plane switching) system, a TFT (thin film transistor) system, and a TN.
(Twisted nematic) method, STN (super twisted nematic) method and the like, especially a novel liquid crystal compound that develops various physical properties suitable for a liquid crystal composition for a vertical alignment method and an IPS method. Liquid crystal compound having at least one of the rings represented by formulas (2-1), (2-2) and (2-3) in the molecule, and a liquid crystal composition having favorable various physical properties using the compound And a liquid crystal display device using the liquid crystal composition. (In the present application, the term “liquid crystal compound” refers to a compound that exhibits a liquid crystal phase and a compound that does not exhibit a liquid crystal phase but is useful as a component of the liquid crystal composition.) Used as a generic term.).

[0002]

BACKGROUND ART Conventionally, various liquid crystal display systems have been proposed. As an example of them, the following display method is mentioned (Latest technology of liquid crystal, edited by the Industrial Research Council (1983)). As a method of using a liquid crystal composition having a positive dielectric anisotropy value, TN
, STN, or TN based AM
(Active matrix) method (TFT method and MIM)
(Metal, insulating film, metal) method, etc.). In addition, as a method of using a liquid crystal composition having a negative dielectric anisotropy value, ECB is used.
(Electric field control birefringence effect) method (including HAN (hybrid molecular arrangement) method and DAP (vertical molecular arrangement) method), DS (dynamic scattering) method, GH (guest host) method, and PC (phase transition) Method. Of these methods,
The mainstream of the method currently in practical use is a method using a liquid crystal composition having a positive dielectric anisotropy value. By comparison,
Practical use of a system using a liquid crystal composition having a negative dielectric anisotropy value has been delayed. In connection with this, the development of liquid crystal compositions having a negative dielectric anisotropy value and the compounds used for the same were also compared with the development of liquid crystal compositions having a positive dielectric anisotropy value and the compounds used for the same. Then, it is not enough.

Under these circumstances, recently, attempts to improve the narrow viewing angle, which is one of the drawbacks of the liquid crystal display, have been actively made. One of the methods is the IPS (in-plane switching) method (R. Kiefer et al., JAPAN DISPLAY '92, 547 (1992), M. Oh)
-e et al., ASIA DISPLAY '95, 577 (1995), Tokuyohei 5-5
05247, JP-A-7-128647, etc.). One of the features of the IPS method is that, in the conventional liquid crystal panel, electrodes are provided on upper and lower substrates, respectively, whereas in the liquid crystal panel of this method, a comb-shaped electrode is provided only on one substrate. Is a point. And another one of this method
One feature is that various liquid crystal compositions can be used regardless of whether the dielectric anisotropy value is positive or negative. Another example of an attempt to improve the narrow viewing angle is a vertical alignment (VA) that utilizes vertical alignment of liquid crystal molecules.
(For example, JP-A-2-176625). One of the features of this method is that a liquid crystal composition having a negative dielectric anisotropy value is used. Against this background,
Liquid crystal compounds and liquid crystal compositions having a negative dielectric anisotropy have been strongly demanded.

[0004] By the way, in any display method,
The liquid crystal composition used is not only a dielectric anisotropy value,
Refractive index anisotropy value (△ n), elastic constant ratio K ₃₃ / K
₁₁ (K _33: bend elastic constant, K _11: splay elastic constant)
It is necessary to adjust other physical property values such as the value of to an optimum value, and further, it is required that the liquid crystal phase be in an appropriate temperature range and that it has a low viscosity even at a low temperature. None of the conventionally known liquid crystalline compounds satisfies all of these conditions by themselves, and usually, a compound having several to twenty and several types of liquid crystal phases and, if necessary, a compound having no more than several types of liquid crystal phases are mixed. The liquid crystal composition prepared as described above is used. Therefore, each liquid crystal compound is
Characteristics such as good compatibility with other liquid crystal compounds and good compatibility in a low temperature range are also required due to demand for use in a low temperature environment.

However, as described above, the conventional display system mainly uses a liquid crystal composition containing a liquid crystal compound having a positive dielectric anisotropy value. The development of compounds and compositions that are
For this reason, the conventional liquid crystal compounds and compositions have not sufficiently responded to such diversifying methods and various characteristics required thereby. For example, even if the dielectric anisotropy value is negative, the absolute value is small, the driving voltage cannot be reduced due to the large elastic constant, the compatibility is poor, and the compound cannot be used in large quantities. There were problems such as difficulty in freely setting the refractive index anisotropy value, high viscosity, and poor chemical and physical stability.

Prior to the present invention, spiro [3.5] in the molecule
Liquid crystalline compounds having nonane-2,7-diyl have already been reported (for example, DE 4408418 A).
1 gazette).

[0007]

Embedded image

However, the compounds disclosed herein have physical properties necessary for utilizing the compounds in a liquid crystal composition, such as an appropriate refractive index anisotropy value, a small elastic constant, and compatibility with other liquid crystal materials. , Low viscosity, high electrical insulation, wide temperature range of liquid crystal phase, chemical and physical stability, etc. are not always satisfactory, in particular, they do not have negative dielectric anisotropy with a large absolute value, Further improvements were required. In addition, there is no idea here to induce a compound having spiro [3.5] nonane-2,7-diyl in a molecule into a liquid crystal compound having a negative dielectric anisotropy value. In particular, for this purpose one of spiro [3.5] nonane-2,7-diyl
Position and / or 3-position regioselectively halogen atom, a cyano _{group, -OCF 3, -OCF 2 H,} -CF 3, -CF
_{2 H, -CFH 2, -CF 2} CF 3, -OCF 2 CF 3, -O
By introducing CF ₂ CF ₂ H or -OCF ₂ CFHCF _3,
1,1-disubstituted spiro [3.5] nonane-2,7-diyl or 1,1,3,3-tetrasubstituted halogenospiro [3.
5] There is no idea leading to nonane-2,7-diyl.

Prior to the present invention, dispiro [5.
1.5.1] Liquid crystalline compounds having tetradecane-3,1,1-diyl have already been reported (for example, JP-T-63-501958).

[0010]

Embedded image

However, the compounds disclosed herein have physical properties necessary for utilizing them in a liquid crystal composition, such as an appropriate refractive index anisotropy value, a small elastic constant, compatibility with other liquid crystal materials, It has no properties such as low viscosity, high electric insulation, wide liquid crystal phase temperature range, and chemical / physical stability, and further improvement has been demanded. In addition, there is no description about negative dielectric anisotropy having a large absolute value here, and a compound having dispiro [5.1.5.1] tetradecane-3,11-diyl in a molecule is obtained by using a dielectric anisotropic material. There is no idea that leads to a liquid crystal compound having a negative property value. In particular, for this purpose dispiro [5.1.5.1] tetradecane-
3,11-diyl at the 7 and / or 14-position regioselectively _{-OCF 3, -OCF 2 H, -CF} 3, -CF 2 H,
-CFH _2, by introducing the -CF ₂ CF ₃ or -OCF ₂ CF _3, 7,7-disubstituted dispiro [5.1.5.1] tetradecane-3,11-diyl or 7,7,14, 14
There is no idea leading to -tetrasubstituted fluorodispiro [5.1.5.1] tetradecane-3,11-diyl.

As described above, studies on liquid crystal compounds having a negative dielectric anisotropy have not been sufficiently conducted. In particular, studies on liquid crystal compounds having characteristics suitable for application to systems such as the VA system and the IPS system have not been sufficient.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a VA system, an IPS system, and an ECB system (HAN).
System, DAP system, etc.), DS system, GH system, PC system, etc., as well as various display systems using compounds or compositions having a negative dielectric anisotropy value.
, STN, or TN based AM
It can also be used for adjusting various characteristics of liquid crystal compositions for various display systems using compounds or compositions having a positive dielectric anisotropy value such as a system (TFT system and MIM system).
It is an object of the present invention to provide a novel liquid crystal compound which has solved the above-mentioned problems, a liquid crystal composition containing the same, and a liquid crystal display device produced using the liquid crystal composition.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, the compound represented by the following general formula (1) has a negative dielectric anisotropy value having a large absolute value. Not only that, it has an appropriate refractive index anisotropy value, a small elastic constant, good compatibility, low viscosity, high chemical and physical stability, and this compound in a liquid crystal composition. By using, the elastic constant is small, the dielectric anisotropy value and the refractive index anisotropy value can be set appropriately, the viscosity is low,
A liquid crystal composition having excellent physical stability, in particular, a liquid crystal composition having a large absolute value and a negative dielectric anisotropy value can be obtained, and a liquid crystal display device can be obtained using the composition. They have found and completed the present invention.

