JPH1045639A - Bisalkenyl derivative, liquid crystalline compound and liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new low-viscosity liquid crystalline compound simultaneously bearing (halogen-substituted) alkenyl and halogen-substituted alkenyl groups on both the terminals, wide in liquid crystal phase temperature range, high in elastic constant ratio, and excellent in solubility at low temperatures, thus useful for liquid crystal display elements. SOLUTION: This new liquid crystalline compound is shown by formula I [A1 to A4 are each trans-1,4-(sila)cyclohexylene, etc.; Z1 to Z3 are each (CH2 )2 , CH=CH, a covalent bond, etc.; Q3 and Q4 are each H, F, Cl or Br; Q1 and Q2 are each the same as Q3 or a 2-5C alkenyl; (l), (m) and (n) are each 0-5; (p) and (q) are each 0 or 1], e.g. 1-(2,2-difluoroethenyl)-trans-4-[trans-4-(3-butenyl) cyclohexyl]cyclohexane. The compound of formula I is obtained by reaction of a compound of formula II (MSG is a group of formula III) with a compound of formula IV (Ph is phenyl; X is Cl, Br or I) to form a compound which is then subjected to a diisobutylaluminum halide into an aldehyde form which, in turn, is reacted with a compound of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal compound and a liquid crystal composition, and more particularly to a novel liquid crystal compound having both an alkenyl group which may be halogen-substituted and a halogen-substituted alkenyl group at both terminals of the compound. ,
The present invention also relates to a liquid crystal composition containing these, and a liquid crystal display device formed using the liquid crystal composition.

[0002]

2. Description of the Related Art A large number of display devices utilizing the anisotropy of the refractive index and the anisotropy of the dielectric constant, which are characteristics of liquid crystal compounds, have been produced. Display elements are widely used in watches, calculators, word processors, televisions, and the like, and demands are increasing year by year. The liquid crystal phase is located between the solid phase and the liquid phase, and the phases are roughly classified into a nematic phase, a smectic phase, and a cholesteric phase. Among them, a display device using a nematic phase is currently most widely used. Further, as a display method applied to a liquid crystal display, a TN (twisted nematic) type, a DS (dynamic scattering) for an electro-optic effect.
Type, guest-host type, DAP type and the like. In particular, recently, the colorization of liquid crystal displays has been further advanced, and the display method is T
In the N-type, a thin film transistor (TFT) system and a super twist nematic (STN) system are mainstream, and these display elements are mass-produced. Many liquid crystal compounds including those at the research stage have been known to date, but at present, there is no substance used as a single liquid crystal substance encapsulated in a display element. This is because the liquid crystal compound expected as a material for a display element is preferably used in the natural world, particularly, a substance showing a liquid crystal phase in a temperature range as wide as possible, especially at room temperature, which is most frequently used as a display element. This is because it must be sufficiently stable against environmental factors and have physical properties sufficient to drive the display element, but no single substance satisfying these conditions has been found. . Therefore, at present, a composition having such characteristics is prepared by mixing several kinds of liquid crystal compounds or non-liquid crystal compounds, and is practically used as a material. These liquid crystal compositions are required to be stable to moisture, light, heat, air, and the like normally existing in a use environment. In addition, it is necessary that the liquid crystal compounds to be mixed are chemically stable in an environment in which they are used with each other. The liquid crystal composition has a refractive index anisotropy value (△ n), a dielectric anisotropy value (△ ε), a viscosity (η), an electric conductivity and an elastic constant ratio K _33.
/ K ₁₁ (K ₃₃ : bend constant, K ₁₁ : splay elastic constant)
It is necessary to take appropriate values of various physical properties such as the values depending on the display method and the shape of the element. It is important that the components in the liquid crystal composition have good mutual solubility. Among these physical property values, those required for the liquid crystal compound used in the STN display mode are particularly those having a wide liquid crystal phase temperature range, low viscosity, and a large elastic constant ratio K ₃₃ / K ₁₁ . Recently, the environment in which display elements are used has been diversified,
Is from the request associated therewith require a material having a wide liquid crystal phase temperature range, also low viscosity is essential characteristic for achieving high-speed response, a larger elastic constant ratio K ₃₃
/ K ₁₁ steeply changes the transmittance near the threshold voltage and enables a display device with high contrast. In general, compounds having an alkenyl group are known to exhibit low viscosity. However, when a compound having an alkyl group is compared with a compound having an alkenyl group, the compound having an alkenyl group has a tendency that although the smecticity is reduced, the liquid crystal phase temperature region is also reduced. Specifically, when comparing compounds (a-1) to (c-2) described in V. Vill, Landolt-Wernstein,
In (a-1) and (a-2) of the bicyclohexyl derivative, the clearing point of (a-2) having an alkenyl group is about 1 ° C. higher than that of (a-1) having an alkyl group. It has increased by about 23 ° C. Therefore, the liquid crystal phase temperature region is reduced by about 22 ° C. The tendency of the clearing point and the melting point of this alkenyl group-substituted product to rise is also seen from the comparison between (b-1) and (b-2) of the cyclohexylphenyl derivative,
The liquid crystal phase temperature region has decreased by about 10 ° C. In the biphenyl derivatives (c-1) and (c-2), the liquid crystal phase temperature region decreased by about 37 ° C. due to a decrease in the clearing point and an increase in the melting point of the alkenyl group-substituted product. In any case, when the alkyl group is substituted with the alkenyl group, it can be seen that the liquid crystal phase temperature range is significantly reduced. In general, compounds having a large elastic constant ratio K ₃₃ / K ₁₁ are disclosed in
Compound (d) described in -30382 or Japanese Patent Publication No.
Compounds having an alkenyl group in the side chain, such as the compound (e) described in No. 2653, are already known. However, these compounds are poor in exhibiting a liquid crystal phase, and even when a liquid crystal phase is developed, the temperature range thereof is very narrow. Therefore, when used as a component of the liquid crystal composition,
Precipitation of crystals or development of a smectic phase may be observed in the low temperature range, and the solubility at low temperature cannot be said to be good.

Embedded image

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the problems of the prior art, particularly wide liquid crystal phase temperature range, low viscosity, large elastic constant ratio K ₃₃ / K _11, at a low temperature It is an object of the present invention to provide a liquid crystal compound having improved solubility, a liquid crystal composition containing the same, and a liquid crystal display device formed using the liquid crystal composition.

[0004]

The invention claimed in the present application is as follows.

(1) General formula (1)

Embedded image (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ).

(2) In the general formula (1), p, q and n are 0, Q ₃ and Q ₄ are F, Z ₃ is a covalent bond, and A
_3. The liquid crystal compound according to the above (1), wherein A ₄ is a trans-1,4-cyclohexylene group. (3) In the general formula (1), p and q are 0, Q ₃ and Q ₄ are F, Z ₃ is a covalent bond, and A ₃ and A ₄ are trans-
The liquid crystal compound according to the above (1), which is a 1,4-cyclohexylene group. (4) In the general formula (1), p and n are 0, q is 1, and Q
₃ , Q ₄ is F, Z ₂ , Z ₃ is a covalent bond, and A ₂ , A
_3. The liquid crystal compound according to the above (1), wherein A ₄ is a trans-1,4-cyclohexylene group.

(5) In the general formula (1), p is 0, q is 1, Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds,
_2. The liquid crystalline compound according to the above (1), wherein ₂ , A ₃ and A ₄ are trans-1,4-cyclohexylene groups. (6) In the general formula (1), p and n are 0, q is 1, and Q
_3, Q ₄ is the F, covalent bond Z _2, Z _3, A ₂ is 1,4-phenylene group, A _3, A ₄ is trans -
The liquid crystal compound according to the above (1), which is a 1,4-cyclohexylene group. (7) In the general formula (1), p is 0, q is 1, Q ₃ , Q
₄ is F, Z ₂ and Z ₃ are covalent bonds, and A ₂ is 1,4-
A phenylene group, and A ₃ and A ₄ are trans-1,4-
The liquid crystal compound according to the above (1), which is a cyclohexylene group.

(8) In the general formula (1), p and n are 0,
q is 1, Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds, A ₂ and A ₃ are 1,4-phenylene groups, and A ₄ is trans-1,4-cyclohexylene group The liquid crystal compound according to the above (1), wherein (9) In the general formula (1), p is 0, q is 1, Q ₃ , Q
₄ is F, Z ₂ and Z ₃ are covalent bonds, A ₂ and A ₃ are 1,4-phenylene groups, and A ₄ is trans-1,4
-The liquid crystalline compound according to the above (1), which is a cyclohexylene group. (10) In the general formula (1), p and q are 1, n is 0, Q
₃ , Q ₄ is F, Z ₁ , Z ₂ , and Z ₃ are covalent bonds;
The liquid crystal compound according to the above (1), wherein ₁ and A _{4 each} represent a trans-1,4-cyclohexylene group, and A ₂ and A _{3 each} represent a 1,4-phenylene group.

(11) In the general formula (1), p and q are 1, Q ₃ and Q ₄ are F, Z ₁ , Z ₂ and Z ₃ are covalent bonds, and A ₁ and A ₄ are trans-1, The liquid crystal compound according to the above (1), which represents a 4-cyclohexylene group and A ₂ and A ₃ are 1,4-phenylene groups. (12) A liquid crystal composition comprising at least one component containing at least one component of the liquid crystalline compound according to any one of (1) to (11), and a liquid crystal display device using the same.