[0015]

Embedded image

(Wherein R ¹ and Y ^{1 each} represent a linear or branched alkyl group having 1 to 30 carbon atoms, and any methylene group in the alkyl group may be -O-, -S-, -CO-, −CS
—, —CH ＝ CH—, —C≡C—, —SiR ² R ³ —, cyclopropane-1,2-diyl, cyclobutane-1,3
-Diyl or bicyclo [1.1.1] pentane-
Although it may be substituted with 1,3-diyl, -O- and -S- are not continuous, and one or more hydrogen atoms in these groups are substituted with a halogen atom or a cyano group. R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and include a ring A ¹ , a ring A ² , a ring A ³ , a ring A ⁴
And ring A ⁵ are each independently a group represented by formula (2-1) or (2-
2) or a ring represented by (2-3), cyclohexane-
1,4-diyl, silacyclohexane-1,4-diyl, silacyclohexane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-
2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl or bicyclo [1.1.1] pentane-1,3-diyl,
At least one of the ring A ¹ , the ring A ² , the ring A ³ , the ring A ⁴ and the ring A ⁵ has the general formula (2-1), (2-2) or (2-
3) and any one or two hydrogen atoms on these rings may be substituted with a halogen atom;

[0017]

Embedded image

(Wherein W ¹ , W ² , W ³ and W ⁴ are each independently a halogen atom, a cyano group, —OCF ₃ , —OCF _{2
H, -CF 3, -CF 2 H} , -CFH 2, -CF 2 CF 3,
—OCF ₂ CF ₃ or a hydrogen atom, and W ¹ , W ² , W
Not all ³ and W ⁴ simultaneously represent a hydrogen atom,
When ^one of W ¹ , W ² , W ³ and W ⁴ is the above substituent other than a hydrogen atom, another substituent bonded to the same carbon atom is also selected from the above substituents other than a hydrogen atom. One of the substituents, wherein W ⁵ , W ⁶ , W ⁷ and W ⁸ are each independently a halogen atom, a cyano group, —OCF ₃ ,
_{OCF 2 H, -CF 3, -CF} 2 H, -CFH 2, -CF 2
CF _3, shows a -OCF ₂ CF ₃ or a hydrogen atom, W ^5,
All of W ⁶ , W ⁷ and W ⁸ do not simultaneously represent a hydrogen atom, and when one of W ⁵ , W ⁶ , W ⁷ and W ⁸ is the above substituent other than a hydrogen atom, When another substituent bonded to an atom also represents one of the above substituents other than a hydrogen atom, and one of W ^{5 and} W ⁶ represents one of a halogen atom or a cyano group Means that the other does not represent a halogen atom, a cyano group or a hydrogen atom, and when one of W ⁷ or W ⁸ represents one of a halogen atom or a cyano group, the other represents a halogen atom, a cyano group or a hydrogen atom. It does not represent a group or a hydrogen atom. ^{) X 1, X 2, X} 3 and X ⁴ each independently represents a single bond or one or more alkylene groups having 1 to 4 carbon atoms which may be substituted with a halogen atom of the hydrogen atoms in the group, Any methylene group in this alkylene group is -O
-, -S-, -CO-, -CS-, -CH = CH-,-
Although it may be substituted by C≡C— or —SiR ² R ³ —, —O— and —S— are not consecutive, and a ¹ ,
a ² , a ³ , a ⁴ and a ⁵ each independently represent 0 or 1, and each atom constituting these compounds may be substituted with its isotope. ) Thus, the compounds of the present invention are not readily conceivable from the prior art mentioned above.

In the general formula (1), R ¹ and Y ¹ are a straight-chain or branched alkyl group having 1 to 30 carbon atoms.
Propyl, butyl, pentyl, hexyl, heptyl, decyl, pentadecyl or icosyl, and isopropyl, sec-butyl, tert.
-Butyl, 2-methylbutyl, isopentyl, isohexyl, 3-ethyloctyl, 3,8-dimethyltetradecyl and 5-ethyl-5-methylnonadecyl. These alkyl groups are -O- and -S
Unless-is continuous, any methylene group in the group is -O
-, -S-, -CO-, -CS-, -CH = CH-,-
C≡C—, —SiR ² R ³ —, cyclopropane-1,2-
It may be substituted with diyl, cyclobutane-1,3-diyl or bicyclo [1.1.1] pentane-1,3-diyl.

Examples of such groups include alkoxy groups,
Alkoxyalkyl group, alkenyl group, alkadienyl group, alkenyloxy group, alkoxyalkenyl group, alkynyl group, alkynyloxy group, alkoxyalkynyl group, silanyl group, alkylsilyl group, alkoxysilyl group, alkylsilylalkyl group, alkoxysilylalkyl group , An alkyldisilanyl group, an alkyldisilanylalkyl group and an alkyltrisilanyl group. One or more hydrogen atoms in these groups may be substituted with a halogen atom. Examples thereof include a halogen-substituted alkyl group, a halogen-substituted alkoxy group, a halogen-substituted alkenyl group, a halogen-substituted alkenyloxy group, and a halogen-substituted alkynyl. And a halogen-substituted alkynyloxy group.

Among these, preferred groups are specifically exemplified. As a group in which a methylene group in an alkyl group is substituted by -O-, methoxy, ethoxy, propoxy, butoxy,
An alkoxy group such as pentyloxy, hexyloxy or nonyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl,
Methoxyoctyl, ethoxymethyl, ethoxyethyl,
Ethoxypropyl, ethoxyhexyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxypentyl, butoxymethyl, butoxyethyl, butoxybutyl, pentyloxymethyl, pentyloxybutyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, heptyloxymethyl Alternatively, an alkoxyalkyl group such as octyloxymethyl and the like may be represented by a branched alkoxy group such as 2-methylpropoxy, 2-methylpentoxy and 1-methylheptoxy.

Examples of the group in which the methylene group in the alkyl group is substituted with -S- include a methylthio, ethylthio, propylthio, butylthio and pentylthio group.

When the methylene group in the alkyl group is -CH = CH
As a group substituted with-an alkenyl group such as vinyl, propenyl, butenyl, pentenyl, hexenyl and decenyl, methoxypropenyl, ethoxypropenyl, pentyloxypropenyl, methoxybutenyl, ethoxybutenyl, pentyloxybutenyl, methoxypentenyl, propoxypentenyl, Alkoxyalkenyl groups such as methoxyhexenyl, propoxyhexenyl, methoxyheptenyl and methoxyoctenyl, alkenyloxy groups such as propenyloxy, butenyloxy, pentenyloxy, octenyloxy and propenyloxymethyl, propenyloxyethyl, propenyloxybutyl, butenyl Oxymethyl, butenyloxyethyl,
Groups such as butenyloxypentyl, pentenyloxymethyl, pentenyloxypropyl, hexenyloxymethyl, hexenyloxyethyl, heptenyloxymethyl and octenyloxymethyl, butadienyl groups such as butadienyl, heptadienyl, hexadienyl, heptadienyl, octadienyl and icosadienyl Can be shown.

Ethynyl, propynyl, butynyl, and the like, wherein the methylene group in the alkyl group is substituted by -C≡C-
Alkynyl groups such as pentynyl and octynyl, ethynyloxy, propynyloxy, butynyloxy, alkynyloxy groups such as pentynyloxy and tetradecynyloxy, methoxypropynyl, methoxypentynyl,
Alkoxyalkynyl groups such as ethoxybutynyl, propoxypropynyl, hexyloxyheptynyl, methoxymethylbutynyl, methoxypropylethynyl and butoxymethylpropynyl can be shown.