(13) As a first component, at least one liquid crystal compound represented by the general formula (1) is contained,

Embedded image (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ) As the second component, general formulas (2), (3) and (4)

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 10 carbon atoms;
₁ is F, Cl, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂
H or CFH ₂ , L ₁ , L ₂ , L ₃ and L ₄
Represents H or F independently of each other, Z ₄ and Z ₅ independently represent — (CH ₂ ) ₂ —, —CH ＝ CH— or a covalent bond, and a represents 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of:

(14) As a first component, at least one liquid crystal compound represented by the general formula (1) is contained,

Embedded image (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ) As the second component, general formulas (5), (6), (7),
(8) and (9)

Embedded image (Wherein, R ₂ represents F, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group (—CH ₂ —) in the alkyl group or alkenyl group)
May be substituted by an oxygen atom (-O-), but two or more methylene groups are not successively substituted by an oxygen atom. Ring A is a trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5
-Diyl group or 1,3-dioxane-2,5-diyl group; ring B is trans-1,4-cyclohexylene group, 1,4-phenylene group or pyrimidine-2,5-
It indicates diyl group, ring C represents trans-1,4-cyclohexylene group or 1,4-phenylene group, the Z ₆ -
(CH ₂ ) ₂ —, —COO— or a covalent bond;
₅ and L ₆ each independently represent H or F, and b and c each independently represent 0 or 1. )

Embedded image (Wherein, R ₃ represents an alkyl group having 1 to 10 carbon atoms;
₇ represents H or F, and d represents 0 or 1. )

Embedded image (Wherein, R ₄ represents an alkyl group having 1 to 10 carbon atoms, ring D and ring E independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group,
₇ and Z ₈ independently represent —COO— or a covalent bond, Z ₉ represents —COO— or —C≡C—,
L ₈ and L ₉ independently represent H or F;
₂ represents F, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g independently represent 0
Or 1 is indicated. )

Embedded image (Wherein, R ₅ and R ₆ are independently of each other having 1 to 1 carbon atoms.
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring G is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and Z ₁₀ represents —C≡C—, —COO—, — (CH
_{2) 2 -, - CH =} CH-C≡C- or indicates a covalent bond, Z ₁₁ represents a -COO- or a covalent bond. )

Embedded image (Wherein, R ₇ and R ₈ are independently of each other having 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring I is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
A 1,4-cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group in which one or more hydrogen atoms on the ring may be substituted with F, and a ring K is trans-1 , 4-cyclohexylene or 1,4-phenylene, wherein Z ₁₂ and Z ₁₄ independently of one another
_{OO -, - (CH 2)} 2 - or indicates a covalent bond, Z ₁₃
Represents -CH = CH-, -C≡C-, -COO- or a covalent bond, and h represents 0 or 1. A liquid crystal composition comprising at least one compound selected from the group consisting of:

(15) As a first component, at least one liquid crystal compound represented by the general formula (1) is contained,

Embedded image (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. As a part of the second component, at least one compound selected from the group consisting of general formulas (2), (3) and (4)
Contains

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 10 carbon atoms;
₁ is F, Cl, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂
H or CFH ₂ , L ₁ , L ₂ , L ₃ and L ₄
Represents H or F independently of each other, Z ₄ and Z ₅ independently represent — (CH ₂ ) ₂ —, —CH ＝ CH— or a covalent bond, and a represents 1 or 2. ) As other parts of the second component, general formulas (5), (6),
(7) containing at least one compound selected from the group consisting of (8) and (9)

Embedded image (Wherein, R ₂ represents F, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group (—CH ₂ —) in the alkyl group or alkenyl group)
May be substituted by an oxygen atom (-O-), but two or more methylene groups are not successively substituted by an oxygen atom. Ring A is a trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5
-Diyl group or 1,3-dioxane-2,5-diyl group; ring B is trans-1,4-cyclohexylene group, 1,4-phenylene group or pyrimidine-2,5-
It indicates diyl group, ring C represents trans-1,4-cyclohexylene group or 1,4-phenylene group, the Z ₆ -
(CH ₂ ) ₂ —, —COO— or a covalent bond;
₅ and L ₆ each independently represent H or F, and b and c each independently represent 0 or 1. )

Embedded image (Wherein, R ₃ represents an alkyl group having 1 to 10 carbon atoms;
₇ represents H or F, and d represents 0 or 1. )

Embedded image (Wherein, R ₄ represents an alkyl group having 1 to 10 carbon atoms, ring D and ring E independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group,
₇ and Z ₈ independently represent —COO— or a covalent bond, Z ₉ represents —COO— or —C≡C—,
L ₈ and L ₉ independently represent H or F;
₂ represents F, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g independently represent 0
Or 1 is indicated. )

Embedded image (Wherein, R ₅ and R ₆ are independently of each other having 1 to 1 carbon atoms.
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring G is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and Z ₁₀ represents —C≡C—, —COO—, — (CH
_{2) 2 -, - CH =} CH-C≡C- or indicates a covalent bond, Z ₁₁ represents a -COO- or a covalent bond. )

Embedded image (Wherein, R ₇ and R ₈ are independently of each other having 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring I is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
A 1,4-cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group in which one or more hydrogen atoms on the ring may be substituted with F, and a ring K is trans-1 , 4-cyclohexylene or 1,4-phenylene, wherein Z ₁₂ and Z ₁₄ independently of one another
_{OO -, - (CH 2)} 2 - or indicates a covalent bond, Z ₁₃
Represents -CH = CH-, -C≡C-, -COO- or a covalent bond, and h represents 0 or 1. A) a liquid crystal composition and a liquid crystal display device using the same.

The liquid crystalline compound represented by the general formula (1) of the present invention is characterized in that it is a bi- to tetracyclic derivative having a halogen atom-substituted alkenyl group and an alkenyl group simultaneously as substituents at both ends of the molecule. These liquid crystal compounds are not only extremely stable physically and chemically under the conditions in which the display element is used, but also have a wide liquid crystal phase temperature range, and their solubility in liquid crystal compositions even at low temperatures. , Low viscosity, and a large elastic constant ratio K ₃₃ / K ₁₁ . In addition, desired physical properties can be arbitrarily adjusted by appropriately selecting a ring structure, a bonding group, or a side chain structure among the molecular constituent elements. Therefore, when the compound of the present invention is used as a component of a liquid crystal composition, good properties are described in detail. 1) Despite having an alkenyl group, it has a wide liquid crystal phase temperature range. 2) Due to low viscosity, a decrease in threshold voltage and an improvement in response speed are observed. 3) It is possible to prepare a stable nematic liquid crystal composition in which no crystals are precipitated and no smectic phase is developed even at a very low temperature. 4) High contrast is possible because the elastic constant ratio K ₃₃ / K ₁₁ is improved. Thus, it is possible to provide a novel liquid crystal composition and a liquid crystal display element which are stable to an external environment, can be used in an increased operating temperature range, can be driven at a low voltage, can respond at high speed, and can achieve high contrast.

Compounds having a halogen-substituted alkenyl group independently as a molecular terminal group have already been disclosed in JP-A-1-175947.
And JP-A-1-308239. However, these compounds have a strong expression of a smectic phase and a narrow liquid crystal phase temperature range. In addition, the elastic constant ratio K ₃₃ / K
₁₁ is not too big. Needless to say, all of the compounds of the present invention show suitable physical properties, but A ₁ and A _{1 of} the formula (1)
_{2, A 3, A 4,} Z 1, Z 2, Z 3, Q 1, Q 2, Q
By using a compound in which ₃ , Q ₄ , l, m, n, p and q are appropriately selected, a liquid crystal composition suitable for the purpose can be prepared. That is, when used in a liquid crystal composition in which the temperature range in which a liquid crystal phase is developed must be on the higher temperature side, p
= Q = 1, a bicyclic or tricyclic compound may be used. If a low-viscosity compound is required, A ₃ and A ₄ may be trans-
A bicyclic compound which is a 1,4-cyclohexylene group may be used. Furthermore, those obtained by substituting fluorine on the 1,4-phenylene group show particularly excellent low-temperature solubility.

If an appropriate value of the refractive index anisotropy is required, A ₁ , A ₂ , A ₃ and A ₄ are 1,4-phenylene groups, and Z ₁ , Z ₂ and Z ₃ are covalent bonds. May be appropriately selected.

Hereinafter, R ₉ is a group represented by the following:

Embedded image

Hereinafter, R ₁₀ is a group represented by the following:

Embedded image

Cyc described below is a trans-1,4-cyclohexylene group, and Phe is a 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom. The compounds of the invention represented by the general formula (1) are classified as follows. Compound having two 6-membered rings R ₉ -A ₃ -A ₄ -R ₁₀ (1a) R ₉ -A ₃ -Z ₃ -A ₄ -R ₁₀ (1b) Compound R having 3 6-membered rings R _{9 -A 2 -A 3 -A 4 -R} 10 (1c) R 9 -A 2 -Z 2 -A 3 -A 4 -R 10 (1d) R 9 -A 2 -A 3 -Z 3 -A 4 —R ₁₀ (1e) R ₉ —A ₂ —Z ₂ —A ₃ —Z ₃ —A ₄ —R ₁₀ (1f) Compound having four 6-membered rings R ₉ —A ₁ —A ₂ —A ₃ — _{A 4 -R 10 (1g) R} 9 -A 1 -Z 1 -A 2 -A 3 -A 4 -R 10 (1h) R 9 -A 1 -A 2 -Z 2 -A 3 -A 4 -R _{10 (1i) R 9 -A 1} -A 2 -A 3 -Z 3 -A 4 -R 10 (1j) R 9 -A 1 -Z 1 -A 2 -Z 2 -A 3 -A 4 -R 10 _{(1k) R 9 -A 1 -Z} 1 -A 2 -A 3 -Z 3 -A 4 -R 10 (1l) R 9 -A 1 -A 2 -Z 2 -A 3 -Z 3 -A 4 - _{10 (1m) R 9 -A 1} -Z 1 -A 2 -Z 2 -A 3 -Z 3 -A 4 -R 10 (1n) Among these compounds, especially those of the formula (1a), and (1c) ( The compound represented by 1g) is preferable for achieving the object of the present invention.

The compound represented by the formula (1a) is further developed into compounds represented by the following formulas (1aa) to (1ac). R ₉ -Cyc-Cy-R ₁₀ (1aa) R ₉ -Phe-Cyc-R ₁₀ (1ab) R ₉ -Phe-Phe-R ₁₀ (1ac) Among these compounds, particularly (1aa) and (1ab)
Are preferred. These bicyclic compounds exhibit broad liquid crystal phase temperature range, a markedly low viscosity, exhibits a large elastic constant ratio K ₃₃ / K _11, significantly only viscosity without lowering clearing points when used in the liquid crystal composition Can be reduced.

The compound represented by the formula (1c) is further developed into compounds represented by the following formulas (1ca) to (1cd). R ₉ -Cyc-Cyc-Cy-R ₁₀ (1ca) R ₉ -Phe-Cyc-Cyc-R ₁₀ (1cb) R ₉ -Phe-Phe-Cyc-R ₁₀ (1 cc) R ₉ -Phe-Phe-Phe —R ₁₀ (1cd) Among these compounds, the compounds represented by (1ca), (1cb) and (1cc) are particularly preferred. These tricyclic compounds also exhibit the same properties as the bicyclic compounds, but when used in a liquid crystal composition, the clearing point can be set higher.

The compound represented by the formula (1g) is further developed into compounds represented by the following formulas (1ga) to (1gc). R ₉ -Cyc-Cyc-Cy-Cy-R ₁₀ (1 ga) R ₉ -Cyc-Phe-Phe-Cyc-R ₁₀ (1 gb) R ₉ -Cyc-Phe-Phe-Phe-R ₁₀ (1gc) Among the compounds, the compound represented by (1 gb) is particularly preferred. These tetracyclic compounds also have a high clearing point and a relatively low viscosity, and when used in a liquid crystal composition, can increase only the clearing point while maintaining the viscosity.

As described above, the formulas (1aa), (1ab),
(1ca), (1cb), (1cc) and (1gb)
Can be said to be particularly preferable examples, and among them, the following formulas (1-1) to
The compound represented by (1-5) can be mentioned.

[0023]

Embedded image

In all of the compounds described above, R ₉ is an alkenyl group in which an arbitrary H atom having 2 to 12 carbon atoms may be substituted by an F atom. Among them, particularly preferred groups are vinyl and 1-propenyl. , 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,5-hexadienyl, 2-fluoroethenyl,
3-fluoro-1-propenyl, 3-fluoro-2-propenyl, 4-fluoro-1-butenyl, 4-fluoro-2-butenyl, 4-fluoro-3-butenyl, 5-fluoro-1-pentenyl, 5- Fluoro-2-pentenyl, 5-fluoro-3-pentenyl, 5-fluoro-4
-Pentenyl, 2,2-difluoroethenyl, 3,3-
Difluoro-2-propenyl, 4,4-difluoro-3
-Butenyl, 5,5-difluoro-4-pentenyl,
6,6-difluoro-5-hexenyl. Also, R
Reference numeral ₁₀ denotes a difluoroalkenyl group in which an arbitrary F atom having 2 to 7 carbon atoms may be substituted by a Cl atom. Among them, particularly preferred groups are 2,2-difluoroethenyl and 3,3.
-Difluoro-2-propenyl, 4,4-difluoro-
3-butenyl, 5,5-difluoro-4-pentenyl,
6,6-difluoro-5-hexenyl, 7,7-difluoro-6-heptenyl, 2-chloro-2-fluoroethenyl, 3-chloro-3-fluoro-2-propenyl,
-Chloro-4-fluoro-3-butenyl, 5-chloro-
5-fluoro-4-pentenyl, 6-chloro-6-fluoro-5-hexenyl, 7-chloro-7-fluoro-6
-Heptenyl.

The liquid crystal composition according to the present invention preferably contains at least one of the compounds represented by formula (1) at a ratio of 0.1 to 99.9% by weight in order to exhibit excellent characteristics. More specifically, the liquid crystal composition provided by the present invention includes, in addition to the first component containing at least one compound (1), another compound group represented by the general formula (1) or a general compound according to the purpose of the liquid crystal composition. It is completed by mixing compounds arbitrarily selected from formulas (2) to (9). The liquid crystal composition provided by the present invention may be a first component containing at least one kind of the liquid crystalline compound represented by the general formula (1). ),
At least one compound selected from the group consisting of (3) and (4) (hereinafter referred to as the second component A) and / or general formulas (5), (6), (7), (8) and (9) ), And a mixture of at least one compound selected from the group consisting of the following (hereinafter, referred to as a second component B). Further, a threshold voltage, a liquid crystal phase temperature region, a refractive index anisotropy value, and a dielectric constant A known compound can be mixed as a third component for the purpose of adjusting the isotropic value, the viscosity, and the like.

Of the second component A, the general formula (2):
As preferred examples of the compounds contained in (3) and (4),
(2-1) to (2-15), (3-1) to (3)
-48) and (4-1) to (4-55).

[0027]

Embedded image

[0028]

Embedded image

Embedded image

Embedded image

Embedded image

[0029]

Embedded image

Embedded image

Embedded image

Embedded image

(However, R ₁ has the same meaning as described above.) The compounds represented by these general formulas (2) to (4) have a positive dielectric anisotropy value and have a high thermal stability. And the chemical stability is very good. The amount of the compound used is suitably in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition, but is preferably 10 to 97% by weight, more preferably 40 to 95% by weight.

Next, among the second component B, preferred examples of the compounds contained in the general formulas (5), (6) and (7) are (5-1) to (5-24) and (5-24). 6-
1) to (6-3) and (7-1) to (7-28).

[0032]

Embedded image

Embedded image

[0033]

Embedded image

[0034]

Embedded image

Embedded image

(However, R ₂ , R ₃ and R ₄ have the same meanings as described above.) The compounds represented by the general formulas (5) to (7) have a positive dielectric anisotropy value. And its value is large, and it is used as a composition component particularly for the purpose of reducing the threshold voltage. It is also used for the purpose of adjusting the viscosity, adjusting the refractive index anisotropy value, expanding the liquid crystal phase temperature range, and further improving the steepness.

Among the second component B, preferred examples of the compounds contained in the general formulas (8) and (9) are (8-1) to (8-8) and (9-1) to (9-1), respectively. 9-1
3) can be mentioned.

[0037]

Embedded image

[0038]

Embedded image

(However, R ₅ and R ₆ have the same meaning as described above.) The compounds represented by formulas (8) and (9) are compounds having a negative or slightly positive dielectric anisotropy value. It is. General formula (8)
Is mainly used for the purpose of decreasing the viscosity and / or adjusting the refractive index anisotropy value. Further, the compound of the general formula (9) is used for the purpose of widening the nematic range such as increasing the clearing point and / or adjusting the refractive index anisotropy value.

Compounds of the general formulas (5) to (9)
It is an indispensable compound when preparing a liquid crystal composition for a TN display mode and a normal TN display mode. The amount of the compounds represented by the general formulas (5) to (9) can be arbitrarily used in the range of 1 to 99% by weight when a liquid crystal composition for a normal TN display mode or STN display mode is prepared. 10
９７97% by weight, more preferably 40-95% by weight. In that case, some of the compounds (2) to (4) may be used.

By using the liquid crystal composition according to the present invention in a TFT liquid crystal display device, the sharpness and the viewing angle can be improved. Since the compound of the formula (1) is a low-viscosity compound, the response speed of a liquid crystal display device using the compound is improved and extremely large.

The liquid crystal compositions used according to the invention are prepared in a manner which is conventional per se. Generally, a method of dissolving various components at a high temperature is used. However, after being dissolved and mixed in an organic solvent in which the liquid crystal dissolves,
The solvent may be distilled off under reduced pressure. Further, the liquid crystal material of the present invention is improved and optimized according to the intended use by appropriate additives. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. For example, a dichroic dye such as a merocyanine-based, styryl-based, azo-based, azomethine-based, azoxy-based, quinophthalone-based, anthraquinone-based, or tetrazine-based dye is added and used as a liquid crystal composition for a guest-host (GH) mode. it can. Alternatively, a liquid crystal composition for a polymer dispersed liquid crystal display (PDLCD) represented by an NCAP formed by microencapsulating a nematic liquid crystal or a polymer network liquid crystal display (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 a birefringence control (ECB) mode or a dynamic scattering (DS) mode.

Further, as a nematic liquid crystal composition containing the compound of the present invention, the following composition examples (Use Examples 1 to 3)
36). However, the compounds in the composition examples are abbreviated according to the rules shown in Table 1. The structure of the optically active compound is as shown below.

[0044]

Embedded image

In the composition examples (use examples), unless otherwise specified, “%” indicates “% by weight”, and “parts” indicates “parts by weight” of the optically active compound with respect to 100 parts by weight of the liquid crystal composition. The viscosity (η) measurement temperature was 20.0 ° C., and the refractive index anisotropy (Δn) measurement temperature and measurement wavelength were 25.
At 0 ° C. and 589 nm, the threshold voltage (Vth) measurement temperature is 25.0 ° C., and the pitch measurement temperature is 25.0 ° C.

[0046]

[Table 1]

As the nematic liquid crystal composition containing the compound of the present invention prepared as described above, the following composition examples can be shown.