The methylene group in the alkyl group is -SiR ² R ³
As a group substituted with-, an alkylsilyl group such as methylsilyl, ethylsilyl, propylsilyl, butylsilyl, pentylsilyl and nonylsilyl, methylsilylmethyl, methylsilylethyl, methylsilylpropyl,
Methylsilylbutyl, methylsilylheptyl, ethylsilylmethyl, ethylsilylethyl, ethylsilylpropyl, ethylsilylhexyl, propylsilylmethyl, propylsilylethyl, propylsilylpropyl, butylsilylmethyl, butylsilylethyl, butylsilylpropyl, pentylsilyl Methyl, hexylsilylmethyl,
Alkylsilylalkyl groups such as hexylsilylethyl, heptylsilylmethyl and octylsilylmethyl, methoxysilyl, ethoxysilyl, propoxysilyl, butoxysilyl, pentyloxysilyl and octyloxysilyl, and other alkoxysilyl groups, silanyl, disilanyl, trisilanyl, tetrasilanyl , Silanyl groups such as pentasilanyl and decasilanyl,

Alkyldisilanyl groups such as methyldisilanyl, ethyldisilanyl, propyldisilanyl, butyldisilanyl, and pentyldisilanyl, and alkyltrisilyl groups such as methyltrisilanyl, ethyltrisilanyl, propyltrisilanyl and hexyltrisilanyl Nyl group, methylnonasilanyl, methyldisilanylmethyl, methyldisilanylethyl, methyldisilanylpentyl, ethyldisilanylmethyl, ethyldisilanylethyl, ethyldisilanylbutyl, ethyldisilanylhexyl, propyl Alkyldisilanylalkyl groups such as disilanylmethyl, butyldisilanylpentyl, pentyldisilanylmethyl, hexyldisilanylethyl and heptyldisilanylmethyl, methyltrisilanylmethyl, methyltrisilanylpentyl, ethyl Alkyltrisilanylalkyl groups such as lysilanylmethyl, ethyltrisilanylpropyl, propyltrisilanylmethyl, propyltrisilanylbutyl, butyltrisilanylmethyl, pentyltrisilanylmethyl and hexyltrisilanylmethyl; methylhexanilanyl Methyl, ethyl heptasilanylmethyl, methyloctacylanylmethyl, 2-fluoroethylsilyl,
3,3-difluoropropylsilyl and 1,2,3
3-tetrafluoropropylsilyl group, trimethylsilyl, dimethylethylsilyl, dimethylpropylsilyl,
Examples thereof include dimethylbutylsilyl, dimethylpentylsilyl and trimethylsilylmethyl.

As a group in which a methylene group in an alkyl group is substituted by -CO- or -CS-, methylcarbonyl, methylthiocarbonyl, ethylcarbonyl, propylcarbonyl, propylthiocarbonyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl , Heptyloxycarbonyl, 2-oxopropyl, 2-oxobutyl, 3-oxobutyl,
-Oxopentyl, 4-oxopentyl, 3-oxohexyl, 5-oxohexyl, 2-oxoheptyl, 3
-Oxoheptyl, 6-oxoheptyl, 2-oxooctyl, 4-oxooctyl, 7-oxooctyl, 3
Groups such as -oxononyl, 6-oxononyl, 8-oxononyl, 2-oxodecyl, 5-oxodecyl and 9-oxodecyl can be shown.

A hydrogen atom in these alkyl groups may be substituted with a halogen atom or a cyano group.
Specifically, fluoromethyl, 2-fluoroethyl, 2-
Chloroethyl, 2-cyanoethyl, 1,2-difluoroethyl, 3-fluoropropyl, 3-chloropropyl,
Halogen-substituted alkyl groups such as 3-cyanopropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 8,8-difluorooctyl; halogen-substituted alkoxy groups such as fluoromethoxy and 2-fluoroethoxy;

3-fluoropropenyl, 4-fluoro-
1-butenyl, 4-fluoro-2-butenyl, 5-fluoro-1-pentenyl, 5-fluoro-2-pentenyl, 5-fluoro-3-pentenyl, 6-fluoro-1
-Hexenyl, 6-fluoro-3-hexenyl, 7-fluoro-5-heptenyl, 3-fluoro-2-propenyl, 3-chloro-1-propenyl, 4-fluoro-3-
Butenyl, 5,5-difluoro-4-pentenyl, 3,
3-difluorohexenyl and 8,8-difluoro-
A halogen-substituted alkenyl group such as 7-octenyl can be shown.

The methylene group in the alkyl group may be cyclopropane-1,2-diyl, cyclobutane-1,3-diyl or bicyclo [1.1.1] pentane-1,3-
Diyl-substituted groups include cyclopropyl, 2-methylcyclopropyl, 2-ethylcyclohexyl,
Propylcyclohexyl, 2-cyclohexylethyl,
It may represent groups such as 3-cyclopropylpropyl, 3-methylcyclobutyl, 3-propylcyclobutyl, 3-propylbicyclo [1.1.1] pentyl and 3-butylbicyclo [1.1.1] pentyl. it can. Among the compounds represented by the general formula (1), a compound in which R ¹ or Y ¹ is an optically active group is particularly useful as a chiral dopant. By using these, the occurrence of a reverse twist domain can be prevented.

When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (1), R ¹ and Y ¹ are an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkenyl group. , An alkoxyalkenyl group or an alkylsilyl group, and more preferably a substituent having low polarity such as an alkyl group, an alkoxy group or an alkoxyalkyl group.

When it is desired to increase the elastic constant ratio K ₃₃ / K ₁₁ of the compound represented by the general formula (1), a double bond may be introduced into R ¹ and / or Y ¹ . When it is desired to lower the viscosity, a double bond, a triple bond or a di-substituted silyl group (—SiR ² R ³ —) may be introduced into R ¹ and / or Y ¹ . When you want to lower the threshold voltage, di-substituted silyl group (-SiR ² R ³ -) may be introduced. (R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.)

Chemical formula of the compound represented by the general formula (1)
When particular attention is paid to physical stability, R ¹ and Y ¹ are an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkenyl group, an alkoxyalkenyl group, an alkylsilyl group, a halogen-substituted alkyl group, a halogen-substituted alkoxy group or a halogen-substituted group. It is preferably an alkenyl group, more preferably an alkyl group, an alkoxy group, an alkoxyalkyl group, a halogen-substituted alkyl group or a halogen-substituted alkoxy group.

In the compound represented by the general formula (1),
Ring A ¹ , ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ are each independently of the general formula (2-1), (2-2) or (2-3)
A cyclohexane-1,4-diyl, silacyclohexane-1,4-diyl, silacyclohexane-2,5-diyl, 1,4-phenylene or bicyclo [1.1.1] pentane-1, Although it is 3-diyl, in order to achieve the object of the present invention, at least one is a ring represented by the general formula (2-1), (2-2) or (2-3).

In the ring represented by formula (2-1) or (2-2), W ¹ , W ² , W ³ and W ⁴ each independently represent a halogen atom, a cyano group, —OCF ₃ , OCF ₂ H,
_{-CF 3, -CF 2 H, -CFH} 2, -CF 2 CF 3, -O
Represents CF ₂ CF ₃ or a hydrogen atom, but not all of W ¹ , W ² , W ³ and W ⁴ are hydrogen atoms at the same time, and among W ¹ , W ² , W ³ and W ⁴ , When one is the above substituent other than a hydrogen atom, another is bonded to the same carbon atom.
The two substituents also represent one of the substituents selected from the above substituents other than a hydrogen atom. In the ring represented by the formula (2-3), W ⁵ , W ⁶ , W ⁷ and W ⁸ are each independently a halogen atom, a cyano group, —OCF ₃ , —OCF ₂ H, —CF ₃ ,
_{-CF 2 H, -CFH 2, -CF} 2 CF 3, -OCF 2 CF 3
Or a hydrogen atom, but not all of W ⁵ , W ⁶ , W ⁷ and W ⁸ are hydrogen atoms at the same time, and W ⁵ , W ⁶ ,
When one of W ⁷ and W ⁸ is the above substituent other than a hydrogen atom, the other substituent bonded to the same carbon atom also represents one of the above substituents other than a hydrogen atom. And when one of W ⁵ or W ⁶ is one of a halogen atom or a cyano group, the other is not a halogen atom, a cyano group or a hydrogen atom, and either of W ⁷ or W ⁸ When one is a halogen atom or a cyano group, the other is a halogen atom,
It cannot be a cyano group or a hydrogen atom. General formula (2
Specific examples of the rings represented by -1) and (2-2) include rings represented by formulas (3-1) to (3-4).