Usage Example 1 V2-HH-VFF (No. 25) 30.0% V-BHH-VFF (No. 7) 19.0% V-BBH-VFF (No. 9) 15.0% 3- HB-C 5.0% 1V2-BEB (F, F) -C 11.0% 3-HB-O2 4.0% 3-HB (F) TB-2 4.0% 3-H2BTB-2 0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

Usage Example 2 V2-HH-VFF (No. 25) 20.0% 1V-BHH-VFF (No. 19) 10.0% V-BBH-VFF (No. 9) 6.0% 3- HB-C 10.0% 1V2-BEB (F, F) -C 12.0% 3-HB-O2 5.0% 3-HHB-1 10.0% 3-HHB-3 10.0% 3- HB (F) TB-2 5.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

Usage Example 3 1V-BHH-VFF (No. 19) 4.0% 1V2-BHH-VFF (No. 118) 10.0% V2-HB-C 10.0% 1V2-HB-C 0% 3-HB-C 26.0% 5-HB-C 12.0% 3-HB (F) -C 8.0% 2-BEB-C 3.0% V2-HHB-1 8.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-H2BTB-4 3.0%

Usage Example 4 V2-HH-VFF (No. 25) 9.0% 1V2-BEB (F, F) -C 11.0% 2O1-BEB (F) -C 5.0% 3O1-BEB ( F) -C 9.0% 3-HB (F) -C 15.0% 1O1-HH-3 3.0% 4-BTB-O2 9.0% 2-HHB (F) -C 13.0% 3-HHB (F) -C 14.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

Use Example 5 1V2-BHH-VFF (No. 118) 5.0% V-BHH-2VFF (No. 8) 10.0% V2-HHH-VFF (No. 29) 5.0% 2- BB-C 5.0% 2O2O-BB-C 4.0% 1O1-HB-C 10.0% 2O1-HB-C 7.0% 2-BEB-C 12.0% 5-PyB-F 8. 0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% V-HHB-1 5.0% 2-PyBH-3 5.0% 3-PyBH -3 5.0% 4-PyBH-3 5.0% 3-PyBB-F 3.0% 4-PyBB-F 3.0% 6-PyBB-2 2.0%

Use Example 6 V2-HH-VFF (No. 25) 3.0% 3-PyB (F) -F 6.0% 3O2O-BEB-C 4.0% 3-BEB-C 12.0% 3-DB-C 10.0% 4-DB-C 10.0% 3-HEB-O4 8.0% 4-HEB-O2 6.0% 5-HEB-O1 6.0% 3-HEB-O2 5.0% 5-HEB-O2 4.0% 3-HHB-1 6.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 10-BEB-2 5.0% 4 -HEB-3 3.0% 5-HEB-1 3.0% 6-PyB-O2 3.0%

Use Example 7 V2-HH-VFF (No. 25) 4.0% 1V-BHH-VFF (No. 19) 3.0% 3-HB-C 20.0% 3-HHB-1 7. 0% 3-HHB-3 8.0% 5-HEB-F 3.0% 7-HEB-F 3.0% 3-HHEB-F 1.0% 5-HHEB-F 1.0% 3-HEB -O4 4.0% 4-HEB-O2 3.0% 5-HEB-O1 3.0% 3-HEB-O2 2.5% 5-HEB-O2 2.0% 3-HB (F) TB- 2 4.0% 3-HB (F) TB-3 4.0% 3-HB (F) VB-4 3.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3 -H2BTB-4 3.0% 5-HHEBB-C 2.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% 3-HE BEB-F 3.0% 3-HH-EMe 2.5% 1O1-HBBH-3 2.0%

Use Example 8 V-BHH-2VFF (No. 8) 6.0% 5-PyB (F) -F 13.0% 2-HB (F) -C 10.0% 3-HB (F) -C 12.0% 3O-BB-C 8.0% 2-HHB-C 6.0% 3-HHB-C 6.0% 4-HHB-C 6.0% 2-HHB (F) -C 5.0% 3-HHB (F) -C 5.0% 3-PyBB-F 7.0% 4-PyBB-F 6.0% 5-HBB-C 5.0% 3-HB (F) EB (F) -C 5.0%

Usage Example 9 V2-HH-VFF (No. 25) 10.0% 2-BEB (F) -C 5.0% 3-BEB (F) -C 7.0% 4-BEB (F) -C 5.0% 5-BEB (F) -C 7.0% 103-HB (F) -C 6.0% 3-HHEB (F) -F 5.0% 4-HHEB (F) -F 5.0% 5-HHEB (F) -F 10.0% 2-HBEB (F) -C 5.0% 3-HBEB (F) -C 5.0% 4-HBEB (F) -C 5. 0% 5-HBEB (F) -C 5.0% 3-HBTB-2 10.0% V2-HH-3 5.0% V2-HHB-1 5.0%

Usage Example 10 V2-HH-VFF (No. 25) 15.0% 1V2-BH-VFF (No. 117) 5.0% V2-HB-C 3.0% 4-BB-2 0% 3-BB-C 5.0% 5-BB-C 5.0% 2-HB (F) -C 5.0% 3-H2B-O2 5.0% 5-H2B-O3 10.0% 3-BEB-C 5.0% 5-HEB-O1 6.0% 5-HEB-O3 6.0% 5-BBB-C 3.0% 4-BPyB-C 3.0% 4-BPyB-5 3.0% 5-HB2B-4 4.0% 5-HBB2B-3 4.0% V2-HH-1O1 3.0% 1V2-HBB-3 5.0%

Usage Example 11 V2-HH-VFF (No. 25) 5.0% V-HH-VFF (No. 1) 5.0% 5-H2B (F) -F 4.0% 7-HB ( F) -F 10.0% 2-HHB (F) -F 12.0% 3-HHB (F) -F 12.0% 5-HHB (F) -F 12.0% 2-H2HB (F) -F 12.0% 3-H2HB (F) -F 6.0% 5-H2HB (F) -F 12.0% 2-HBB (F) -F 2.5% 3-HBB (F) -F 2.5% 5-HBB (F) -F 5.0%

Use Example 12 V2-HH-VFF (No. 25) 7.0% 7-HB (F, F) -F 2.0% 2-HHB (F) -F 10.0% 3-HHB ( F) -F 14.0% 5-HHB (F) -F 14.0% 2-H2HB (F) -F 4.0% 3-H2HB (F) -F 2.0% 5-H2HB (F) -F 4.0% 3-HHB (F, F) -F 8.0% 4-HHB (F, F) -F 4.0% 3-H2HB (F, F) -F 6.0% 4- H2HB (F, F) -F 5.0% 5-H2HB (F, F) -F 5.0% 3-HH2B (F, F) -F 8.0% 5-HH2B (F, F) -F 7.0%

Use Example 13 1V2-HHH-VFF (No. 41) 8.0% 7-HB (F, F) -F 5.0% 3-HBB (F, F) -F 5.0% 5- HBB (F, F) -F 5.0% 3-HHB (F, F) -F 7.0% 5-HHB (F, F) -F 5.0% 3-HH2B (F, F) -F 8.0% 5-HH2B (F, F) -F 5.0% 3-H2HB (F, F) -F 10.0% 4-H2HB (F, F) -F 10.0% 5-H2HB ( F, F) -F 10.0% 3-HHEB (F, F) -F 8.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 0% 3-HBEB (F, F) -F 2.0% 5-HBEB (F, F) -F 2.0% 3-HHHB (F, F) -F 2.0% 5-HH2BB (F, F) -F 2.0%

Usage Example 14 1V2-BH-VFF (No. 117) 5.0% V2-BH-VFF (No. 27) 5.0% 5-HB-F 2.0% 7-HB (F)- F 3.0% 2-HHB (F) -F 14.0% 3-HHB (F) -F 14.0% 5-HHB (F) -F 14.0% 3-HB-O2 5.0% 3-HHB-F 4.0% 3-HHB-1 6.0% 3-HHB-3 6.0% 2-HBB-F 6.0% 3-HBB-F 5.0% 3-HHEB-F 3.0% 5-HHEB-F 3.0% 3-HBEB-F 3.0% 3-HHEBB-F 2.0%

Usage Example 15 V2-HH-VFF (No. 25) 5.0% 1V2-BHH-VFF (No. 118) 3.0% 7-HB (F, F) -F 7.0% 3- HB-CL 5.0% 7-HB-CL 5.0% 2-BTB-O1 10.0% 2-HBB (F) -F 2.5% 3-HBB (F) -F 2.5% 5 -HBB (F) -F 5.0% 3-HBB (F, F) -F 7.0% 5-HBB (F, F) -F 10.0% 2-HHB-CL 5.0% 3- HHB-CL 3.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-4 6.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0 % 3-H2HB (F) -CL 4.0% 5-H2HB (F) -CL 3.0% 3-H2BB (F, F) -F 3.0%

Usage Example 16 V2-HH-VFF (No. 25) 5.0% 1V2-BH-VFF (No. 117) 5.0% 5-HB-F 10.0% 6-HB-F 5. 0% 7-HB-F 5.0% 2-HHB-OCF3 5.0% 3-HHB-OCF3 5.0% 5-HHB-OCF3 5.0% 3-HH2B-OCF3 6.0% 5-HH2B -OCF3 6.0% 3-HB (F) B-3 4.0% 5-HB (F) B-3 4.0% 2-HBB (F) -F 10.0% 3-HBB (F) -F 10.0% 5-HBB (F) -F 15.0%

Usage Example 17 V2-HH-VFF (No. 25) 6.0% V-HH-2VFF (No. 116) 3.0% 1V2-HH-VFF (No. 37) 3.0% 5- HB-F 3.0% 6-HB-F 3.0% 7-HB-F 3.0% 3-HHB-OCF2H 7.0% 5-HHB-OCF2H 7.0% 3-HHB (F, F ) -OCF2H 9.0% 5-HHB (F, F) -OCF2H 9.0% 2-HHB-OCF3 6.0% 3-HHB-OCF3 6.0% 4-HHB-OCF3 6.0% 5- HHB-OCF3 6.0% 3-HH2B (F) -F 7.0% 5-HH2B (F) -F 7.0% 3-HHEB (F) -F 4.0% 5-HHEB (F)- F 5.0%

Use Example 18 V2-HH-VFF (No. 25) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB -O2 14.7% 5-HEB-O2 11.7% T _NI = 67.7 (° C.) η = 19.6 (mPa · s)

Use Example 19 V2-HHH-VFF (No. 29) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB -O2 14.7% 5-HEB-O2 11.7% _TNI = 89.6 (° C) η = 25.7 (mPa · s)

Usage Example 20 V2-HH-2VFF (No. 115) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB -O2 14.7% 5-HEB-O2 11.7% _TNI = 69.5 (° C) η = 20.5 (mPa · s)

Usage Example 21 V2-HH-VFF (No. 25) 10.0% V2-HH-2VFF (No. 115) 8.0% 1V2-BEB (F, F) -C 5.0% 3- HB-C 25.0% 1-BTB-3 5.0% 3-HH-4 3.0% 3-HHB-1 11.0% 3-HHB-3 9.0% 3-H2BTB-2 4. 0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% T _NI = 93 0.3 (° C.) η = 13.9 (mPa · s) Δn = 0.147 V _th = 2.08 (V) When 0.8 part of CM33 is added to 100 parts of the composition, the pitch is 10.5 μm. Met.