[0036]

Embedded image

The general formulas (2-1), (2-2) and (2)
Other than the ring represented by -3), preferred as ring A ¹ , ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ are cyclohexane-1,4-diyl, 1,4-phenylene, and Rings in which carbon atoms constituting these rings are substituted by nitrogen atoms or silicon atoms, and rings in which non-adjacent carbon atoms constituting these rings are substituted by oxygen atoms can be mentioned.
When a cis-trans isomer is present in these six-membered rings, a preferred steric structure is a trans-form.

Specifically, the following rings are exemplified. Bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, trans-silacyclohexane-1,4-diyl, trans -Silacyclohexane-2,5-diyl, 1,4-phenylene,
1,3-dioxane-2,5-diyl, pyrimidine-
2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dithiane-
2,5-diyl, 1,3-oxathiane-2,5-diyl, and bicyclo [2.2.2] octane-1,4-
Jiyl) etc. A hydrogen atom on these rings may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkyl group. More specifically, such rings include the rings shown below. 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-en-1,4-diyl, 2,2- Dichlorobicyclo [1.1.1] pentane-1,3-diyl,
Trans-1-methylsilacyclohexane-1,4-diyl, trans-1-methylsilacyclohexane-2,
5-diyl, fluoro-1,4-phenylene, 2,3-
Difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, chloro-1,4-phenylene,
2,3-dichloro-1,4-phenylene, 3,5-dichloro-1,4-phenylene, 2-fluoro-3-chlorophenylene and 3-fluoro-5-chlorophenylene.

Chemical formula of the compound represented by the general formula (1)
When particular attention is paid to physical stability, ring A ¹ , ring A ² , ring A
^3, the preferred ring to the ring A ⁴ and ring A ⁵ are of the general formula (2
The rings represented by 1), (2-2) and (2-3), and other than those, preferred for the ring A ¹ , the ring A ² , the ring A ³ , the ring A ⁴ and the ring A ⁵ are as follows: Example 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-en-1,4-diyl, 2,3- Difluoro-1,4-phenylene and 2,2-dichlorobicyclo [1.1.1] pentane-
1,3-diyl. As a ring in which a hydrogen atom on the ring is substituted with a fluorine atom, a chlorine atom, a cyano group or an alkyl group,
Bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-1,4-diyl, trans-silacyclohexane-1,4-diyl, trans -Silacyclohexane-2,5-diyl, 1,4-phenylene, 1,3-
Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridazine-3,6
-Diyl, 1,3-dithiane-2,5-diyl, and 1,3-oxathiane-2,5-diyl.

When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (1), the ring A ¹ ,
Preferred rings for ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ are those represented by formulas (2-1), (2-2) and (2-3). , Ring A ¹ , ring A ² , ring A ³ , ring A ⁴
And preferred compounds are exemplified below in the ring A ^5. 1-cyano-trans-cyclohexane-1,4-diyl,
2,2-difluoro-trans-cyclohexane-1,
4-diyl, 2-fluorocyclohex-1-ene-
1,4-diyl, 2,3-difluoro-1,4-phenylene, and 2,2-dichlorobicyclo [1.1.1]
Trans-cyclohexane-, such as pentane-1,3-diyl, in which a hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom, a cyano group or an alkyl group;
1,4-diyl, cyclohex-1-ene-1,4-diyl, trans-silacyclohexane-1,4-diyl, trans-silacyclohexane-2,5-diyl,
1,4-phenylene and pyridazine-3,6-diyl.

In the compound represented by the general formula (1),
X ¹ , X ² , X ³ and X ⁴ are each independently a single bond or an alkylene group having 1 to 4 carbon atoms in which at least one hydrogen atom in the group may be substituted by a halogen atom; one or more methylene groups in group ^{-SiR 2 R 3 -, - O-} ,
-CO-, -CS-, -CH = CH- or -C≡C-
May be substituted, but -O- is not consecutive. Preferably, they are a single bond, ethylene and butylene. The methylene group constituting the alkylene group is -SiR ² R ³
-, -O-, -CO-, -CS-, -CH = CH- or -C≡C- are exemplified below. 1,
2-disilanediyl, 1,1,2,2-tetramethyldisilanediyl, 1,4-tetrasilanediyl, 1-silaethylene, 1,1-dimethyl-1-silaethylene, 1-
Sila-1,4-butylene and 2-sila-1,4--SiR ² R ³ of the butylene - group having the methyleneoxy,
1-oxy-1,4-butylene, 2-oxy-1,4-
Groups having -O- such as butylene and an ester bond, -C such as vinylene, 1-butenylene and 2-butenylene;
A group having H = CH-,

Groups having -C≡C-, such as ethynylene, 1-butynylene, 2-butynylene and 3-butynylene;
And a group in which one or more hydrogen atoms in each of the above groups are substituted with a halogen atom, for example, fluoromethyleneoxy, oxyfluoromethylene, 1,1-difluoroethylene,
2,2-difluoroethylene, 1,2-difluorovinylene, 1-fluorovinylene, 1-chloro-2-fluorovinylene, 1,2-difluoro-1-butenylene,
2,3-difluoro-2-butenylene, and 3,4-
Difluoro-3-butenylene, other 3-oxy-1-
Butenylene and 4-oxy-1-butenylene.

When it is desired to further increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (1), X ¹ ,
Preferred groups for X ² , X ³ and X ⁴ are shown below. A single bond, ethylene, butylene, and the methylene group in these ethylene and butylene groups is -SiR ² R ^3- , -O
-, -CO-, -CS-, -CH = CH- or -C}
C-substituted groups.

When it is desired to increase the elastic constant ratio (K ₃₃ / K ₁₁ ) of the compound represented by the general formula (1), X ¹ , X ² , X
Either ³ and X ⁴ 1 one or more may be introduced double bond. When you want to lower the viscosity, X ^1, X ^2, in any one or more double bonds X ³ and X ^4, triple bonds or -SiR ² R ³ - can be introduced. When you want to lower the threshold voltage, -SiR ² R ³ - it can be introduced.

Chemical formula of the compound represented by the general formula (1)
When particular attention is paid to physical stability, preferred groups for X ¹ , X ² , X ³ and X ⁴ are exemplified below. Single bond, ethylene, butylene, and their ethylene and methylene groups in the butylene group ^{-SiR 2 R 3 -, - O} -, - CO- or been substituted with -CS-.

The compound of the present invention represented by the general formula (1) has a large absolute value of a negative dielectric anisotropy value. Therefore, by mainly using the compound of the present invention, a liquid crystal composition having a negative dielectric anisotropy value can be prepared.
Such a liquid crystal composition is, inter alia, a VA system, an IPS
It is useful for producing a device using a liquid crystal composition having a negative dielectric anisotropy value, such as a method. Further, by mixing the compound of the present invention with another liquid crystal compound or composition, an appropriate setting of the dielectric anisotropy value can be performed, so that the application range of the other liquid crystal compound or composition is expanded. be able to. The compound of the present invention represented by the general formula (1) has a small elastic constant and the temperature dependence of the constant is small. Therefore, a novel liquid crystal composition having a low driving voltage can be prepared by using the compound of the present invention.

The compound of the present invention represented by the general formula (1) has good compatibility with other liquid crystal compounds. For this reason, when the compound of the present invention is compounded in a liquid crystal composition, problems such as precipitation of the compound hardly occur. Further, the compound of the present invention can be incorporated in a large amount into the liquid crystal composition, and as a result, the excellent properties of the compound of the present invention can be strongly reflected in the liquid crystal composition.

The compound of the present invention represented by the general formula (1) can obtain a desired value of the refractive index anisotropy value by appropriately designing its structure. More specifically, the compound of the present invention can be prepared by appropriately selecting R ^{1 to} R ³ , Y ¹ , ring A ¹ to ring A ⁵ , X ^{1 to} X ⁴ and a ^{1 to} a ^5. Index anisotropy value can be obtained. More specifically, the refractive index anisotropy value can be adjusted by appropriately selecting the rings A ¹ , A ² , A ³ , A ⁴ and A ⁵ . That is, when a particularly high refractive index anisotropy value is required, a ring having many sites having a resonance structure such as an aromatic ring may be selected. When a low refractive index anisotropy value is required, a ring having many sites having no resonance structure, such as a trans-cyclohexane-1,4-diyl ring, may be selected. By freely choosing the refractive index anisotropy value,
The degree of freedom in designing a liquid crystal panel is increased.