Usage Example 22 V2-HHH-VFF (No. 29) 8.0% 201-BEB (F) -C 5.0% 3O1-BEB (F) -C 15.0% 4O1-BEB (F) -C 13.0% 5O1-BEB (F) -C 13.0% 2-HHB (F) -C 15.0% 3-HHB (F) -C 15.0% 3-HB (F) TB- 2 4.0% 3-HB (F) TB-3 4.0% 3-HB (F) TB-4 4.0% 3-HHB-O1 4.0% T _NI = 94.5 (° C.) η = 85.5 (mPa · s) Δn = 0.149 V _th = 0.90 (V)

Usage Example 23 V2-HH-VFF (No. 25) 4.0% V2-HH-2VFF (No. 115) 9.0% V2-HHH-VFF (No. 29) 8.0% 5- PyB-F 4.0% 3-PyB (F) -F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB- 2 2.0% 6-PyB-O5 3.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PyBB-F 6.0% 3-HHB-1 6.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T _NI = 99.4 (° C.) η = 28.5 (mPa · s) Δn = 0.191 V _th = 2.32 (V)

Usage Example 24 V2-HH-VFF (No. 25) 25.0% 3-DB-C 10.0% 4-DB-C 10.0% 2-BEB-C 12.0% 3-BEB -C 4.0% 3-PyB (F) -F 6.0% 5-HEB-O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 10-BEB-2 4.0% 3-HHB-1 6.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% T _NI = 67.3 (° C.) η = 31.0 (mPa · s) Δn = 0.121 V _th = 1.28 (V)

Usage Example 25 V2-HH-2VFF (No. 115) 4.0% 3-HB-C 18.0% 7-HB-C 3.0% 1O1-HB-C 10.0% 3-HB (F) -C 10.0% 4-PyB-2 2.0% 1O1-HH-3 7.0% 2-BTB-O1 7.0% 3-HHB-1 7.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 8.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3 -PyBH-3 3.0% 3-PyBB-2 3.0% T _NI = 81.4 (° C.) η = 16.9 (mPa · s) Δn = 0.137 V _th = 1.77 (V)

Usage Example 26 1V2-HH-VFF (No. 37) 5.0% 1V2-HH-2VFF (No. 38) 8.0% 2O1-BEB (F) -C 5.0% 3O1-BEB ( 10. F) -C 12.0% 5O1-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 10.0% 3-HH-EMe 5.0% 3-HB-O2 0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0% 2O1-HBEB (F) -C 2.0% 3-HB (F) EB (F) -C 2.0% 3-HBEB (F, F) -C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3- HHB-3 13.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0%

Usage Example 27 1V-HH-VFF (No. 13) 5.0% 1V-HH-2VFF (No. 14) 5.0% V2-HHH-VFF (No. 29) 8.0% 2O1- BEB (F) -C 5.0% 3O1-BEB (F) -C 12.0% 5O1-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 16.0% 3- HH-4 3.0% 3-HHB-F 3.0% 3-HHB-O1 4.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7. 0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 5.0%

Usage Example 28 V2-HH-VFF (No. 25) 20.0% V2-HHH-VFF (No. 29) 4.0% 2-BEB-C 12.0% 3-BEB-C 0% 4-BEB-C 6.0% 3-HB-C 28.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HHB -1 7.0% T _NI = 60.4 (° C.) η = 18.2 (mPa · s) Δn = 0.112 V _th = 1.31 (V)

Usage Example 29 1V2-HH-VFF (No. 37) 5.0% 1V-HH-VFF (No. 13) 5.0% 1V2-HH-2VFF (No. 38) 5.0% 1V- HH-2VFF (No. 14) 5.0% 2-BEB-C 10.0% 5-BB-C 12.0% 7-BB-C 7.0% 1-BTB-3 7.0% 10- BEB-5 12.0% 2-HHB-1 4.0% 3-HHB-F 4.0% 3-HHB-1 7.0% 3-HHB-O1 4.0% 3-HHB-3 13. 0%

Usage Example 30 V2-HH-2VFF (No. 115) 20.0% 1V2-BEB (F, F) -C 6.0% 3-HB-C 18.0% 2-BTB-1 0% 5-HH-VFF 10.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 11.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB -4 4.0% 3-HHB-1 4.0% T _NI = 83.1 (° C.) η = 11.7 (mPa · s) Δn = 0.132 V _th = 2.10 (V)

Usage Example 31 V2-HHH-VFF (No. 29) 8.0% 2-HB-C 5.0% 3-HB-C 12.0% 3-HB-O2 15.0% 2-BTB -1 3.0% 3-HHB-F 4.0% 3-HHB-O1 5.0% 3-HHB-3 14.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0 % 2-HHB (F) -F 7.0% 3-HHB (F) -F 7.0% 5-HHB (F) -F 7.0% 3-HHB (F, F) -F 5.0 % T _NI = 103.0 (° C.) η = 17.2 (mPa · s) Δn = 0.099 V _th = 2.56 (V)

Usage Example 32 V2-HH-VFF (No. 25) 3.0% V2-HHH-VFF (No. 29) 5.0% 3-BEB (F) -C 8.0% 3-HB- C 8.0% V-HB-C 8.0% 1V-HB-C 8.0% 3-HH-2V 14.0% 3-HH-2V1 7.0% V2-HHB-1 15.0% 3-HHEB-F 7.0% 3-H2BTB-2 6.0% 3-H2BTB-3 6.0% 3-H2BTB-4 5.0% T _NI = 101.3 (° C.) η = 15.2 (MPa · s) Δn = 0.132 V _th = 2.25 (V)

Usage Example 33 V2-HH-2VFF (No. 115) 31.0% 1V2-BEB (F, F) -C 12.0% 3-HB-C 4.0% 3-HB-O2 5% 3-HHB-1 3.5% 1-BHH-VFF 20.0% 3-HB (F) TB-2 4.0% 3-HB (F) TB-3 4.0% 3-HB ( F) TB-4 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% T _NI = 100.4 (° C.) η = 14.1 (MPa · s) Δn = 0.133 V _th = 2.16 (V) The pitch when adding 2.0 parts of CN to 100 parts of the composition was 10.6 μm.

Usage Example 34 V2-HH-VFF (No. 25) 28.0% 1V2-BEB (F, F) -C 12.0% 3-HB-C 4.0% 3-HB-O2 5% 3-HHB-1 8.5% 1-BHH-VFF 20.0% 3-HB (F) TB-2 5.0% 3-HB (F) TB-3 5.0% 3-H2BTB- 2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% T _NI = 100.5 (° C.) η = 13.9 (mPa · s) Δn = 0.132 V _th = 2.14 (V) When 1.81 parts of CN was added to 100 parts of the composition, the pitch was 12.3 μm.

Usage Example 35 V2-HH-VFF (No. 25) 15.0% 2O1-BEB (F) -F 10.0% 3O1-BEB (F) -F 26.0% 1V2-BEB (F, F) -C 5.0% 2-HHB (F) -C 14.0% 3-HHB (F) -C 14.0% 3-HB (F) TB-2 5.0% 3-HB (F ) TB-3 5.0% 3-HHB-1 6.0% T _NI = 85.3 (° C.) η = 51.1 (mPa · s) Δn = 0.143 V _th = 0.96 (V)

Usage Example 36 V2-HH-VFF (No. 25) 8.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 5.0% 5- HBEB (F, F) -F 3.0% 3-HB-C 20.0% 1V2-BEB (F, F) -C 30.0% 3-HHB-3 10.0% 3-HHB-O15 3.0% 3-HHEB-F 3.0% 5-HHEB-F 3.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% T _NI = 77.0 (° C.) η = 34.0 (mPa · s) Δn = 0.137 V _th = 0.98 (V)

[0084]

[Production Method of Compound] The compound (1) of the present invention can be easily produced by making full use of ordinary organic synthetic chemistry techniques. For example, it can be easily synthesized by appropriately selecting and combining known reactions described in books such as Organic Synthesis, Organic Reactions, New Laboratory Chemistry Course, and magazines. That is, the liquid crystalline compound of the present invention can be prepared according to a known method using the Wittig reaction, for example, the method described in Organic Reactions, Vol.
Sodium methylate, potassium tert-butoxide (t-Bu) in an ether solvent such as HF and diethyl ether.
The triphenylphosphonium halide derivative of ( 12 ) is reacted with the aldehyde derivative ( 11 ) in the presence of a base such as OK) and butyllithium to obtain ( 13 ). Then, in toluene, diisobutylaluminum halide (hereinafter, referred to as
The aldehyde derivative ( 14 ) can be obtained by reacting (abbreviated as DIBAL) with ( 13 ), and the compound of the present invention can be obtained by further reacting ( 15 ) with triphenylphosphine in ( 14 ) in dimethylformamide (1) can be manufactured.

[0085]

Embedded image

When Q ₁ = Q ₂ ≠ H, 1 = 0, the following method is preferable. That is, ( 17 ) can be obtained by reacting ( 16 ) and triphenylphosphine on an aldehyde derivative ( 11 ) in N, N-dimethylformamide (hereinafter abbreviated as DMF), and then ( 13 ) The compound (1) of the present invention can also be produced by causing ( 17 ) to perform a series of operations from (1) to ( 17 ).

[0087]

Embedded image

Compounds in which A ₁ , A ₂ , A ₃ and A ₄ are silacyclohexane rings are described in JP-A-7-7014.
8, JP-A-7-112990 and JP-A-7-14
It can be manufactured according to the method disclosed in No. 9770.

The thus obtained liquid crystalline compound (1) of the present invention has a wide liquid crystal phase temperature range, is low in viscosity, has a large elastic constant ratio K ₃₃ / K _11, and has various other properties. Easily mixed with low temperature liquid crystal materials even at low temperatures,
It is extremely excellent as a component of a nematic liquid crystal composition suitable for a type display system.

[0090]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The structure of the compound was confirmed by a nuclear magnetic resonance spectrum (hereinafter abbreviated as ¹ H-NMR), a mass spectrum (hereinafter abbreviated as MS), and the like. In the examples,
In NMR, d is a doublet, t is a triplet, m is a multiplet,
J represents a coupling constant. In MS, M ⁺ represents a molecular ion peak, and the value in parentheses represents an ion intensity. Cr is a crystalline phase, S is a smectic phase, N is a nematic phase, I is
so indicates an isotropic liquid phase, and all units of the phase transition temperature are ° C.
It is.

Example 1 1- (2,2-difluoroethenyl) -trans-4-
(Trans-4- (3-butenyl) cyclohexyl) cyclohexane (in the formula (1), A ₃ and A ₄ are trans-1,4-cyclohexylene groups, Z ₃ is a covalent bond, Q is
₁ , Q ₂ is H, Q ₃ , Q ₄ is F, l, n, p, q are 0,
Preparation of compound (No. 25) wherein m is 2:

Stage 1 A mixture of 165.6 grams (463.6 mmol) of methyltriphenylphosphonium bromide and 1.5 liters of THF was cooled to -50 ° C under a stream of nitrogen. To this mixture was added 57.2 g (509.8 mmol) of t-BuOK and stirred for 1 hour. This mixture was added with trans-4- (trans-4- (2-formylethyl) cyclohexyl)
100.0 grams of methyl cyclohexanecarboxylate (3
56.6 mmol) in 1 liter of THF at -50 ° C.
The following was added dropwise. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 500 ml of water was added, and the mixture was extracted with 500 ml of toluene. The organic layer was washed three times with 200 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: a mixed solvent of ethyl acetate / heptane = 1/10) to obtain crude trans-4- (trans-
34.8 grams of methyl 4- (3-butenyl) cyclohexyl) cyclohexanecarboxylate were obtained.

2nd stage 34.8 g (125.0 mmol) of this crude product was dissolved in 500 ml of toluene, and the solution was dissolved in a nitrogen stream at -5 g.
Keep DIBAL in a 1.0 M toluene solution 12
5 ml were added dropwise. After stirring at the same temperature for 1 hour, the reaction was terminated by gradually pouring the reaction solution into water. It was washed three times with 300 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude trans-
30.3 grams of 4- (trans-4- (3-butenyl) cyclohexyl) cyclohexanecarbaldehyde were obtained.

Step 3 The crude product, trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexanecarbaldehyde, 30.3 g (122.0 mmol) and triphenylphosphine 41.6 g (158. (6 mmol) was added to 600 ml of a mixed solvent of toluene / DMF (1/5), and the mixture was heated while stirring under a nitrogen stream. 10
37.2 grams (244.0 mmol) of sodium chlorodifluoroacetate at a temperature of 0-110 ° C
In 400 ml of DMF was added dropwise while maintaining the same temperature. After completion of the dropwise addition, the mixture was stirred for 30 minutes and allowed to cool to room temperature. One liter of water and one liter of heptane were added to the reaction mixture, and after sufficiently stirring, the mixture was filtered through celite. Further, the aqueous layer was extracted with 500 ml of heptane, and the organic layer was washed three times with 700 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent:
Heptane) to give a crude product of 1- (2,2-difluoroethenyl) -trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexane. The crude product was recrystallized from Solmix to obtain 13.3 g (yield 13.2%) of the title compound. Phase transition temperature: Cr-7.1S-4.9N4
9.7 Iso ¹ H-NMR: δ: (ppm): 0.50 to 2.38
(M, 24H), 3.99 (d, d, d, 1H, J _HF
= 22.9, 9.2, J = 6.3), 4.80-5.1.
5 (m, 2H), 5.82 (d, d, t, 1H, J _HF
= 17.2, 10.0, J = 6.7). MS: m / e =
282 (M ⁺ ), 225, 211, 135, 95, 8
1,67.

Example 2 1- (4,4-Difluoro-3-butenyl) -trans-4- (trans-4- (trans-4-ethenylcyclohexyl) cyclohexyl) cyclohexane ((1)
In the formula, A ₂ , A ₃ and A ₄ are trans-1,4-cyclohexylene groups, Z ₂ and Z ₃ are covalent bonds, Q ₁ and Q ₂
Is a compound (No. 6) wherein H, Q ₃ and Q ₄ are F, l, m and p are 0, q is 1 and n is 2.

Stage 1 A mixture of 128.1 grams (358.6 mmol) of methyltriphenylphosphonium bromide and 1.5 liter of THF was cooled to -50 ° C under a stream of nitrogen. To this mixture, 44.3 g (394.8 mmol) of t-BuOK was added and stirred for 1 hour. This mixture was added with 2- (trans-4
100.0 grams (275.8 mmol) of methyl-(trans-4- (trans-4-formylcyclohexyl) cyclohexyl) cyclohexyl) ethanecarboxylate
Was added dropwise while maintaining a temperature of −50 ° C. or lower. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 500 ml of water was added, and the mixture was extracted with 500 ml of toluene. The organic layer was washed three times with 200 ml of water and dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure,
The residue was subjected to silica gel column chromatography (developing solvent: a mixed solvent of ethyl acetate / heptane = 1/8) to obtain crude 2- (trans-4- (trans-4- (trans-4-ethenylcyclohexyl)). Methyl cyclohexyl) cyclohexyl) ethanecarboxylate 37.8
Grams were obtained.

2nd stage 37.8 g (104.8 mmol) of this crude product was dissolved in 500 ml of toluene, and the solution was dissolved in a stream of nitrogen for 5 minutes.
Keeping the temperature at 0 ° C or lower, DIBAL 1.0M toluene solution 10
5 ml were added dropwise. After stirring at the same temperature for 1 hour, the reaction was terminated by gradually pouring the reaction solution into water. It was washed three times with 300 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 32.9 g of crude 3- (trans-4- (trans-4- (trans-4-ethenylcyclohexyl) cyclohexyl) cyclohexyl) propanal.

Step 3 The crude product 3- (trans-4- (trans-4- (trans-4-ethenylcyclohexyl) cyclohexyl) cyclohexyl) propanal 32.9 g (9
9.5 mmol) and 33.9 g (129.2 mmol) of triphenylphosphine in toluene / DMF (1 /
The mixture was added to 600 ml of the mixed solvent of 5), and the temperature was increased while stirring under a nitrogen stream. When the temperature reaches 100 to 110 ° C, sodium chlorodifluoroacetate 30.
A solution of 3 grams (198.7 mmol) dissolved in 300 ml of DMF was added dropwise while maintaining the same temperature.
After completion of the dropwise addition, the mixture was stirred for 30 minutes and allowed to cool to room temperature. One liter of water and one liter of heptane were added to the reaction mixture, and after sufficiently stirring, the mixture was filtered through celite. Further, the aqueous layer was extracted with 500 ml of heptane, and the organic layer was washed three times with 700 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: heptane) to give 1-
(4,4-difluoro-3-butenyl) -trans-4
A crude product of-(trans-4- (trans-4-ethenylcyclohexyl) cyclohexyl) cyclohexane was obtained. The crude product was recrystallized from Solmix to obtain 14.5 g (yield 14.4%) of the title compound. MS: m / e = 364 (M ⁺ ).

Example 3 1- (2,2-difluoroethenyl) -trans-4-
(Trans-4- (4- (3-butenyl) phenyl) cyclohexyl) cyclohexane (In the formula (1), A
₂ is a 1,4-phenylene group, A ₃ and A ₄ are trans-
A 1,4-cyclohexylene group, Z ₂ and Z ₃ are a covalent bond,
Q ₁ and Q ₂ are H, Q ₃ and Q ₄ are F, l, n and p are 0, q
Of compound (No. 31) wherein is 1 and m is 2:

Stage 1 A mixture of 130.3 grams (364.8 mmol) of methyltriphenylphosphonium bromide and 1.5 liters of THF was cooled to -50 ° C under a stream of nitrogen. To this mixture was added 45.0 g (401.0 mmol) of t-BuOK and stirred for 1 hour. This mixture was added with trans-4- (trans-4- (4- (2-formylethyl) phenyl))
Cyclohexyl) methyl cyclohexanecarboxylate 10
A solution of 0.0 gram (280.5 mmol) in 1 liter of THF was added dropwise while keeping the temperature at -50 ° C or lower. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 500 ml of water was added, and the mixture was extracted with 500 ml of toluene. Organic layer with water 20
Washed three times with 0 ml and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: a mixed solvent of ethyl acetate / heptane = 1/8) to obtain crude trans-4.
-(Trans-4- (4- (3-butenyl) phenyl)
Cyclohexyl) methyl cyclohexanecarboxylate 3
7.8 grams were obtained.

2nd stage 37.8 g (106.6 mmol) of this crude product was dissolved in 500 ml of toluene, and the solution was dissolved in a stream of nitrogen for 5 minutes.
Keeping the temperature at 0 ° C or lower, DIBAL 1.0M toluene solution 10
7 ml was dropped. After stirring at the same temperature for 1 hour, the reaction was terminated by gradually pouring the reaction solution into water. It was washed three times with 300 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude trans-
31.8 grams of 4- (trans-4- (4- (3-butenyl) phenyl) cyclohexyl) cyclohexanecarbaldehyde were obtained.

Third Step Trans-4- (trans-4- (4- (3
-Butenyl) phenyl) cyclohexyl) cyclohexanecarbaldehyde 31.8 g (98.0 mmol) and triphenylphosphine 33.4 g (12
7.3 mmol) was added to 600 ml of a mixed solvent of toluene / DMF (1/5), and the mixture was heated with stirring under a nitrogen stream. When the temperature reached 100 to 110 ° C., 29.9 g of sodium chlorodifluoroacetate (1
(96.1 mmol) in 300 ml of DMF was added dropwise while maintaining the same temperature. After dropping,
The mixture was stirred for 30 minutes and allowed to cool to room temperature. One liter of water and one liter of heptane were added to the reaction mixture, and after sufficiently stirring, the mixture was filtered through celite. Further, the aqueous layer was extracted with 500 ml of heptane, and the organic layer was extracted with 700 ml of water.
Washed twice and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: heptane) to give 1- (2,2-difluoroethenyl) -trans-4- (trans-4-
A crude product of (4- (3-butenyl) phenyl) cyclohexyl) cyclohexane was obtained. The crude product was recrystallized from Solmix to obtain 14.4 g (yield 14.3%) of the title compound. MS: m / e = 358 (M ^<+> ).

Example 4 1- (2,2-difluoroethenyl) -trans-4-
(4- (4- (trans-4- (3-butenyl) cyclohexyl) phenyl) phenyl) cyclohexane (In the formula (1), A ₁ and A ₄ are trans-1,4-
Cyclohexylene group, A ₂ and A ₃ are 1,4-phenylene groups, Z ₁ , Z ₂ , and Z ₃ are covalent bonds, Q ₁ and Q ₂ are H, Q ₃
, Q ₄ is F, l, n is 0, p, q is 1, m is 2 Compound (No.35)) Preparation of

Stage 1 A mixture of 107.4 grams (300.6 mmol) of methyltriphenylphosphonium bromide and 1 liter of THF was cooled to -50 ° C under a stream of nitrogen. T-
37.1 grams (330.6 mmol) of BuOK were added and stirred for 1 hour. This mixture was added with trans-4- (4-
A solution of 100.0 g (231.2 mmol) of methyl (4- (trans-4- (2-formylethyl) cyclohexyl) phenyl) phenyl) cyclohexanecarboxylate in 1 liter of THF was added dropwise at -50 ° C or lower.
After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 500 ml of water was added, and the mixture was extracted with 500 ml of toluene.
The organic layer was washed three times with 200 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: a mixed solvent of ethyl acetate / heptane = 1/7) to give crude trans-4- (4- (4- (trans -4- (3-
33.9 grams of methyl butenyl) cyclohexyl) phenyl) phenyl) cyclohexanecarboxylate were obtained.

Stage 2 33.9 g (78.7 mmol) of this crude product was dissolved in 350 ml of toluene, and dissolved in a nitrogen stream at -50 g.
While maintaining the temperature at not more than 70 ° C., 79 ml of a 1.0 M toluene solution of DIBAL was added dropwise. After stirring at the same temperature for 1 hour, the reaction was terminated by gradually pouring the reaction solution into water. Water 20
It was washed three times with 0 ml and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the crude trans-4-
28.4 grams of (4- (4- (trans-4- (3-butenyl) cyclohexyl) phenyl) phenyl) cyclohexanecarbaldehyde were obtained.

Third stage: Trans-4- (4- (4- (trans-4- (3-butenyl) cyclohexyl) phenyl) phenyl) cyclohexanecarbaldehyde (28.4 g, 70.9 mmol) and triphenylphosphine 24 .2 grams (9
2.3 mmol) was added to 400 ml of a mixed solvent of toluene / DMF (1/5), and the mixture was heated while stirring under a nitrogen stream. When the temperature reached 100 to 110 ° C., 21.6 g of sodium chlorodifluoroacetate (1
(41.7 mmol) in 200 ml of DMF was added dropwise while maintaining the same temperature. After dropping,
The mixture was stirred for 30 minutes and allowed to cool to room temperature. 600 ml of water and 600 ml of heptane were added to the reaction mixture, and the mixture was sufficiently stirred and then filtered through celite. The aqueous layer was further extracted with heptane (300 ml), and the organic layer was extracted with water (35).
It was washed three times with 0 ml and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: heptane).
1- (2,2-difluoroethenyl) -trans-4-
(4- (4- (trans-4- (3-butenyl) cyclohexyl) phenyl) phenyl) cyclohexane was obtained. The crude product was recrystallized from Solmix to give 13.9 g (13.8% yield) of the title compound. MS: m / e = 434 (M ^<+> ).

Example 5 1- (4,4-Difluoro-3-butenyl) -trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexane (in the formula (1), A ₃ and A ₄ are A compound in which trans-1,4-cyclohexylene group, Z ₃ is a covalent bond, Q ₁ and Q ₂ are H, Q ₃ and Q ₄ are F, l, p and q are 0, m and n are 2 (No. .115)):

First stage: methoxymethyltriphenylphosphonium chloride 6
A mixture of 6.4 grams (193.7 mmol) and 600 mL of THF was cooled to -50 ° C under a stream of nitrogen.
20.1 grams of t-BuOK (179.1) was added to this mixture.
Mmol) and stirred for 1 hour. To this mixture, a solution of 37.0 g (148.9 mmol) of trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexanecarbaldehyde in 400 mL of THF was added dropwise while maintaining the temperature at -50 ° C or lower. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 250 ml of water was added, and the mixture was extracted with 300 ml of toluene. The organic layer was washed three times with 200 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: toluene / heptane =
(3/7 mixed solvent) to obtain 16.1 g of crude 1- (2-methoxyethenyl) -trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexane.

Stage 2 16.0 g (57.9 mmol) of this crude product was dissolved in 200 ml of toluene, and 87% formic acid 3
0.6 g (578.3 mmol) was added, and the mixture was heated under reflux for 3 hours. The reaction solution was washed twice with 200 ml of water, three times with 100 ml of saturated sodium bicarbonate and twice with water.
It was washed three times with 00 ml and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 14.8 g of a crude product of trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexylacetaldehyde.

Stage 3 Methoxymethyltriphenylphosphonium chloride 2
A mixture of 5.2 grams (73.5 mmol) and 300 mL of THF was cooled to -50 ° C under a stream of nitrogen. To this mixture, 7.6 g (67.8 mmol) of t-BuOK was added and stirred for 1 hour. To this mixture, a solution of 14.8 g (56.5 mmol) of the crude product of trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexylacetaldehyde in 150 mL of THF was added dropwise while maintaining the temperature at -50 ° C or lower. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the mixture was further stirred for 5 hours. The solvent was distilled off under reduced pressure, 150 ml of water was added, and the mixture was extracted with 200 ml of toluene. 100 organic layers
Washed three times with milliliter and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: a mixed solvent of toluene / heptane = 3/7) to give crude 1- (3-methoxypropenyl) -trans-4-. (Trans-4- (3
-Butenyl) cyclohexyl) cyclohexane 12.8
Grams were obtained.

Stage 4 12.1 g (41.7 mmol) of this crude product was dissolved in 200 ml of toluene, and 87% formic acid 2
2.0 g (415.8 mmol) was added, and the mixture was heated under reflux for 3 hours. The reaction solution was washed twice with 200 ml of water, three times with 100 ml of saturated sodium bicarbonate and twice with water.
It was washed three times with 00 ml and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 11.5 g of crude trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexylpropanal.

Step 5 Trans-4- (trans-4- (3-butenyl) cyclohexyl) cyclohexylpropanal 1 of the crude product
1.5 g (41.6 mmol) and 14.2 g (54.1 mmol) of triphenylphosphine were added to 100 ml of a mixed solvent of toluene / DMF (1/5), and the mixture was heated with stirring under a nitrogen stream. did. 100-11
When the temperature reached 0 ° C., 12.7 g (83.3 mmol) of sodium chlorodifluoroacetate was added to DMF1.
A solution dissolved in 00 ml was added dropwise while maintaining the same temperature. After completion of the dropwise addition, the mixture was stirred for 30 minutes and allowed to cool to room temperature. 200 ml of water and 200 ml of heptane were added to the reaction mixture, and after sufficiently stirring, the mixture was filtered through celite. Further, the aqueous layer was extracted with 200 ml of heptane, and the organic layer was washed three times with 300 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: heptane) to give 1- (4,4-difluoro-
3-butenyl) -trans-4- (trans-4- (3
A crude product of -butenyl) cyclohexyl) cyclohexane was obtained. This crude product was recrystallized from Solmix,
5.1 g (11.7% yield) of the title compound were obtained. Phase transition temperature: Cr-7.0 S _B 49.0 N 6
9.0 Iso ¹ H-NMR: δ: (ppm): 0.40 to 2.55
(M, 28H), 4.10 (d, d, t, 1H, J _HF
= 25.3, J = 7.7, J _HF = 3.1), 4.80
~ 5.20 (m, 2H), 5.82 (d, d, t, 1
H, J _HF = 17.1, 9.9, J = 6.7). MS: m / e = 310 (M ⁺ ), 253, 239, 13
7, 95, 81, 67.

The following compounds can be prepared according to the methods of Examples 1 to 5.

[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]

The compound of the present invention, that is, the alkenyl group which may be halogen-substituted and the bi- to tetracyclic compound having a halogen-substituted alkenyl group at both terminals of the molecule are all 1) having an alkenyl group. Despite this, it has a wide liquid crystal phase temperature range. For example, JP-A-1-175947
, Trans-4- (trans-4-propylcyclohexyl) -1- (2,2-difluoro-1)
-Ethenyl) cyclohexane having a liquid crystal phase temperature range of about 47
° C, of which the temperature range of the _SB phase is about 40 ° C. In contrast, the compound of the present invention, 1- (2,2-difluoroethenyl) -trans-4- (trans-4- (3-
Butenyl) cyclohexyl) cyclohexane liquid crystal temperature region not express S _B phase is about 56 ° C., remarkably improving seen. 2) Due to low viscosity, a decrease in threshold voltage and an improvement in response speed are observed. 3) It is possible to prepare a stable nematic liquid crystal composition in which no crystals are precipitated and no smectic phase is developed even at a very low temperature. 4) High contrast is possible because the elastic constant ratio K ₃₃ / K ₁₁ is improved. Thus, it is possible to provide a novel liquid crystal composition and a liquid crystal display element which are stable to an external environment, can be used in an increased operating temperature range, can be driven at a low voltage, can respond at high speed, and can achieve high contrast.

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C07C 25/24 7106-4H C07C 25/24 43/192 7419-4H 43/192 69/75 69/75 69 / 773 69/773 C07D 239/26 C07D 239/26 C09K 19/08 C09K 19/08 19/42 19/42 G02F 1/13 500 G02F 1/13 500

Claims (15)

[Claims] 1. A compound of the general formula (1) (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ). 2. In the general formula (1), p, q and n are 0, Q ₃ and Q ₄ are F, Z ₃ is a covalent bond, and A ₃ and A
The liquid crystal compound according to claim 1, wherein ₄ is a trans-1,4-cyclohexylene group. 3. In the general formula (1), p and q are 0, Q
_3, Q ₄ is the F, Z ₃ is a covalent bond, A liquid crystalline compound according to claim 1 A _3, A ₄ are trans-1,4-cyclohexylene group. 4. In the general formula (1), p and n are 0, q is 1, Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds.
_2, A _3, liquid crystalline compound according to claim 1 A ₄ is trans-1,4-cyclohexylene group. 5. In the general formula (1), p is 0, q is 1,
Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds, and A ₂ ,
Liquid crystalline compound according to claim 1 A _3, A ₄ are trans-1,4-cyclohexylene group. 6. In the general formula (1), p and n are 0, q is 1, Q ₃ and Q ₄ are F, Z ₂ Z ₃ is a covalent bond, and A ₂
Is a 1,4-phenylene group, and A ₃ and A ₄ are trans-1,4-cyclohexylene groups. 7. In the general formula (1), p is 0, q is 1,
Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds, A ₂ is a 1,4-phenylene group, and A ₃ and A ₄ are trans-
The liquid crystal compound according to claim 1, which is a 1,4-cyclohexylene group. 8. In the general formula (1), p and n are 0, q is 1, Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds.
_2. The liquid crystal compound according to claim 1, wherein A ₃ is a 1,4-phenylene group and A ₄ is a trans-1,4-cyclohexylene group. 9. In the general formula (1), p is 0, q is 1,
Q ₃ and Q ₄ are F, Z ₂ and Z ₃ are covalent bonds, and A ₂ ,
A ₃ is a 1,4-phenylene group, and A ₄ is trans-
The liquid crystal compound according to claim 1, which is a 1,4-cyclohexylene group. 10. In the general formula (1), p and q are 1, n
Is 0, Q ₃ and Q ₄ are F, Z ₁ , Z ₂ and Z ₃ are covalent bonds, A ₁ and A ₄ are trans-1,4-cyclohexylene groups, and A ₂ and A ₃ are 1 The liquid crystal compound according to claim 1, which is a 1,4-phenylene group. 11. In the general formula (1), p and q are 1, Q
₃ and Q ₄ are F, Z ₁ , Z ₂ and Z ₃ are covalent bonds, and A ₁
, A ₄ is a trans-1,4-cyclohexylene group, and A ₂ and A ₃ are 1,4-phenylene groups.
The liquid crystal compound according to the above. 12. A liquid crystal composition comprising two or more components containing at least one component of the liquid crystalline compound according to claim 1, and a liquid crystal display device using the same. 13. A liquid crystal display device comprising as a first component at least one liquid crystal compound represented by the general formula (1): (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ) As the second component, general formulas (2), (3) and (4) (Wherein, R ₁ represents an alkyl group having 1 to 10 carbon atoms;
₁ is F, Cl, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂
H or CFH ₂ , L ₁ , L ₂ , L ₃ and L ₄
Represents H or F independently of each other, Z ₄ and Z ₅ independently represent — (CH ₂ ) ₂ —, —CH ＝ CH— or a covalent bond, and a represents 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of: 14. A composition comprising at least one liquid crystal compound represented by the general formula (1) as a first component: (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. ) As the second component, general formulas (5), (6), (7),
(8) and (9) (Wherein, R ₂ represents F, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group (—CH ₂ —) in the alkyl group or alkenyl group)
May be substituted by an oxygen atom (-O-), but two or more methylene groups are not successively substituted by an oxygen atom. Ring A is a trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5
-Diyl group or 1,3-dioxane-2,5-diyl group; ring B is trans-1,4-cyclohexylene group, 1,4-phenylene group or pyrimidine-2,5-
It indicates diyl group, ring C represents trans-1,4-cyclohexylene group or 1,4-phenylene group, the Z ₆ -
(CH ₂ ) ₂ —, —COO— or a covalent bond;
₅ and L ₆ each independently represent H or F, and b and c each independently represent 0 or 1. ) (Wherein, R ₃ represents an alkyl group having 1 to 10 carbon atoms;
₇ represents H or F, and d represents 0 or 1. ) (Wherein, R ₄ represents an alkyl group having 1 to 10 carbon atoms, ring D and ring E independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group,
₇ and Z ₈ independently represent —COO— or a covalent bond, Z ₉ represents —COO— or —C≡C—,
L ₈ and L ₉ independently represent H or F;
₂ represents F, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g independently represent 0
Or 1 is indicated. ) (Wherein, R ₅ and R ₆ are independently of each other having 1 to 1 carbon atoms.
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring G is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and Z ₁₀ represents —C≡C—, —COO—, — (CH
_{2) 2 -, - CH =} CH-C≡C- or indicates a covalent bond, Z ₁₁ represents a -COO- or a covalent bond. ) (Wherein, R ₇ and R ₈ are independently of each other having 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring I is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
A 1,4-cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group in which one or more hydrogen atoms on the ring may be substituted with F, and a ring K is trans-1 , 4-cyclohexylene or 1,4-phenylene, wherein Z ₁₂ and Z ₁₄ independently of one another
_{OO -, - (CH 2)} 2 - or indicates a covalent bond, Z ₁₃
Represents -CH = CH-, -C≡C-, -COO- or a covalent bond, and h represents 0 or 1. A liquid crystal composition comprising at least one compound selected from the group consisting of: 15. A liquid crystal display device comprising as a first component at least one liquid crystal compound represented by the general formula (1): (Where A ₁ , A ₂ , A ₃ and A ₄ are each independently
Trans-1,4-cyclohexylene group, trans-
1,4-silacyclohexylene group or 1,4-phenylene group in which one or more hydrogen atoms on a six-membered ring may be substituted with a halogen atom, pyrimidine-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithiane-
2,5-diyl group or tetrahydrothiopyran-2,
Shows 5-diyl _{group, Z 1, Z 2, Z} 3 are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - CH = C
H -, - C≡C -, - COO -, - OCO -, - CH 2
_{O -, - OCH 2 -,} - CF = CF- or indicates the covalent bond. Q ₁ and Q ₂ are each independently H, F, Cl, B
indicates r or alkenyl group having 2 to 5 carbon atoms, Q _3, Q
₄ each independently represents H, F, Cl or Br;
l, m, and n each independently represent an integer of 0 to 5, p, q
Each independently represents an integer of 0 or 1. As a part of the second component, at least one compound selected from the group consisting of general formulas (2), (3) and (4)
Contains the following: (Wherein, R ₁ represents an alkyl group having 1 to 10 carbon atoms;
₁ is F, Cl, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂
H or CFH ₂ , L ₁ , L ₂ , L ₃ and L ₄
Represents H or F independently of each other, Z ₄ and Z ₅ independently represent — (CH ₂ ) ₂ —, —CH ＝ CH— or a covalent bond, and a represents 1 or 2. ) As other parts of the second component, general formulas (5), (6),
It contains at least one compound selected from the group consisting of (7), (8) and (9). (Wherein, R ₂ represents F, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group (—CH ₂ —) in the alkyl group or alkenyl group)
May be substituted by an oxygen atom (-O-), but two or more methylene groups are not successively substituted by an oxygen atom. Ring A is a trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5
-Diyl group or 1,3-dioxane-2,5-diyl group; ring B is trans-1,4-cyclohexylene group, 1,4-phenylene group or pyrimidine-2,5-
It indicates diyl group, ring C represents trans-1,4-cyclohexylene group or 1,4-phenylene group, the Z ₆ -
(CH ₂ ) ₂ —, —COO— or a covalent bond;
₅ and L ₆ each independently represent H or F, and b and c each independently represent 0 or 1. ) (Wherein, R ₃ represents an alkyl group having 1 to 10 carbon atoms;
₇ represents H or F, and d represents 0 or 1. ) (Wherein, R ₄ represents an alkyl group having 1 to 10 carbon atoms, ring D and ring E independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group,
₇ and Z ₈ independently represent —COO— or a covalent bond, Z ₉ represents —COO— or —C≡C—,
L ₈ and L ₉ independently represent H or F;
₂ represents F, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g independently represent 0
Or 1 is indicated. ) (Wherein, R ₅ and R ₆ are independently of each other having 1 to 1 carbon atoms.
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring G is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and Z ₁₀ represents —C≡C—, —COO—, — (CH
_{2) 2 -, - CH =} CH-C≡C- or indicates a covalent bond, Z ₁₁ represents a -COO- or a covalent bond. ) (Wherein, R ₇ and R ₈ are independently of each other having 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group (—CH ₂ —) may be substituted by an oxygen atom (—O—), but it is difficult that two or more methylene groups are successively substituted by an oxygen atom. Absent. Ring I is trans-1,4
A cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group;
A 1,4-cyclohexylene group, a 1,4-phenylene group or a pyrimidine-2,5-diyl group in which one or more hydrogen atoms on the ring may be substituted with F, and a ring K is trans-1 , 4-cyclohexylene or 1,4-phenylene, wherein Z ₁₂ and Z ₁₄ independently of one another
_{OO -, - (CH 2)} 2 - or indicates a covalent bond, Z ₁₃
Represents -CH = CH-, -C≡C-, -COO- or a covalent bond, and h represents 0 or 1. A) a liquid crystal composition and a liquid crystal display device using the same.