Each of the compounds of the present invention represented by the general formula (1) is chemically and physically stable, and the liquid crystal composition using the compound has high specific resistance and high voltage holding ratio. It has high stability against external factors such as ultraviolet rays and heating, and has sufficient chemical and physical stability as a component of a practical liquid crystal composition.

The phase transition temperature of the compound of the present invention represented by the general formula (1) can be adjusted by appropriately selecting the number of rings. That is, a structure having four or more rings is required when a particularly high clearing point is required, a three-ring structure is required when a medium clearing point is required, and a two-ring structure is required when a particularly low clearing point is required. You just have to select More specifically,
The compound of the present invention represented by the general formula (1) includes a ¹ , a ² ,
By appropriately selecting a ³ , a ⁴ and a ⁵ , the phase transition temperature can be adjusted. That is, when a particularly high clearing point is required, the structure of four or more rings satisfying a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≧ 4 is used. When a medium clearing point is required, a ¹ + a ² + a ^{3 is used.} + A ⁴ + a ⁵ = 3, and when a particularly low clearing point is required, a ¹ + a ² + a ³ + a ⁴ +
What is necessary is just to select the bicyclic structure in which a ⁵ = 2.

The compounds of the present invention show exactly the same properties when the constituent atoms are substituted with their isotopes, and such substituted forms are also preferred.

As described above, the compound of the present invention represented by the general formula (1) has various physical properties suitable as an electro-optical display material. By using the compound of the present invention, a novel liquid crystal composition having good characteristics can be prepared. In addition, by appropriately designing the structure, a liquid crystal compound having characteristics according to the intended use, and a liquid crystal composition and a device using the same can be obtained. For example, the compound of the present invention is characterized by exhibiting a large negative dielectric anisotropy value. It can be added to a composition having a value to adjust its dielectric anisotropy value and other properties. More specifically, the compound of the present invention or a liquid crystal composition using the same may be prepared in various display systems (for example, a VA system, an IPS system, and an ECB system) using a compound or a composition having a negative dielectric anisotropy value. HAN system or DAP system), DS system, GH
System or PC system), especially the VA system, IPS
It can be preferably used for the method. Various display methods using a compound or a composition having a positive dielectric anisotropy value (for example,
Various characteristics (for example, a dielectric anisotropy value, an elastic constant, and the like) of a liquid crystal composition for a TN mode, an STN mode, or an AM mode (TFT mode or MIM mode) based on the TN mode.
Refractive index anisotropy, viscosity, or chemical and physical stability)
It can also be used for improvement and adjustment.

The aforementioned R ^{1 to} R ³ , Y ¹ , ring A ¹ to ring A ⁵ , X ¹
All the compounds of the present invention, suitably selected and combined from X ⁴ and a ^{1 to} a ⁵ , are preferred compounds having the characteristics unique to the compounds of the present invention, and more preferred compounds are those represented by the general formula (2) -1), (2-2) or (2-
It is a compound containing at least one ring represented by 3). One group of compounds having particularly preferable properties among such a group of compounds is represented by the following formulas (1-1) to (1-10).
It is a compound represented by 8).

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

Wherein R ¹ , Y ¹ , ring A ¹ to ring A ⁵ and X
^{1 to} X ⁴ have the same meanings as described above, and -SP- is any of the groups represented by formulas (2-1), (2-2) and (2-3). ) Of the above compound groups (1-1) to (1-108),
(1-1) to (1-6) show particularly low viscosity, and
32) to (1-108) show particularly high nematic-isotropic liquid phase transition temperatures.

The liquid crystalline compound of the present invention represented by the general formula (1) can be produced by a general organic synthesis method. Of these methods, only one example is shown below. For example, the ring site represented by the general formula (3-1) can be constructed according to a known method.

[0063]

Embedded image

(Wherein MG1 and MG2 represent organic compound residues (mesogens)) That is, the 4-methylidenecyclohexane derivative (15) is converted to trichloroacetic acid chloride according to the method described in, for example, JP-A-7-506117. With 1,1-dichloro-2
-An oxospiro [3.5] nonane derivative (16),
Next, Grignard reagent (MG
2-MgBr) to give (17), and then sequentially dehydrated with acid to (18), hydrogenated to (19),
Sodium hydroxide acts on (20) and finally diethylaminosulfur trifluoride (DAST) acts on (21) (the compound of the general formula (1) in which the spiro ring is the aforementioned (3-1)). Can be induced.

The ring site represented by the general formula (2-3) can also be constructed according to a known method.

[0066]

Embedded image

(Wherein, MG3, MG4 and MG5 represent organic compound residues (mesogens)) That is, for example, Organic Synthesis (vol.5), 297
According to the method of page (1973), cyclohexanecarboxylic acid chloride derivative (22) is dimerized to give dispiro [5.
1.5.1] Tetradecane-7,14-dione derivative (23). Then, phosphorus pentabromide is allowed to act on this derivative by a conventional method to obtain (24). (24) is the action of potassium cyanide (25)
And then potassium hydroxide to (26), sulfur tetrafluoride to (27), hydrogen deprotection to (28), alkyl bromide (MG3-Br) to (28). To 29), to (30) by oxidation of the hydroxyl group,
By the action of Grignard reagent (MG4-MgBr), (3
It can be led to 1), to (32) by dehydration with an acid, and finally to (33) by hydrogenation.

All the compounds of the present invention can be produced by appropriately combining the above-mentioned reactions according to the properties of the compounds. In addition, all the above-mentioned reactions are known, but it goes without saying that other known reactions can be used if necessary.

Hereinafter, the liquid crystal composition of the present invention will be described. The liquid crystal composition according to the present invention contains 0.1 to 99.9% by weight of at least one compound represented by the general formula (1).
Is preferable in order to exhibit excellent characteristics. More specifically, the liquid crystal composition provided by the present invention comprises, in addition to a first component containing at least one compound represented by the general formula (1), a compound represented by the general formula (4) depending on the purpose of the liquid crystal composition. It is completed by mixing compounds selected from the compound group represented by (14) in an appropriate ratio. Among the compounds represented by the general formulas (4) to (6),
The compounds preferably used in the liquid crystal composition of the present invention include the following compounds. (R ⁴ and Y ² have the same meaning as described above.)

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

The compounds represented by the general formulas (4) to (6) are compounds having a positive dielectric anisotropy value, have excellent thermal stability and chemical stability, and particularly have a voltage holding property. High rate,
Alternatively, it is a preferable compound when a liquid crystal composition for a TFT system requiring high reliability such as a large specific resistance value is prepared. When preparing a liquid crystal composition for a TFT mode, the amount of the compounds represented by the general formulas (4) to (6) is 0.1 to 99.9% by weight based on the total weight of the liquid crystal composition. Although it can be used in the range, it is preferably 10 to 97% by weight, more preferably 40 to 95% by weight. Further, the compounds represented by the general formulas (9) to (11) may be further contained for the purpose of adjusting the viscosity. When preparing liquid crystal compositions for the STN mode and the TN mode, general formulas (4) to
The compound represented by (6) can be used. In that case, the use amount of 50% by weight or less is preferable.

Among the compounds represented by formulas (7) and (8), the following compounds can be preferably used in the liquid crystal composition of the present invention. (R ⁵ ,
Y ³ and R ⁶ have the same meaning as described above. )

[0075]

Embedded image

[0076]

Embedded image

The compounds represented by the general formulas (7) and (8) have a positive and large dielectric anisotropy value and are used particularly for the purpose of reducing the threshold voltage of the liquid crystal composition. Also,
It is also used for the purpose of expanding the nematic range such as adjusting the refractive index anisotropy value and increasing the clearing point. Further, it is also used for the purpose of improving the steepness of the VT curve of the liquid crystal composition for STN mode or TN mode.

The compounds represented by the general formulas (7) and (8) are preferred especially when preparing liquid crystal compositions for STN mode and TN mode. General formula (7)-
When the use amount of the compound represented by (8) is increased, the threshold voltage of the liquid crystal composition decreases, and the viscosity increases.
Therefore, as long as the viscosity of the liquid crystal composition satisfies the required characteristics,
It is advantageous to use a large amount because it can be driven at a low voltage.
The amount of the compound represented by the general formulas (7) to (8) is S
When preparing a TN mode or a liquid crystal composition for the TN mode, it can be used in the range of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, more preferably 40 to 95% by weight.
% By weight.

Among the compounds represented by formulas (9) to (11), the following compounds can be mentioned as compounds preferably used in the liquid crystal composition of the present invention. (R ⁷ and R ⁸ have the same meaning as described above.)

[0080]

Embedded image

The compounds represented by the general formulas (9) to (11) are compounds having a small absolute value of dielectric anisotropy and being almost neutral. The compound represented by the general formula (9) is mainly used for adjusting the viscosity or adjusting the refractive index anisotropy value.
Further, the compounds represented by the general formulas (10) and (11) are used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. Increasing the amount of the compounds represented by the general formulas (9) to (11) increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, it is preferable to use a large amount as long as the required value of the threshold voltage of the liquid crystal composition is satisfied. The amount of the compounds represented by the general formulas (9) to (11) is preferably 40% by weight or less, more preferably 35% by weight or less when a liquid crystal composition for a TFT system is prepared. Further, when preparing a liquid crystal composition for STN mode or TN mode, preferably 70% by weight or less,
It is more preferably at most 60% by weight.

Among the compounds represented by the general formulas (12) to (14), the following compounds can be mentioned as compounds preferably used in the liquid crystal composition of the present invention. (R
⁹ and R ¹⁰ have the same meaning as described above. )

[0083]

Embedded image

The compounds represented by the general formulas (12) to (14) are compounds having a negative value of dielectric anisotropy like the compounds represented by the general formula (1), and are N-type liquid crystals. It is used as a base compound of the composition or for adjusting the dielectric anisotropy of a P-type liquid crystal composition. As another application, the compound represented by the general formula (12) is a bicyclic compound, and is mainly used for adjusting a threshold voltage, adjusting a viscosity, or adjusting a refractive index anisotropy value. The compound represented by the general formula (13) is used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. The compound represented by the general formula (14) is used for the purpose of increasing the nematic range, reducing the threshold voltage, and increasing the refractive index anisotropy value.

The compounds represented by the general formulas (12) to (14) are mainly used for an N-type liquid crystal composition. When the amount of the compound is increased, the threshold voltage of the liquid crystal composition is reduced. Becomes larger. Therefore, it is desirable to use a small amount as long as the required value of the threshold voltage of the liquid crystal composition is satisfied. However, since these compounds have an absolute value of negative dielectric anisotropy of 5 or less, if the content is less than 40% by weight, low voltage driving may not be performed in some cases. The amount of the compounds represented by the general formulas (12) to (14) is N
When preparing a liquid crystal composition for a TFT type TFT,
% By weight or more, more preferably 50 to 95% by weight. Further, for the purpose of controlling the elastic constant and improving the steepness of the VT curve of the liquid crystal composition, the general formula (1)
The compounds represented by 2) to (14) may be mixed with the P-type composition in some cases. General formulas (12) to (14) in this case
Is preferably 30% by weight or less.

In the liquid crystal composition of the present invention, OCB
(Optically Compensated Birefringence) Except for special cases such as a liquid crystal composition for a method, for the purpose of inducing a helical structure of the liquid crystal composition to adjust a necessary twist angle and preventing reverse twist (reverse twist), An optically active compound is added. Although any known optically active compounds can be used for such a purpose, preferred examples include the following optically active compounds.

[0087]

Embedded image

The liquid crystal composition of the present invention is usually added with these optically active compounds to adjust the twist pitch.
The pitch of the twist is preferably adjusted in the range of 40 to 200 μm for a liquid crystal composition for a TFT mode and a TN mode. 6 to 2 if the liquid crystal composition is for STN mode.
It is preferable to adjust to a range of 0 μm. In addition, bistable T
In the case of the N (Bistable TN) system, it is preferable to adjust the thickness to a range of 1.5 to 4 μm. Further, two or more optically active compounds may be added for the purpose of adjusting the temperature dependency of the pitch.

The liquid crystal composition of the present invention is prepared by a conventional method. Generally, a method of dissolving various components at a high temperature is used. Further, the liquid crystal composition of the present invention is a merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone,
Further, a dichroic dye such as a tetrazine-based dye can be added to use as a liquid crystal composition for GH mode. Alternatively, a liquid crystal composition for a polymer dispersed liquid crystal display device (PDLCD) represented by an NCAP manufactured by microencapsulating a nematic liquid crystal or a polymer network liquid crystal display device (PNLCD) formed by forming a three-dimensional network polymer in the liquid crystal. It can also be used as an object. In addition, it can be used as a liquid crystal composition for ECB mode and DS mode.

[0090]

EXAMPLES The production methods and use examples of the compounds of the present invention will be described in more detail with reference to the following examples. The present invention is not limited by the embodiments. In the description of the examples, N is a specified concentration (gram equivalent / l),
M indicates a molar concentration (mol / l).

Example 1 1,1-Difluoro-2- (2- (trans-4-
(2,3-difluoro-4-ethoxyphenyl) cyclohexyl) ethyl) -7-n-propylspiro [3.
5] Production of Nonane ( 12 , Compound No. 2-49)

[0092]

Embedded image

First Step Synthesis of 1- (2,3-difluorophenyl) -4- (2-hydroxyethylidene) cyclohexane ( 2 ) In a three-necked flask (3000 ml), 2-hydroxyethyltriphenylphosphonium bromide (387.3) was added.
g, 1.00 mol) and tetrahydrofuran (hereinafter abbreviated as THF) (1200 ml) were added, and the mixture was stirred at −30 ° C. under a nitrogen stream. Here, potassium t-butoxide (1
23.4 g, 1.10 mol) in small portions.
After stirring at 1 ° C. for 1 hour, 4- (4-ethoxy-2,3-difluorophenyl) cyclohexanone ( 1 ) (254.3)
g, 1.00 mol) in THF (800 ml).
The solution was added dropwise at a temperature not higher than ° C. After the dropwise addition, the mixture was returned to room temperature and stirred for 3 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted three times with toluene. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. N-Heptane (1000 ml) was added to the residue and stirred for 1 hour. The insoluble solid was filtered off, the filtrate was concentrated under reduced pressure, and the obtained syrup-like substance was purified by silica gel column chromatography (elution solvent: toluene) to obtain ( 2 ) (2)
46.5 g, 0.873 mol; yield 87%). MS / 282 (M ^<+> ).

Second stage trans-1- (2,3-difluorophenyl) -4-
Synthesis of (2-hydroxyethyl) cyclohexane ( 3 ) In a three-necked flask (2000 ml), ( 2 ) (246.0 g, 0.871 mol) obtained in the first step and ethyl acetate (1000 ml) were put. Dissolve, then 5
% Pd-C (20.00 g) was added. 4 under normal temperature and normal pressure
After performing catalytic reduction for one hour, the catalyst is filtered off, the filtrate is concentrated under reduced pressure, and the obtained residue is recrystallized three times with toluene to obtain ( 3 )
(124.4 g, 0.437 mol; yield 50%) was obtained. MS / 284 (M ^<+> ).

Third stage trans-1- (2,3-difluorophenyl) -4-
Synthesis of (2-bromoethyl) cyclohexane ( 4 ) In a three- necked flask (1000 ml), ( 3 ) (124.0 g, 0.436 mol) obtained in the second step and dichloromethane (400 ml) were placed, and the mixture was cooled to -10 under a nitrogen stream. ° C
With stirring. Here, phosphorus tribromide (39.37 g, 0.1
45 mol) at 0 ° C. or lower. After the dropwise addition, the mixture was returned to room temperature and stirred overnight. After completion of the reaction, the reaction solution was poured into a large amount of water, and the separated organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off. The residue was recrystallized from ethanol to give ( 4 ) (134.6 g, 0.1 g).
388 mol; yield 89%). MS / 347 (M ^<+> ).

Stage 4 Synthesis of 1-methylidene-4-n-propylcyclohexane ( 6 ) In a three-necked flask (3000 ml), methyltriphenylphosphonium bromide (357.2 g, 1.00 mol) was added.
l) and THF (1500 ml) were added, and the mixture was stirred at −10 ° C. under a nitrogen stream. Here, potassium t-butoxide (1
23.4 g, 1.10 mol) was added little by little, and -10 was added.
After stirring at 1 ° C. for 1 hour, 4-propylcyclohexanone ( 5 ) (140.2 g, 1.00 mol) in THF (2
00 ml) solution was added dropwise below 0 ° C. After the dropwise addition, the mixture was returned to room temperature and stirred for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted three times with toluene. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. N-Heptane (100
0 ml) and stirred for 1 hour. The insoluble solid was separated by filtration, and the residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent: toluene).
( 6 ) (123.6 g, 0.894 mol; yield 89)
%). MS / 138 (M ^<+> ).

Fifth Step Synthesis of 1,1-dichloro-2-oxo-7-n-propylspiro [3.5] nonane ( 7 ) A three-necked flask (3000 ml) was obtained in the fourth step ( 6 ). (123.1 g, 0.890 mol) and diethyl ether (1500 ml) were added, and the mixture was stirred at room temperature under a nitrogen stream. Here, a zinc (95%)-copper (5%) alloy (81.4
0 g) was added in small portions. Then, trichloroacetyl chloride (161.9 g, 0.890 mol) was added dropwise at room temperature. After the dropwise addition, the mixture was gently heated to reflux for 8 hours. After completion of the reaction, the insolubles were filtered off, the filtrate was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. The obtained oil was distilled under reduced pressure to obtain ( 7 ) (12).
9.1 g, 0.518 mol; yield: 58%). MS / 249 (M ^<+> ).

Sixth stage 1,1-dichloro-2-hydroxy-2- (2- (trans-4- (2,3-difluoro-4-ethoxyphenyl) cyclohexyl) ethyl) -7-n-propylspiro [ 3.5] Synthesis of Nonane ( 8 ) Metallic magnesium (11.26 g, 0.463 mol) and THF (1) were placed in a three-necked flask (3000 ml).
30 ml) and stirred at room temperature under a nitrogen stream. The ( 4 ) (134.0 g, 0.386 m) obtained in the third stage was added thereto.
ol) in THF (400 ml). After the start of the reaction, the dropwise addition was continued while adjusting the dropwise addition rate so that THF was gently refluxed. After the completion of the dropwise addition, the mixture was heated and refluxed for another 1 hour. Subsequently, the solution was cooled to 0 ° C., and a THF (250 ml) solution of ( 7 ) (96.16 g, 0.386 mol) obtained in the fifth step was added dropwise, followed by stirring at room temperature for 3 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution was added dropwise, and the mixture was extracted three times with toluene. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. The residue was recrystallized from a mixed solvent of n-heptane / ethyl acetate (10/1) to give ( 8 ) (157.
2 g, 0.304 mol; yield 79%). MS / 518 (M ^<+> ).

Seventh stage 2- (2- (trans-4- (2,3-difluoro-4)
-Ethoxyphenyl) cyclohexyl) ethyl) -3,
Synthesis of 3-dichloro-7-n-propylspiro [3.5] nonene ( 9 ) In an eggplant flask (2000 ml) equipped with a cooling tube and a Dean-Stark apparatus, ( 8 ) (15) obtained in the sixth step
6.5 g, 0.302 mol), toluene (600 m
l) and p-toluenesulfonic acid monohydrate (6.30)
g, 0.0331 mol) and heated to reflux for 4 hours while distilling off the produced water. After completion of the reaction, the organic phase was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine in that order, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. The residue was recrystallized with a mixed solvent of n-heptane / ethyl acetate (20/1) to obtain ( 9 ) (128.2 g, 0.257 mol; yield: 85%). MS / 500 (M ^<+> ).

Eighth stage 1,1-dichloro-2- (2- (trans-4- (2,
Synthesis of 3-difluoro-4-ethoxyphenyl) cyclohexyl) ethyl) -7-n-propylspiro [3.5] nonane ( 10 ) Obtained in a three-neck flask (2000 ml) in the seventh step ( 9 ) ( 127.6 g, 0.255 mol) and ethyl acetate (1200 ml) to dissolve and add 1%
Was added 5% Pd-C (12.7 g) loaded with sulfur. After performing catalytic reduction under normal temperature and normal pressure for 3 hours, the catalyst was filtered off. The residue obtained by concentrating the filtrate under reduced pressure was recrystallized twice with a mixed solvent of n-heptane / ethanol (50/1) to give ( 10 ) (121.5 g, 0.242 mol; yield 95%). Obtained. MS / 502 (M ^<+> ).

Ninth step 1-oxo-2- (2- (trans-4- (2,3-difluoro-4-ethoxyphenyl) cyclohexyl) ethyl) -7-n-propylspiro [3.5] nonane ( 1
1 ) Synthesis of ( 10 ) (121.0 g, 0.241 mol) obtained in the eighth step and methanol (400 ml) were placed in a three-necked flask (1000 ml) and stirred under ice-cooling. Here, sodium hydroxide (19.30 g, 0.483 mol)
l) methanol (200 ml) and water (100 m
A solution of the mixed solvent of 1) was added dropwise at 0 ° C. After stirring at room temperature for 2 hours, the mixture was concentrated under reduced pressure at room temperature until the volume became approximately half.
The concentrate was poured into a large amount of water and extracted three times with n-heptane. The organic phase was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. The residue was recrystallized from ethanol ( 11 ) (62.39 g, 0.1
(40 mol; yield: 58%). MS / 447 (M ^<+> ).

Tenth stage 1,1-difluoro-2- (2- (trans-4-
(2,3-difluoro-4-ethoxyphenyl) cyclohexyl) ethyl) -7-n-propylspiro [3.
5] Synthesis of nonane ( 12 ) The eggplant flask (100ml) obtained in the ninth stage ( 1)
1 ) (4.92 g, 0.0110 mol), benzene (50 ml) and diethylaminosulfur trifluoride (5.
33 g, 0.0331 mol) under a nitrogen stream.
Heated to reflux for an hour. After the reaction, pour the reaction solution into water,
Extracted twice with benzene. The organic phase was washed with 1N hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off after filtering off the desiccant. The residue was recrystallized three times with ethanol to give the title compound ( 12 ) (1.20 g, 0.0257).
mol, yield: 23%). MS / 469 (M ⁺ ), Composition of mother liquid crystal A

[0103]

Embedded image

Five kinds of ester compounds represented by the above general formula and having different alkyl groups (R ¹¹ , R ¹² ) at both terminals were mixed at the following ratio to prepare mother liquid crystals A. Δε = −1.5, Δn = 0.087 85 wt% of the above mother liquid crystals A and 15w of the title compound (12)
The values of this compound obtained by extrapolation from Δε and Δn (measured at 25 ° C.) of a composition consisting of t% are shown. Δε = −4.2, Δn = 0.071. The following compounds can be prepared by a method similar to that of Example 1.

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

Embedded image

[0169]

Embedded image

[0170]

Embedded image

[0171]

Embedded image

[0172]

Embedded image

[0173]

Embedded image

[0174]

Embedded image

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

As described above, the present invention has a low viscosity, a large absolute value, a negative dielectric anisotropy value, a controlled optical anisotropy value, a high specific resistance value, and a high specific resistance value. It is possible to provide a liquid crystal compound which has a voltage holding ratio and is stable against chemicals, heat and ultraviolet irradiation, a liquid crystal composition containing the same, and a liquid crystal display device manufactured using the liquid crystal composition. It became.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 213/26 C07D 213/26 213/30 213/30 239/26 239/26 319/06 319/06 C07F 7/08 C07F 7 / 08 C09K 19/32 C09K 19/32 19/34 19/34

Claims (13)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ and Y ¹ represent a linear or branched alkyl group having 1 to 30 carbon atoms, and any methylene group in the alkyl group may be -O-, -S-, -CO-, -CS- , -CH =
CH—, —C≡C—, —SiR ² R ³ —, cyclopropane-1,2-diyl, cyclobutane-1,3-diyl, or bicyclo [1.1.1] pentane-1,3-diyl Although it may be substituted, -O- and -S- are not continuous, and one or more hydrogen atoms in these groups may be substituted with a halogen atom or a cyano group, and R ² And R ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 3 carbon atoms, and each of ring A ¹ , ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ is Independently, general formula (2-1), (2-2) or (2)
Ring represented by -3), cyclohexane-1,4-diyl, silacyclohexane-1,4-diyl, silacyclohexane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine -2,5-diyl,
1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl or bicyclo [1.1.1] pentane-1,3-diyl, which includes ring A ¹ , ring A ² , ring A
^3, at least one of the general formulas of the rings A ⁴ and ring A ⁵ (2-1), a ring represented by (2-2) or (2-3), also any on these rings One or two hydrogen atoms of may be replaced with a halogen atom, (Wherein W ¹ , W ² , W ³ and W ⁴ are each independently a halogen atom, a cyano group, —OCF ₃ , —OCF ₂ H, —C
_{F 3, -CF 2 H, -CFH} 2, -CF 2 CF 3, -OCF 2
Represents CF ₃ or a hydrogen atom, but includes W ¹ , W ² , W ³ and W
Not all of ⁴ show hydrogen atoms at the same time, and W ¹ ,
When one of W ² , W ³ and W ⁴ is the above substituent other than a hydrogen atom, the other substituent bonded to the same carbon atom is also one of the substituents selected from the above substituents other than a hydrogen atom. Wherein W ⁵ , W ⁶ , W ⁷ and W ⁸ are each independently a halogen atom, a cyano group, —OCF ₃ , —OCF
_{2 H, -CF 3, -CF 2} H, -CFH 2, -CF 2 CF 3,
—OCF ₂ CF ₃ or a hydrogen atom, but W ⁵ , W ⁶ , W
Not all ⁷ and W ⁸ simultaneously represent a hydrogen atom,
When one of W ⁵ , W ⁶ , W ⁷ and W ⁸ is the above-mentioned substituent other than a hydrogen atom, another substituent bonded to the same carbon atom is also selected from the above-mentioned substituents other than a hydrogen atom. When one of W ⁵ or W ⁶ represents a halogen atom or a cyano group, the other does not represent a halogen atom, a cyano group or a hydrogen atom; When one of W ^{7 and} W ⁸ represents one halogen atom or a cyano group, the other does not represent a halogen atom, a cyano group, or a hydrogen atom. ^{) X 1, X 2, X} 3 and X ⁴ each independently represents a single bond or one or more alkylene groups having 1 to 4 carbon atoms which may be substituted with a halogen atom of the hydrogen atoms in the group, Any methylene group in this alkylene group is -O-, -S
-, -CO-, -CS-, -CH = CH-, -C≡C-
Or -SiR ² R ^3- ;
-And -S- are not continuous, and a ¹ , a ² ,
a ³ , a ⁴ and a ⁵ each independently represent 0 or 1,
Further, each atom constituting these compounds may be substituted with its isotope. )). 2. The liquid crystal compound according to claim 1, wherein the halogen atom in the ring represented by formula (2-1) or (2-2) is a fluorine atom. 3. The ring represented by the general formula (2-1) is represented by the formula (3-1) or (3-2), and the ring represented by the general formula (2-2)
The liquid crystal compound according to claim 1, wherein the ring represented by is a formula (3-3) or (3-4). Embedded image 4. A liquid crystal composition comprising at least two components, comprising at least one kind of the liquid crystal compound according to claim 1. Description: 5. A compound containing at least one compound according to any one of claims 1 to 3 as a first component,
A liquid crystal composition comprising, as a second component, at least one compound selected from the group consisting of compounds represented by formulas (4), (5) and (6). Embedded image (Wherein, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with —O— or —CH ＝ CH—,
One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y ² is a fluorine atom, a chlorine atom, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H ,
-CFH _2, -OCF ₂ CF ₂ H or -OCF ₂ CFHC
Shows the F _3, L ¹ and L ² represents a hydrogen atom or a fluorine atom each independently, Z ¹ and Z ² are each independently -
_{(CH 2) 2 -, -} (CH 2) 4 -, - COO -, - CF 2
_{O -, - OCF 2 -,} - CH = CH- or a single bond, the ring Q ¹ is trans - cyclohexane-1,4-diyl, 1,3-dioxane-2,5-diyl or a hydrogen atom, a fluorine Represents 1,4-phenylene which may be substituted with an atom, and ring Q ² represents trans-cyclohexane-
1,4-diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom, and each atom constituting these compounds may be substituted by its isotope. ) 6. A compound containing at least one compound according to claim 1 as a first component,
A liquid crystal composition comprising, as the second component, at least one compound selected from the group consisting of compounds represented by formulas (7) and (8). Embedded image (Wherein, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms;
At least one methylene group may be substituted with -O- or -CH = CH-, and one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom;
³ represents a cyano group or —C≡C—CN, and ring Q ³ represents trans-cyclohexane-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2, Represents 5-diyl, and ring Q ⁴ is trans-
Cyclohexane-1,4-diyl, pyrimidine-2,5
-Diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom, ring Q ⁵ represents trans-cyclohexane-1,4-diyl or 1,4-phenylene, and Z ³ represents- (CH ₂ ) ₂ —, —COO— or a single bond, L ³ , L ⁴ and L ⁵ each independently represent a hydrogen atom or a fluorine atom, b, c and d each independently represent 0 or 1 And each atom constituting these compounds may be substituted with its isotope. ) 7. A compound containing at least one compound according to any one of claims 1 to 3 as a first component,
The second component contains at least one compound selected from the compound group consisting of the general formulas (4), (5) and (6), and the third component has a general formula (9)
A liquid crystal composition comprising at least one compound selected from the group consisting of (10) and (11). Embedded image (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms;
One or more methylene groups may be substituted with an oxygen atom or -CH = CH-, and one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom;
Ring Q ⁶ , ring Q ⁷ and ring Q ⁸ are each independently trans-
Cyclohexane-1,4-diyl, pyrimidine-2,5
-Diyl or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom, wherein Z ⁴ and Z ⁵ are each independently —C≡C—, —COO—, — (CH ₂ )
_{It represents 2-} , -CH = CH- or a single bond, and each atom constituting these compounds may be substituted with its isotope. ) 8. A compound containing at least one compound according to any one of claims 1 to 3 as a first component,
As the second component, general formulas (12), (13) and (1)
A liquid crystal composition comprising at least one compound selected from the compound group consisting of 4). Embedded image (Wherein, R ⁹ and R ¹⁰ each independently represent a carbon number of 1 to 10)
Wherein at least one non-adjacent methylene group in the alkyl group is an oxygen atom or -CH = CH-
And may be substituted with 1 in this alkyl group.
Two or more hydrogen atoms may be substituted by a fluorine atom, and ring Q ⁹ and ring Q ¹⁰ each independently represent trans-cyclohexane-1,4-diyl or 1,4-phenylene, L ⁶ and L ⁷ each independently represents a hydrogen atom or a fluorine atom, but does not represent a hydrogen atom at the same time,
Z ⁶ and Z ⁷ are each independently — (CH ₂ ) ₂ —, —CO
It represents O- or a single bond, and each atom constituting these compounds may be substituted with its isotope. ) 9. A compound containing at least one compound according to any one of claims 1 to 3 as a first component,
The second component contains at least one compound selected from the compound group consisting of the general formulas (9), (10) and (11), and the third component has the general formula (1)
2) A liquid crystal composition comprising at least one compound selected from the group consisting of compounds (13) and (14). 10. The method according to claim 1, wherein the first component is
And at least one compound selected from the compound group consisting of the general formulas (7) and (8) as a second component, and a third component The general formulas (9) and (1)
A liquid crystal composition comprising at least one compound selected from the group consisting of compounds (0) and (11). 11. The first component according to claim 1, wherein
And at least one compound selected from the group consisting of the general formulas (4), (5) and (6) as a second component. , As the third component, the general formula (7)
And at least one compound selected from the compound group consisting of (8) and at least a compound selected from the compound group consisting of the general formulas (9), (10) and (11) as the fourth component. A liquid crystal composition comprising one type. 12. A liquid crystal composition according to claim 4, further comprising at least one optically active compound. 13. A liquid crystal display device comprising the liquid crystal composition according to claim 4. Description: