JPH09268137A - Liquid crystal alkynyltolan compound, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new liquid crystal compound, having a sufficiently large Δn, excellent in compatibility with another liquid crystal compound, especially in low temperature compatibility, chemically stable and useful for producing a liquid crystal composition or a liquid crystal display element. SOLUTION: A liquid crystal compound of formula I [R1 is a 1-10C alkyl, a 1-10C alkoxy, cyano or a halogen; R2 is a 1-5C alkyl and one methylene group in the R2 may be substituted with O; X1 and X2 are each H or a halogen; A and B are each a signal bond, a 1,4-phenylene ring or a 1,4-cylohexylene ring (these rings may be each substituted with halogen atom)], e.g. 4-[2-(4- propylphenyl)ethynyl]-1-(3-pentynl)benzene of formula II. A compound of formula I, e.g. a compound whose B is a signal bond or 1,4-phenylene ring, is obtained by brominating a 1-hydroxyalkyl, treating the brominated product with Mg to lead to a Grignard reagent, subsequently treating 4,4'-dibromobiphenyl with the reagent to lead to a compound of formula III and further reacting the resultant reaction product with a compound of formula IV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel liquid crystal compound having suitable physical properties, a liquid crystal composition having suitable physical properties using the above-mentioned novel liquid crystal compound, and a liquid crystal display using the liquid crystal composition. Provide the element.

[0002]

2. Description of the Related Art A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal compound, and its display method is a fertile nematic type (TN type) or a super-fertile nematic type. (STN type), dynamic scattering type (DS type), guest / host type (GH type), DAP type (ECB) type? Etc. are known. Further, as these driving methods, a static driving method, a time division driving method, an active matrix driving method, a dual frequency driving method and the like are known. Several kinds of liquid crystal compounds are mixed and used in order to express the respective characteristics required for these various liquid crystal display elements, but sometimes there are more than 20 kinds of liquid crystal compounds. Therefore, each liquid crystal compound is required to have good compatibility with other liquid crystal compounds, and particularly recently, display devices have come to be used in harsh environments, and have low temperature compatibility. It came to be requested. Further, the required properties of the liquid crystal compound used differ depending on the respective applications, but it is required that all liquid crystal compounds are stable against external environmental factors such as moisture, air, heat and light. .

In order to exhibit suitable characteristics in a liquid crystal display device, one of the characteristics required of a liquid crystal composition or a liquid crystal compound constituting the liquid crystal composition is a refractive index anisotropy value (Δ
n). The display contrast and the viewing angle are greatly influenced by the product (Δn · d) of the refractive index anisotropy value (Δn) and the cell thickness (d). One method for shortening the response time of the liquid crystal composition to changes in the electric field is to reduce the cell thickness, but it is important to reduce the cell thickness while keeping the product (Δn · d) at a desired value. A liquid crystal composition having Δn is required. In order to prepare a liquid crystal composition having a large Δn, a liquid crystal compound having a large Δn is required. As a compound having a relatively large Δn, Japanese Patent Application Laid-Open No. 61-5031 discloses a tolan compound represented by the general formula (10). Cryst. Liq. Cryst. , 4
8 , 175 (1978) discloses a butadiyne derivative represented by the general formula (11).
JP-A-2-180840 discloses an alkynyl tran represented by the general formula (13).

[0004]

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However, the compound represented by the general formula (10) does not have a sufficiently large Δn, and the compound represented by the general formula (11) has a large Δn as compared with the compound represented by the general formula (10). However, the chemical stability, particularly the heat resistance and the light resistance are extremely low, and the compound represented by the formula (12) has a high viscosity because an oxygen atom is contained in the alkynyloxy group of the side chain. The compound represented by (13) has a drawback that the compatibility with other liquid crystal compounds is poor because the triple bond in the side chain is directly connected to the benzene ring.

[0006]

It is an object of the present invention to provide a liquid crystalline compound having properties that make up for the drawbacks of the prior art, that is, having a sufficiently large Δn and compatibility with other liquid crystalline compounds, in particular A novel liquid crystal compound having excellent low-temperature compatibility and being chemically stable, a liquid crystal composition containing the compound, and a display device using the liquid crystal composition.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a compound having a novel structure and having improved properties as compared with known liquid crystalline compounds. Thus, the present invention has been completed. That is, the first invention of the present application is based on the general formula (1):

[0008]

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(Wherein R 1 represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, a cyano group, or a halogen atom, R 2 represents an alkyl group having 1 to 5 carbon atoms, and 1 in R 2
One methylene group (-CH2-) may be replaced by an oxygen atom, X1 and X2 each independently represent a hydrogen atom or a halogen atom, and A and B each independently represent a single bond or a 1,4-phenylene ring. Or a 1,4-cyclohexylene ring, and these rings may be substituted with a halogen atom, and p represents 1 to 5), and is a liquid crystal compound represented by the following second invention. Is a compound represented by the above general formula (1), in which both A and B are co-unitary,
The third invention of the present application is the compound represented by the above general formula (1), wherein A is a 1,4-cyclohexylene ring, and the fourth invention of the present application is the compound wherein A is a 1,4-phenylene ring. A fifth aspect of the present invention is a compound represented by the general formula (1):
B is a compound represented by the above general formula (1), wherein B is a 1,4-cyclohexylene ring, and a sixth invention of the present application is at least one liquid crystal compound represented by the above general formula (1). A seventh aspect of the present invention is a liquid crystal composition comprising at least two components, characterized in that
As a component, at least one compound represented by the general formula (1) is contained, and as a second component, the general formula (2),
(3) and (4)

[0010]

[Chemical 6]

(In the formula, R3 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, Y represents a fluorine atom or a chlorine atom, Q1 and Q2 each independently represent a hydrogen atom or a fluorine atom, and r Represents 1 or 2, and Z1 and Z2 each independently represent -CH2CH2- or a single bond), which is a liquid crystal composition containing at least one compound selected from the group consisting of The eighth invention of the present application contains at least one compound represented by the general formula (1) as a first component, and as the second component, the general formulas (5), (6), (7), (8) ), And (9)

[0012]

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(In the formula, R4 represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in any of them, any methylene group (-CH2-) is an oxygen atom (-O-). It may be substituted by, but two or more methylene groups are not continuously substituted by oxygen atoms, Z3 represents --CH2 CH2-, --COO--, or a single bond, and Q3 and Q4 are independent of each other. Represents a hydrogen atom or a fluorine atom, (E) represents a cyclohexane ring, a benzene ring, or a 1,3-dioxane ring, s represents 0 or 1, and R5 represents an alkyl group having 1 to 10 carbon atoms. , Q5 represents a hydrogen atom or a fluorine atom, and k represents 0 or 1.
R6 represents an alkyl group having 1 to 10 carbon atoms, (G) represents a cyclohexane ring or a benzene ring, Q6 and Q7 each independently represent a hydrogen atom or a fluorine atom, and Z4 represents -COO- or a single bond. And h is 0 or 1: R
7 and R8 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or an alkoxymethyl group,
(H) represents a cyclohexane ring, a pyrimidine ring, or a benzene ring, (J) represents a cyclohexane ring or a benzene ring, and Z5 represents -C≡C-, -COO-, -CH2CH2.
-Or a single bond: R9 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, R10 represents an alkyl group, an alkoxy group or an alkoxymethyl group having 1 to 10 carbon atoms, and (K) is cyclohexane. A ring or a pyrimidine ring, (L) and (M) each independently represent a cyclohexane ring or a benzene ring, and Z6 is -COO- or -CH2.
CH2-or a single bond, Z7 is -C≡C-, -CO
O-, or a single bond, and Q8 represents a hydrogen atom or a fluorine atom) is a liquid crystal composition containing at least one compound selected from the group consisting of Is a liquid crystal display device using a liquid crystal composition containing at least one kind of liquid crystal compound represented by the general formula (1) and comprising at least two components, and the tenth invention of the present application is the sixth invention of the present application. To a liquid crystal display device using the liquid crystal composition according to any one of the eighth to eighth inventions. The eleventh invention of the present application provides a compound represented by the general formula (34) which is an official intermediate for the production of the compound represented by the general formula (1).

[0014]

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(In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, one methylene group (-CH2-) in R2 may be replaced by an oxygen atom, and X represents a halogen atom,
p represents 1 to 5). Among the liquid crystal compounds of the present invention represented by the general formula (1), preferred compounds are compounds represented by the general formulas (1-a) to (1-d).

[0016]

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(In the formula, R1, R2, p, X1 and X2 have the same meanings as described above, and X3 and X4 each independently represent a hydrogen atom or a halogen atom.) ) To (1-d) all have suitable properties, but the terminal alkynyl group is a 2-butynyl group, a 2-pentynyl group, a 2-hexynyl group, a 2-heptynyl group, a 3-pentynyl group. Group, 3-hexynyl group, 3-heptynyl group, 4-hexynyl group, 4-
Heptynyl group, 5-heptynyl group, 5-octynyl group,
A 6-octynyl group, a 6-nonenyl group, a 2-undecynyl group, a 3-undecynyl group, or a 4-undecynyl group is preferable, and among them, a 2-butynyl group, a 2-pentynyl group, a 2-hexynyl group, 2 -Heptinyl group, 3
Those which are a -pentynyl group, a 3-hexynyl group, a 3-heptynyl group, a 4-hexynyl group, or a 4-heptynyl group are particularly preferable. Each of the compounds represented by the general formula (1) has a large Δn, low viscosity, and good compatibility with other liquid crystal compounds. Moreover, both are extremely stable chemically.

The liquid crystalline compounds of the present invention all show suitable physical properties, but in the general formula (1), R1, R2, X1, X2,
By appropriately selecting p, A, and B, it is possible to obtain a compound having physical properties according to the characteristics of the target liquid crystal composition. For example, when used in a liquid crystal composition having a high liquid crystal temperature range, a tricyclic or tetracyclic compound in which a ring is introduced into A or B is used in a liquid crystal composition having a low liquid crystal temperature range. Systemic or tricyclic compounds can be used. In particular, when a liquid crystal composition having a dielectric anisotropy value is obtained, a compound having a positive dielectric anisotropy value (P-type compound) is usually used, and R in the general formula (1) is used.
When 1 is a halogen atom or a cyano group, P
Type compounds can be provided. Furthermore, if a large dielectric anisotropy value is required, at least one of X1, X2, X3, and X4
The object is achieved by introducing a halogen atom into one. In order to obtain a compound having a negative dielectric anisotropy value (N-type compound), an alkyl group or an alkoxy group having a small dipole moment, for example, may be introduced into R1. All the compounds represented by the general formula (1) have a very large Δn, but when a larger refractive index anisotropy value is required, a compound in which A and B are 1,4-phenylene rings is used. do it.

The liquid crystal compounds of the present invention represented by the general formula (1) do not all show a liquid crystal phase. However, each of the liquid crystal compounds represented by the general formula (1) has good compatibility with other liquid crystal compounds, and when mixed with other liquid crystal compounds, does not lower or reduce the nematic phase temperature range. . Therefore, the liquid crystal compound represented by the general formula (1) having excellent optical properties as described above is a useful constituent element of a liquid crystal composition even if it does not exhibit a liquid crystal phase by itself.

The liquid crystal composition according to the present invention has the general formula (1):
At least one type of liquid crystal compound represented by
It is contained in a proportion of 99.9% by weight, and preferably, in the first component containing at least one kind of the compound represented by the general formula (1), depending on the physical properties of the target liquid crystal composition, It is obtained by mixing a compound selected from the group of compounds represented by formulas (2) to (9). General formula (2) preferably used in the liquid crystal composition of the present invention
The following compounds can be illustrated as a compound of (4).

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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(In the formula, R3 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms.) All the compounds represented by the general formulas (2) to (4) have positive dielectric anisotropy. Therefore, the thermal stability and the chemical stability are extremely excellent, and in particular, high reliability such as high voltage holding ratio or large specific resistance value is required.
It is a useful compound when preparing a liquid crystal composition for FT (AM-LCD). STN display method or normal T
The compounds represented by the general formulas (2) to (4) can be used also when preparing a liquid crystal composition for the N display mode. In the liquid crystal composition of the present invention, the general formula (2)
When the liquid crystal composition for TFT is prepared, the amount of the compound represented by (4) is 1 to the total weight of the liquid crystal composition.
It can be appropriately selected and used in the range of 99% by weight,
It is preferably 97% by weight, more preferably 40 to 95% by weight, and the compounds represented by the general formulas (5) to (9) may be used in combination.

Examples of the compounds represented by the general formulas (5) to (7) that are preferably used in the liquid crystal composition of the present invention include the following compounds.

[0032]

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[0033]

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[0034]

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[0035]

[Chemical 21]

(In the formula, R4 represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in any of them, any methylene group (-CH2-) is an oxygen atom (-O-). , But two or more methylene groups are not continuously replaced by oxygen atoms, and R5 and R6 each independently represent an alkyl group having 1 to 10 carbon atoms.) General formula ( The compounds represented by 5) to (7) all have a positive dielectric anisotropy and a large value, and therefore are used for the purpose of particularly reducing the threshold voltage of the liquid crystal composition. It is also used for the purpose of widening the nematic range such as increasing the clearing point, for adjusting the viscosity, adjusting the anisotropy of refractive index, and improving the steepness of threshold characteristics. Examples of the compounds of the general formulas (8) and (9) preferably used in the liquid crystal composition of the present invention include the following compounds.

[0037]

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[0038]

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[0039]

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(In the formula, R7 and R8 each independently represent an alkyl group, an alkoxy group, or an alkoxymethyl group having 1 to 10 carbon atoms, and R9 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, R10 represents an alkyl group, an alkoxy group, or an alkoxymethyl group having 1 to 10 carbon atoms.) The compounds represented by the general formulas (8) and (9) each have a negative dielectric anisotropy value or It is a weakly positive compound. The compound represented by the general formula (8) is mainly used for the purpose of decreasing the viscosity of the liquid crystal composition and / or adjusting the refractive index anisotropy value. The compound represented by the general formula (9) is used for the purpose of widening the nematic range such as increasing the clearing point of the liquid crystal composition and / or adjusting the refractive index anisotropy value. As described above, the compounds of the general formulas (5) to (9) are useful compounds when preparing a liquid crystal composition for a normal TN display system, particularly a liquid crystal composition for an STN display system. In the liquid crystal composition of the present invention, the general formula (5)
The amount of the compound represented by (9) is 1 in the case of preparing a liquid crystal composition for TN display mode and STN display mode.
Can be used in the range of up to 99% by weight, but 10 to 97% by weight
Is preferable, more preferably 40 to 95% by weight,
The compounds of the general formulas (2) to (4) can be used in combination.

By using the liquid crystal composition of the present invention in a TFT liquid crystal display device, the steepness of the electro-optical characteristics at the threshold value and the viewing angle can be improved. Moreover, since the compound represented by the general formula (1) is a low-viscosity compound, the response speed of the liquid crystal display device using this is improved. The liquid crystal composition of the present invention is prepared by a conventional method, for example, a method of dissolving various components with each other at a high temperature. Further, the liquid crystal composition of the present invention is subjected to intended improvements and optimized by appropriate additives according to its use. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. For example, by inducing a helical structure of liquid crystal to adjust a necessary twist angle, a reverse-twist
t) to prevent chiral doping (chiral dop)
ant) etc. are added.

For the purpose of using the liquid crystal composition of the present invention as a liquid crystal composition for guest host (GH) mode,
Merocyanine, styryl, azo, azomethine,
Azoxy-based, quinophthalone-based, anthraquinone-based and tetrazine-based dichroic dyes can be added.
The liquid crystal composition of the present invention is a polymer dispersion represented by NCAP prepared by encapsulating a nematic liquid crystal in a microcapsule or a polymer network liquid crystal display device (PNLCD) in which a three-dimensional knitted polymer is introduced into the liquid crystal. It can be used as a liquid crystal composition for a liquid crystal display device (PDLCD), or as a liquid crystal composition for a birefringence control (ECB) type or a dynamic scattering (DS) type. The following composition examples can be given as the nematic liquid crystal composition containing the compound of the present invention thus prepared.

Composition Example 1 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentynyl) benzen 5% 4- (2- (4-pentylphenyl) ethynyl) -1- (3- Pentynyl) benzene 5% 4- (2- (4-methoxyphenyl) ethynyl) -1- (3-pentynyl) benzene 5% 4- (4-ethylcyclohexyl) -2-fluorobenzonitrile 3% 4- ( 4-propylcyclohexyl) benzonitrile 10% 4- (4-methoxymethylcyclohexyl) benzonitrile 7% 4'-methoxymethyl-4-pentylbicyclohexane 5% 4-fluorophenyl = 4-pentylcyclohexanecarboxylate 5% 4-fluorophenyl = 4-heptylcyclohexanecarboxylate 5% 4-fluorophenyl = 4 ′ -Propylbicyclohexanecarboxylate 3% 4-fluorophenyl = 4'-pentylbicyclohexanecarboxylate 3% 4- (4'-ethylbicyclohexyl) -2-fluorobenzonitrile 5% 4- (4 ' -Propylbicyclohexyl) -2-fluorobenzonitrile 5% 4- (4'-ethylbicyclohexyl) -1,2-difluorobenzene 5% 4- (4'-propylbicyclohexyl) -1,2-difluorobenzene 5 % 4- (4'-pentylbicyclohexyl) -1,2-difluorobenzene 5% 4- (4'-ethylbicyclohexyl) -1-methylbenzene 5% 4- (4'-propylbicyclohexyl) -1- Methylbenzene 10% 4- (4'-Propylbicyclohexyl) -1-fluorobenzene 4%

Composition Example 2 4- (2- (4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene 10% 4'-ethyl-4-cyanobiphenyl 8.5% 4'-butyl-4 -Cyanobiphenyl 8% 4- (4-propylcyclohexyl) benzonitrile 4.8% 4- (4-pentylcyclohexyl) benzonitrile 6.4% 4- (4-heptylcyclohexyl) benzonitrile 4.8% 4- ( 4-Methoxymethylcyclohexyl) benzonitrile 11% 4-butoxyphenyl = 4-propylcyclohexanecarboxylate 4% 4-ethoxyphenyl = 4-butylcyclohexanecarboxylate 3% 4-methoxyphenyl = 4-pentylcyclohexanecarboxy Rat 3% 4-ethoxyphenyl = 4-propylcyclo Hexanecarboxylate 2.5% 4-ethoxyphenyl = 4-pentylcyclohexanecarboxylate 2% 4- (4'-ethylbicyclohexyl) benzonitrile 4% 4- (4'-propylbicyclohexyl) benzonitrile 4% 4- (4'-propylbicyclohexyl) -1-methoxybenzene 5% 4- (4'-propylbicyclohexyl) -1-methylbenzene 7% 4- (4'-propylbicyclohexyl) -1-propyl Benzene 12%

Composition Example 3 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (3-pentenyl) benzene 8% 3,5-difluoro-4-cyanophenyl = 4- (3 -Pentenyl) benzoate 3% 3-Fluoro-4-cyanophenyl = 4-ethoxymethylbenzoate 5% 3-Fluoro-4-cyanophenyl = 4-propoxymethylbenzoate 10% 3-Fluoro- 4-Cyanophenyl = 4-butoxymethylbenzoate 10% 3-Fluoro-4-cyanophenyl = 4-pentoxymethylbenzoate 9% 4- (4-propylcyclohexyl) -1-ethoxybenzene 16% 4- (4'-ethylbicyclohexyl) -3-fluorobenzonitrile 12% 4- (4'-propylbicyclohexyl) -3 -Fluorobenzonitrile 12% 4- (2- (2-Fluoro-4- (4-ethylcyclohexyl) phenyl) ethynyl) -1-ethylbenzene 5% 4- (2- (2-Fluoro-4- (4- Propylcyclohexyl) phenyl) ethynyl) -1-ethylbenzene 5% 4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethynyl) -1-ethylbenzene 5%

Composition Example 4 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentynyl) benzen 7% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl)- 1- (3-Pentenyl) benzene 6% 2- (3,4-difluorophenyl) -5-propylpyrimidine 8% 4'-butyl-4-cyanobiphenyl 5% 4'-pentyl-4-cyanobiphenyl 5% 2 -(4-Ethylphenyl) -5-propylpyrimidine 8% 2- (4-ethylphenyl) -5-butylpyrimidine 8% 2- (4'-fluorobiphenylyl) -5-propylpyrimidine 5% 2- (4 '-Fluorobiphenylyl) -5-butylpyrimidine 5% 2- (4'-fluorobiphenylyl) -5-pentylpyrimidine 5% 4- (4'-propynyl Biphenylyl) -1-methylbenzene 5% 4- (4'-propylbiphenylyl) -1-propylbenzene 7% 4- (2- (4- (2- (4-ethylcyclohexyl) ethyl) phenyl) ethynyl) -1-ethylbenzene 3% 4- (2- (4- (2- (4-ethylcyclohexyl) ethyl) phenyl) ethynyl) -1-propylbenzene 3% 4- (2- (4- (2- (4 -Ethylcyclohexyl) ethyl) phenyl) ethynyl) -1-butylbenzene 3% 4- (2- (4- (2- (4-propylcyclohexyl) ethyl) phenyl) ethynyl) -1-ethylbenzene 3% 4- (2- (4- (2- (4-propylcyclohexyl) ethyl) phenyl) ethynyl) -1-propylbenzene 3% 4- (2- (4- (2- (4-propyl) Chlohexyl) ethyl) phenyl) ethynyl) -1-butylbenzene 3% 4- (2- (4-ethylphenyl) ethynyl) -1-methylbenzene 2% 4- (2- (4-methylphenyl) ethynyl)- 1-hexylbenzene 4% 4- (2- (4-butylphenyl) ethynyl) -1-butylbenzene 2%

Composition Example 5 4- (2- (4-pentylphenyl) ethynyl) -1- (3-pentynyl) benzen 8% 4- (2- (4-propylphenyl) ethynyl) -1- (2- Pentynyl) benzene 8% 4- (4-heptylcyclohexyl) -3,4-difluorobenzene 4% 4- (2- (4-heptylcyclohexyl) ethyl) -3,4-difluorobenzene 6% 4- (4 '-Ethylbiphenylyl) -3,4-difluorobenzene 10% 4- (4'-propylbiphenylyl) -3,4-difluorobenzene 10% 4- (4'-pentylbiphenylyl) -3,4-difluoro Benzene 10% 4- (4- (2- (4- (ethylcyclohexyl) ethyl) cyclohexyl) -3,4-difluorobenzene 3% 4- (4- (2- (4-p- Pyrcyclohexyl) ethyl) cyclohexyl) -3,4-difluorobenzene 1.5% 4- (4- (2- (4-pentylcyclohexyl) ethyl) cyclohexyl) -3,4-difluorobenzene 3% 4 '-(4 -Ethylcyclohexyl) -3,4-difluorobiphenyl 4% 4 '-(4-propylcyclohexyl) -3,4-difluorobiphenyl 4% 4'-(4-pentylcyclohexyl) -3,4-difluorobiphenyl 8% 4 '-(4-Ethylcyclohexyl) -4-fluorobiphenyl 4% 4'-(4-propylcyclohexyl) -4-fluorobiphenyl 4% 4 '-(4-pentylcyclohexyl) -4-fluorobiphenyl 2% 4- ( 4'-Propylbicyclohexyl) -1-fluorobenzene 3.5% 4- (4'-Propylbicyclohexyl) -1-methylbenzene 7%

Composition Example 6 4- (2- (4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene 8% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl)- 1- (3-Pentenyl) benzene 5% 4- (4-propylcyclohexyl) -1-chlorobenzene 4% 4- (4-pentylcyclohexyl) -1-chlorobenzene 4% 4- (4-heptylcyclohexyl) -1-chlorobenzene 5% 4- (4- (4-ethylcyclohexyl) cyclohexyl) -1-chlorobenzen 5% 4- (4- (4-propylcyclohexyl) cyclohexyl) -1-chlorobenzen 7% 4- (4- (4- (4- Pentylcyclohexyl) cyclohexyl) -1-chlorobenzene 6% 4 ′-(4-ethylcyclohexyl) -3 , 4-difluorobiphenyl 5% 4 '-(4-propylcyclohexyl) -3,4-difluorobiphenyl 5% 4'-(4-pentylcyclohexyl) -3,4-difluorobiphenyl 10% 4 '-(4-propyl Cyclohexyl) -3,4,5-trifluorobiphenyl 12% 4 '-(4-pentylcyclohexyl) -3,4,5-trifluorobiphenyl 12% 4- (4- (2- (4-propylcyclohexyl) ethyl) ) Cyclohexyl) -2-fluoro-1-chlorobenzene 3% 4- (2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1-ethylbenzene 3% 4- (2- (2- Fluoro-4- (4-propylcyclohexyl) phenyl) ethenyl) -1-ethylbenzene 3%

Composition Example 7 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentynyl) benzen 5% 4- (2- (4-methoxyphenyl) ethynyl) -1- (3- Pentynyl) benzene 6% 4- (2- (4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene 5% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl)- 1- (3-Pentynyl) benzene 6% 2- (3,4-Difluorophenyl) -5-propylpyrimidine 10% 2- (3,4-Difluorophenyl) -5-pentylpyrimidine 10% 2- (4- ( 4-ethylcyclohexyl) phenyl) -5-propylpyrimidine 5% 2- (4- (4-ethylcyclohexyl) phenyl) -5-butylpyrimidine 5% 2- (4- ( -Propylcyclohexyl) phenyl) -5-ethylpyrimidine 5% 2- (4- (4-propylcyclohexyl) phenyl) -5-propylpyrimidine 5% 2- (4- (4-propylcyclohexyl) phenyl) -5 -Butylpyrimidine 5% 2- (4'-fluorobiphenyl) -5-propylpyrimidine 6% 2- (4'-fluorobiphenyl) -5-butylpyrimidine 6% 2- (4'-fluorobiphenyl) -5-pentyl Pyrimidine 6% 2- (4-Ethylphenyl) -5-ethylpyrimidine 5% 2- (4-Ethylphenyl) -5-propylpyrimidine 5% 2- (4-Ethylphenyl) -5-butylpyrimidine 5%

Composition Example 8 4- (2- (4-methoxyphenyl) ethynyl) -1- (3-pentynyl) benzen 10% 4-cyanophenyl = 4-ethylbenzoate 3% 4-cyanophenyl = 4- Propylbenzoate 3% 2- (4-Cyanophenyl) -5-propyl-1,3-dioxane 7% 2- (4-Cyanophenyl) -5-butyl-1,3-dioxane 8% 2- ( 4-Cyanophenyl) -5-pentyl-1,3-dioxane 3.4% 4'-methoxymethyl-4-propylbicyclohexane 6% 4'-methoxymethyl-4-pentylbicyclohexane 10% methyl = 4'- Propylbicyclohexanecarboxylate 10% Methyl = 4'-pentylbicyclohexanecarboxylate 7% 4- (4'-propylbicyclohexyl) ) -1-Propylbenzene 10% 4- (4'-propylbicyclohexyl) -1-methoxybenzene 5% 4-butoxyphenyl = 4-propylcyclohexanecarboxylate 3.2% 4-ethoxyphenyl = 4-Butylcyclohexanecarboxylate 2.4% 4-methoxyphenyl = 4-pentylcyclohexanecarboxylate 2.4% 4-ethoxyphenyl = 4-propylcyclohexanecarboxylate 2% 4 -Ethoxyphenyl = 4-pentylcyclohexanecarboxylate 1.6% 4-propylphenyl = 4-butylcyclohexanecarboxylate 3% 4-pentylphenyl = 4-pentylcyclohexanecarboxylate 3 %

Composition Example 9 4- (2- (4-pentylphenyl) ethynyl) -1- (3-pentynyl) benzene 7% 4- (2- (4-propylphenyl) ethynyl) -1- (2- Pentynyl) benzene 7% 4- (2- (4- (4-pentylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene 7% 4- (4- (3-butenyl) cyclohexyl) benzonitrile 7 % 4- (4- (3-Pentenyl) cyclohexyl) benzonitrile 7% 4- (4-propylcyclohexyl) benzonitrile 10% 4- (4-methoxymethylcyclohexyl) benzonitrile 3% 4- (4-ethoxymethylcyclohexyl) ) Benzonitrile 3% 4- (2- (4-ethylphenyl) ethynyl) -1-methoxybenzene 3% 4- (2- (4-Pentylphenyl) ethynyl) -1-methoxybenzene 3% 4'-methoxymethyl-4-pentylbicyclohexane 5% 4'-propyl-4-butylbicyclohexane 5% 4- (4'-ethylbicyclohexyl) Benzonitrile 2% 4- (4'-propylbicyclohexyl) benzonitrile 3% 4- (4'-propylbicyclohexyl) -1-methoxybenzene 4% 4- (4'-propylbicyclohexyl) -1-methylbenzene 7% 4- (4'-propylbicyclohexyl) -1-propylbenzene 8% 4- (2- (4- (2- (4-propylcyclohexyl) ethyl) phenyl) ethynyl) -1-ethylbenzene 3% 4 -(2- (4- (2- (4-propylcyclohexyl) ethyl) phenyl) ethynyl) -1-p Pirubenzen 3% 4- (2- (4- (2- (4-propylcyclohexyl) ethyl) phenyl) d ethynyl) -1-butylbenzene 3%

Composition Example 10 4- (2- (4-Pentylphenyl) ethynyl) -1- (3-pentynyl) benzen 7% 4- (2- (4-methoxyphenyl) ethynyl) -1- (3- Pentynyl) benzene 7% 4- (2- (4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene 7% 4- (4-pentylcyclohexyl) -1-fluorobenzene 8% 4- (4 -Heptylcyclohexyl) -1-fluorobenzene 8% 4- (4'-ethylbicyclohexyl) -1-trifluoromethoxybenzene 5% 4- (4'-propylbicyclohexyl) -1-trifluoromethoxybenzene 5% 4 -(4'-Pentylbicyclohexyl) -1-trifluoromethoxybenzene 5% 4- (4'-Propylbicyclohexyl) -1- Fluoromethoxy-2,6-difluorobenzene 15% 4- (4'-pentylbicyclohexyl) -1-difluoromethoxy-2,6-difluorobenzene 15% 2 ', 6'-difluoro-4'-(4-propyl Cyclohexyl) -3,4-difluorobiphenyl 6% 2 ', 6'-difluoro-4'-(4-pentylcyclohexyl) -3,4-difluorobiphenyl 6% 4-trifluoromethoxyphenyl = 4'- Propylbicyclohexanecarboxylate 3% 4-Trifluoromethoxyphenyl = 4'-pentylbicyclohexanecarboxylate 3%

Composition Example 11 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentynyl) benzen 9% 4- (2- (4-pentylphenyl) ethynyl) -1- (3- Pentynyl) benzene 9% 4- (4-pentylcyclohexyl) -1-fluorobenzene 8% 4- (4-hexylcyclohexyl) -1-fluorobenzene 8% 4- (4-heptylcyclohexyl) -1-fluorobenzene 8 % 4- (4'-ethylbicyclohexyl) -1-trifluoromethoxybenzene 6% 4- (4'-propylbicyclohexyl) -1-trifluoromethoxybenzene 6% 4- (4'-butylbicyclohexyl)- 1-trifluoromethoxybenzene 6% 4- (4'-pentylbicyclohexyl) -1-trifluoromethoxybenzene Zen 6% 4- (2- (4'-propylbicyclohexyl) ethyl) -1-trifluoromethoxybenzene 5% 4- (2- (4'-pentylbicyclohexyl) ethyl) -1-trifluoromethoxybenzene 5 % 4 '-(4-propylcyclohexyl) -3,4-difluorobiphenyl 8% 4'-(4-pentylcyclohexyl) -3,4-difluorobiphenyl 8% 2'-fluoro-4 '-(4-propylcyclohexyl) ) -4- (4-Propylcyclohexyl) biphenyl 4% 2'-fluoro-4 '-(4-pentylcyclohexyl) -4- (4-propylcyclohexyl) biphenyl 4%

Composition Example 12 4- (2- (4-pentylphenyl) ethynyl) -1- (3-pentynyl) benzen 5% 4- (2- (4-methoxyphenyl) ethynyl) -1- (3- Pentynyl) benzene 5% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene 5% 4- (4- (2-propenyl) cyclohexyl) benzonitrile 4 % 4'-butyl-4-ethylbiphenyl 4% 4'-propyl-4-cyanobiphenyl 5% 4'-pentyl-4-cyanobiphenyl 5% 4- (4-ethylcyclohexyl) -2-fluorobenzonitrile 5% 4- (2- (4-propylcyclohexyl) ethyl) -1-ethoxybenzene 5% 4- (2- (4-pentylcyclohexyl) ethyl)- 1-propoxybenzene 8% 4-cyanophenyl = 4-propylbenzoate 5% 4-methoxyphenyl = 4-pentylcyclohexanecarboxylate 6% 4-propoxyphenyl = 4-pentylcyclohexanecarboxylate 6% 1 ''-pentyl-4-cyanota-phenyl 4% 2- (4-cyanophenyl) -5- (4-butylphenyl) pyrimidine 4% 2- (4-pentylphenyl) -5- (4-butylphenyl) Pyrimidine 4% 4- (2- (4- (4-pentylcyclohexyl) phenyl) ethyl) -1-butylbenzene 4% 4- (2- (4 '-(4-pentylcyclohexyl) biphenylyl) ethyl) -1- Propylbenzene 4% 4 '-(1-propenyl) -4-methoxymethylbicyclohexane 6% 4'-(4 -(3-Pentenyl) cyclohexyl) -4-propylbiphenyl 6%

Composition Example 13 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentenyl) benzen 10% 4- (2- (4-methoxyphenyl) ethynyl) -1- (3- Pentenyl) benzene 10% 3,4-difluorophenyl = 4-butylcyclohexanecarboxylate 5% 3,4-difluorophenyl = 4-pentylcyclohexanecarboxylate 5% 3-fluoro-4-cyanophenyl = 4 -Ethylbenzoate 4% 3-Fluoro-4-cyanophenyl = 4-propylbenzoate 4% 3-Fluoro-4-cyanophenyl = 4-butylbenzoate 6% 3-Fluoro-4-cyanophenyl = 4 -Pentyl benzoate 6% 4- (4- (3-methoxypropyl) cyclohexyl) -2-fluorobenzonitrile 6% 3,4-difluorophenyl = 4′-propylbicyclohexanecarboxylate 4% 3,4-difluorophenyl = 4′-pentylbicyclohexanecarboxylate 4% 3-fluoro-4-cyanophenyl = 4 -(4-Ethylcyclohexyl) benzoate 5% 3-fluoro-4-cyanophenyl = 4- (4-propylcyclohexyl) benzate 5% 3-fluoro-4-cyanophenyl = 4- (4- Butylcyclohexyl) benzoate 5% 3-fluoro-4-cyanophenyl = 4- (4-pentylcyclohexyl) benzato 5% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1-Ethylbenzene 10% 4 '-(3-butenyl) -4-propylbicyclohexane 3% 4- (4 - (3-butenyl) bicyclohexyl) -1-methylbenzene 3%

Composition Example 14 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentenyl) benzen 6% 4- (2- (4-pentylphenyl) ethynyl) -1- (3- Pentenyl) benzene 6% 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (3-pentenyl) benzene 5% 4- (4-heptylcyclohexyl) -1,2,6- Trifluorobenzene 3% 4- (4'-propylbicyclohexyl) -1-fluorobenzene 3% 4- (4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl) -1,2,6-trifluorobenzene 7% 4- (4- (2- (4- (4-butylcyclohexyl) ethyl) cyclohexyl) -1,2,6-trifluorobenzene 7% 4- (4- (2- ( -Pentylcyclohexyl) ethyl) cyclohexyl) -1,2,6-trifluorobenzene 7% 4- (4'-propylbicyclohexyl) -1,2,6-trifluorobenzene 5% 4- (4'-butylbi) Cyclohexyl) -1,2,6-trifluorobenzene 3% 4- (2- (4'-propylbicyclohexyl) ethyl) -1,2,6-trifluorobenzene 12% 4- (2- (4'-pliers Rubicyclohexyl) ethyl) -1,2,6-trifluorobenzene 10% 4 '-(4-propylcyclohexyl) -3,4,5-trifluorobiphenyl 10% 4'-(4-pentylcyclohexyl) -3,4 , 5-Trifluorobiphenyl 10% 4 '-(4'-propylbicyclohexyl) -3,4,5-trifluorobiphenyl 3% 4 '-(2- (4'-propylbicyclohexyl) ethyl) -3,4,5-trifluorobiphenyl 3%

The compound represented by the general formula (1) of the present invention can be easily produced by making use of usual organic synthetic chemistry techniques as shown below. [When B is a Single Bond or 1,4-Phenylene Ring in General Formula (1)] 1-Hydroxyalkynes (14)
For example, J. Am. Chem. Soc. , 71 , 12
92 (1949) according to the method of phosphorus tribromide,
Org. Synth. , V, 249 (197
Bromide (15) is obtained by acting triphenylphosphine dibromide according to the method of 3). (15)
Reacting magnesium with Grignard reagent (16)
After that, J. Chem. Soc. Chem. Com
mun. , 144 (1972) or J. Am. Ch
em. Soc. , 94 , 4374 (1972), 4,4′-dibromobiphenyl or p-dibromobenzene is allowed to act in the presence of a catalyst to obtain an alkynyl bromobenzene derivative (17). The final coupling reaction can be suitably carried out by various methods. Org. Chem. , 28 , 2163, 3313
The target compound of the general formula (1) can be produced by reacting the alkenylbromobenzene derivative (17) with the arylacetylene derivative (18) according to the method of (1963). When a substituent active in this reaction is present in the molecule of the arylacetylene derivative (18), milder conditions such as J. Org. Chem. , 42 , 182
1 (1977).

[0058]

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The aryl acetylene derivative (18) is prepared from dibromide (22), which can be easily produced by adding bromine to the corresponding styrene derivative according to J. Org. Che
m. , 38 , 1367 (1973), it can be easily produced by treating with a base.

[0060]

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Further, 1-hydroxyalkynes (14)
Some of them, such as 2-butyn-1-ol and 3
-Pentin-1-ol can be a commercially available product, but other products are Org. Synth. , I, 306 (194
1) or J. Am. Chem. Soc. , 73 , 1
24 (1951) according to the method of 1-alkynes (2
It can be produced by sequentially reacting 3) with alkyllithium and cyclic ether.

[0062]

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[When B is a 1,4-cyclohexylene ring in the general formula (1)] J. Org. Chem. ,
50 , 5761 (1985) or Tetrahed
ron Lett. , 3463 (1984), the bromocyclohexane derivative (19) is treated with alkyllithium and zinc bromide sequentially under ultrasonic irradiation to form a zinc compound (20), which is then treated with a Grignard reagent in the presence of a catalyst. The compound (21) is obtained by reacting (16). J. Org. Chem. , 28 , 2163, 33
According to the method of 13 (1963), the target compound of the general formula (1) can be produced by reacting the compound (21) with the arylacetylene derivative (18) in the presence of a catalyst.

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The bromocyclohexane derivative (19) is
By a conventional method, for example, US Pat. No. 4,405,488 (1
According to the method of 983), cyclohexanedione monoketal (26) is allowed to act on 4-chlorophenylmagnesium bromide (25) to dehydrate compound (27), and then the protecting group is removed under acidic conditions to remove compound (28). ),
J. Org. Chem. , 30 , 766 (1965) or Bull. Chem. Soc. Jpn. , 39 ,
Hydrogenation according to the method of 1129 (1966),
J. Am. Chem. Soc. , 86 , 1571 (19
64) or J. Org. Chem. , 6 , 852
The carbonyl group is reduced according to the method of (1941), and then, for example, Org. Synth. , V, 249 (19
It can be produced by bromination according to the method of 73).

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The alkynyl bromobenzene derivative (17) can also be produced by the following method. From the Grignard reagent prepared from 1-halogenoalkene and p-dibromobenzene, J. Chem. Soc. Che
m. Commun. 144 (1972), J. Am.
Chem. Soc. , 94 , 4374 (1972), and alkenylbenzene derivative (31) produced by the method.
Dibromide (32) was obtained by treating bromine with alkynyl bromobenzene derivative (33).
Is obtained. J. Org. Chem. , 40 , 2250
According to the method of (1975), an alkynyl bromobenzene derivative (17) can be produced by treating the alkynyl bromobenzene derivative (33) with alkyllithium and then reacting with an alkyl halide.

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[0069]

[Examples] Hereinafter, the production method and use examples of the compound of the present invention will be described in more detail with reference to Examples. In each example, C is a crystal, N is a nematic phase, S
Indicates a smectic phase, I indicates an isotropic liquid, and the unit of the phase transition temperature is ° C. Example 1 4- (2- (4-propylphenyl) ethynyl) -1-
(3-Pentynyl) benzene (in the general formula (1), R
Production of compound No. 18) wherein 1 is a propyl group, R2 is a methyl group, l is 2, and A and B are single bonds.

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First Stage Preparation of 4-bromo-1- (3-pentynyl) benzene. To a mixture of sufficiently dried magnesium (100 mmol) and tetrahydrofuran (THF) 20 ml, commercially available 3
-Pentyn-1-ol and phosphorus tribromide from J. Am. C
hem. Soc. , 71 , 1292 (1949). 1-Bromo-3-pentyne (95 mmo
A solution of l) in 100 ml of THF was added dropwise at 40 ° C. or lower for 1 hour to prepare a Grignard reagent. p-dibromobenzene (150 mmol), bis (triphenylphosphine) nickel (II) dichloride (7.5 mmol),
And 150 ml of THF were gradually added dropwise (about 1 hour) to the Grignard reagent at 0 ° C or lower.
After heating and stirring under reflux for 1 hour, the mixture was allowed to cool to room temperature. To the reaction solution were added 200 ml of toluene and 200 ml of water and well stirred, and the organic layer was washed 3 times with 200 ml of brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure at 30 ° C. or lower, the residue was purified by silica gel column chromatography (eluting solvent: heptane / toluene mixture), and further distilled under reduced pressure to give oily 4-bromo-1- (3-
Pentynyl) benzene (61 mmol) was obtained. Also,
p-Diiodobenzene was used instead of p-dibromobenzene to give 4-iodo-1- (3-pentynyl) benzene. Boiling point: 122-123 ° C / 1 mmHg

Stage 2 Preparation of title compound. 4-propylphenylacetylene (61 mmol) was dissolved in 80 ml of tetrahydrofuran (THF) to obtain -78.
Cooled to ℃, butyl lithium hexane 1.6M
The solution (corresponding to 61 mmol) was gradually added dropwise while maintaining -78 ° C. Further, a 0.5 M solution of zinc chloride in THF (equivalent to 61 mmol) was added dropwise at the same temperature, and the temperature was gradually returned to room temperature. Tetrakis (triphenylphosphine) palladium (0) (3 mmol) was added to the obtained yellow reaction solution.
And 4-bromo-1- (3-pentynyl) obtained in the first step
Benzene (61 mmol) was added all at once, and the mixture was heated under stirring and reflux for 1 hour. After allowing the reaction solution to cool, 100 ml of toluene and 100 ml of water were added and well stirred, and 100 ml of the organic layer was added.
The extract was washed 3 times with brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (eluting solvent: heptane), and recrystallized twice from 25 ml of ethanol to obtain the title compound (48 mmol). The melting point of this product is 70.
0 to 70.5 ° C., and various spectral data well supported the structure. MS: 286 (M ⁺ ),

Example 2 2-Pentin-1-in place of 1-Bromo-3-pentyne
According to the method of Example 1, 4- (2- (4
-Propylphenyl) ethynyl) -1- (2-pentynyl) benzene (Compound No. 17) was synthesized. This product had a melting point of 52.0 ° C and an SI point of 47.0 ° C.

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Example 3 4-pentylphenylacetylene was used in place of 4-propylphenylacetylene, and the procedure of Example 1 was repeated.
-(2- (4-pentylphenyl) ethynyl) -1-
(3-Pentynyl) benzene (Compound No. 22) was synthesized. The melting point of this product was 59.0 to 60.0 ° C.

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Example 4 According to the method of Example 1, except that 4-methoxyphenylacetylene was used instead of 4-propylphenylacetylene, 4
-(2- (4-Methoxyphenyl) ethynyl) -1-
(3-Pentynyl) benzene (Compound No. 16) was synthesized. The melting point of this product was 91.0 to 91.5 ° C.

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Example 5 4- (2- (4- (4-propylcyclohexyl) phenyl) was prepared according to the method of Example 1 using 4- (4-propylcyclohexyl) phenylacetylene instead of 4-propylphenylacetylene. ) Ethynyl) -1- (3-pentynyl) benzene (Compound No. 63) was synthesized. This shows a liquid crystal phase, CN point: 126 ° C., NI point: 2
It was 10 ° C.

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The following compounds are synthesized according to the above Examples 1-5. The compounds of Examples 1-5 are also reposted. Compound No. 1 4- (2- (4-methylphenyl) ethynyl) -1-
(2-butynyl) benzene compound number 2 4- (2- (3-fluoro-4-methylphenyl) ethynyl) -1- (2-butynyl) benzene compound number 3 4- (2- (3,5-difluoro- 4-Methylphenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 4 4- (2- (4-methoxyphenyl) ethynyl) -1-
(2-butynyl) benzene Compound No. 5 4- (2- (4-ethylphenyl) ethynyl) -1-
(2-butynyl) benzene Compound No. 6 4- (2- (4-propylphenyl) ethynyl) -1-
(2-butynyl) benzene compound number 7 4- (2- (3-fluoro-4-propylphenyl) ethynyl) -1- (2-butynyl) benzene compound number 8 4- (2- (3,5-difluoro- 4-Propylphenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 9 4- (2- (4-propoxyphenyl) ethynyl) -1
-(2-butynyl) benzene

Compound No. 10 4- (2- (4-pentylphenyl) ethynyl) -1-
(2-butynyl) benzene compound number 11 4- (2- (3-fluoro-4-pentylphenyl) ethynyl) -1- (2-butynyl) benzene compound number 12 4- (2- (4-hexylphenyl) ethynyl ) -1-
(2-Butynyl) benzene Compound No. 13 4- (2- (4-methylphenyl) ethynyl) -1-
(2-butynyl) benzene compound number 14 4- (2- (3-fluoro-4-methylphenyl) ethynyl) -1- (2-pentynyl) benzene compound number 15 4- (2- (3,5-difluoro-) 4-Methylphenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 16 4- (2- (4-methoxyphenyl) ethynyl) -1-
(3-Pentynyl) benzene C 91.0-91.
5 I Compound No. 17 4- (2- (4-propylphenyl) ethynyl) -1-
(2-Pentynyl) benzene (CI 52.0
C, SI 47.0 C) Compound No. 18 4- (2- (4-propylphenyl) ethynyl) -1-
(3-Pentynyl) benzene C 70.0-70.
5 I Compound No. 19 4- (2- (3-Fluoro-4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene

Compound No. 20 4- (2- (3,5-difluoro-4-propylphenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 21 4- (2- (4-propoxyphenyl) ethynyl) -1
-(2-Pentynyl) benzene Compound No. 22 4- (2- (4-pentylphenyl) ethynyl) -1-
(3-Pentynyl) benzene C 59.0-60.
0 I compound number 23 4- (2- (3-fluoro-4-pentylphenyl) ethynyl) -1- (2-pentynyl) benzene compound number 24 4- (2- (4-hexylphenyl) ethynyl) -1-
(2-Pentynyl) benzene Compound No. 25 4- (2- (4-methylphenyl) ethynyl) -1-
(2-hexynyl) benzene compound number 26 4- (2- (3-fluoro-4-methylphenyl) ethynyl) -1- (2-hexynyl) benzene compound number 27 4- (2- (3,5-difluoro-) 4-Methylphenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 28 4- (2- (4-methoxyphenyl) ethynyl) -1-
(2-hexynyl) benzene compound number 29 4- (2- (4-ethylphenyl) ethynyl) -1-
(2-hexynyl) benzene

Compound No. 30 4- (2- (4-propylphenyl) ethynyl) -1-
(2-hexynyl) benzene compound number 31 4- (2- (3-fluoro-4-propylphenyl) ethynyl) -1- (2-hexynyl) benzene compound number 32 4- (2- (3,5-difluoro-) 4-Propylphenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 33 4- (2- (4-propoxyphenyl) ethynyl) -1
-(2-hexynyl) benzene compound number 34 4- (2- (4-methylphenyl) ethynyl) -1-
(2-Heptinyl) benzene Compound No. 35 4- (2- (3-Fluoro-4-methylphenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 36 4- (2- (3,5-difluoro- 4-Methylphenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 37 4- (2- (4-methoxyphenyl) ethynyl) -1-
(2-Heptinyl) benzene Compound No. 38 4- (2- (4-ethylphenyl) ethynyl) -1-
(2-Heptinyl) benzene Compound No. 39 4- (2- (4-propylphenyl) ethynyl) -1-
(2-heptynyl) benzene

Compound No. 40 4- (2- (3-Fluoro-4-propylphenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 41 4- (2- (4-methylphenyl) ethynyl) -1 −
(2-octynyl) benzene Compound No. 42 4- (2- (3-fluoro-4-methylphenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 43 4- (2- (3,5-difluoro- 4-Methylphenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 44 4- (2- (4-ethylphenyl) ethynyl) -1-
(3-octynyl) benzene Compound No. 45 4- (2- (4-propylphenyl) ethynyl) -1-
(4-octynyl) benzene compound number 46 4- (2- (4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene compound number 47 4- (2- (3-fluoro-4) -(4-Methylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl)
Benzene compound number 48 4- (2- (3,5-difluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene compound number 49 4- (2- (4- (4 -Methoxycyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene

Compound No. 50 4- (2- (4- (4-ethylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 51 4- (2- (4- (4-propylcyclohexyl)) Phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 52 4- (2- (3-fluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 53 4- (2- (3,5-difluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 54 4- (2- (4- (4-propoxycyclohexyl)) Phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 55 4- (2- (4- (4-pentylcyclohexyl)) phenyl Nyl) ethynyl) -1- (2-butynyl) benzene compound number 56 4- (2- (3-fluoro-4- (4-pentylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene compound number 57 4- (2- (4- (4-hexylcyclohexyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 58 4- (2- (4- (4-methylcyclohexyl) phenyl) ethynyl) -1 -(2-butynyl) benzene compound number 59 4- (2- (3-fluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene

Compound No. 60 4- (2- (3,5-difluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 61 4- (2- (4- (4-Methoxycyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 62 4- (2- (4- (4-ethylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 63 4- (2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene
CN: 126 ° C., NI: 210 ° C. Compound No. 64 4- (2- (3-Fluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 65 4- (2 -(3,5-Difluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 66 4- (2- (4- (4-propoxycyclohexyl) phenyl) ethynyl) -1- (2-Pentynyl) benzene compound number 67 4- (2- (4- (4-pentylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene compound number 68 4- (2- (3- Fluoro-4- (4-pentylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene Compound No. 69 4- 2- (4- (4-hexylcyclohexyl) phenyl) ethynyl) -1- (2-pentynyl) benzene

Compound No. 70 4- (2- (4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 71 4- (2- (3-fluoro-4- (4 -Methylcyclohexyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 72 4- (2- (3,5-difluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2- Hexynyl) benzene Compound No. 73 4- (2- (4- (4-methoxycyclohexyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 74 4- (2- (4- (4-ethylcyclohexyl)) Phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 75 4- (2- (4- (4-propylcyclohexyl)) Phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 76 4- (2- (3-fluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 77 4- (2- (3,5-difluoro-4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 78 4- (2- (4- (4-propoxycyclohexyl)) Phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 79 4- (2- (4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-heptynyl) benzene

Compound No. 80 4- (2- (3-Fluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (4-heptynyl) benzene Compound No. 81 4- (2- (3,5- Difluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 82 4- (2- (4- (4-methoxycyclohexyl) phenyl) ethynyl) -1- (2- Heptinyl) benzene compound number 83 4- (2- (4- (4-ethylcyclohexyl) phenyl) ethynyl) -1- (2-heptynyl) benzene compound number 84 4- (2- (4- (4-propylcyclohexyl)) Phenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 85 4- (2- (3-fluoro-4- (4-propyl) Chlohexyl) phenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 86 4- (2- (4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 87 4- (2- (3-Fluoro-4- (4-methylcyclohexyl) phenyl) ethynyl) -1- (4-octynyl) benzene Compound No. 88 4- (2- (3,5-difluoro-4- (4-methyl) Cyclohexyl) phenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 89 4- (2- (4- (4-ethylcyclohexyl) phenyl) ethynyl) -1- (2-octynyl) benzene

Compound No. 90 4- (2-((4-4-propylcyclohexyl) phenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 91 4- (4- (2- (4-methylphenyl)) Ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 92 4- (4- (2- (3-fluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 93 4- (4- (2- (3,5-difluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-butynyl)
Cyclohexane Compound No. 94 4- (4- (2- (4-methoxyphenyl) ethynyl)
Phenyl) -1- (2-butynyl) cyclohexane Compound No. 95 4- (4- (2- (4-ethylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 96 4- (4- ( 2- (4-propylphenyl) ethynyl)
Phenyl) -1- (2-butynyl) cyclohexane Compound No. 97 4- (4- (2- (3-fluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 98 4- (4- (2- (3,5-difluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 99 4- (4- (2- (4-propoxyphenyl) ethynyl) Phenyl) -1- (2-butynyl) cyclohexane

Compound No. 100 4- (4- (2- (4-pentylphenyl) ethynyl)
Phenyl) -1- (2-butynyl) cyclohexane Compound No. 101 4- (4- (2- (3-fluoro-4-pentylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 102 4- (4- (2- (4-hexylphenyl) ethynyl)
Phenyl) -1- (2-butynyl) cyclohexane Compound No. 103 4- (4- (2- (4-methylphenyl) ethynyl) phenyl) -1- (2-butynyl) cyclohexane Compound No. 104 4- (4- ( 2- (3-Fluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane Compound No. 105 4- (4- (2- (3,5-difluoro-4-methylphenyl) ethynyl) Phenyl) -1- (2-pentynyl) cyclohexane Compound No. 106 4- (4- (2- (4-methoxyphenyl) ethynyl)
Phenyl) -1- (3-pentynyl) cyclohexane Compound No. 107 4- (4- (2- (4-ethylphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane Compound No. 108 4- (4- ( 2- (4-propylphenyl) ethynyl)
Phenyl) -1- (2-pentynyl) cyclohexane Compound No. 109 4- (4- (2- (3-fluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane

Compound No. 110 4- (4- (2- (3,5-difluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane Compound No. 111 4- (4- (2- (4-propoxyphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane Compound No. 112 4- (4- (2- (4-pentylphenyl) ethynyl)
Phenyl) -1- (2-pentynyl) cyclohexane compound number 113 4- (4- (2- (3-fluoro-4-pentylphenyl) ethynyl) phenyl) -1- (2-pentynyl) cyclohexane compound number 114 4- (4- (2- (4-hexylphenyl) ethynyl)
Phenyl) -1- (2-pentynyl) cyclohexane Compound No. 115 4- (4- (2- (4-methylphenyl) ethynyl) phenyl) -1- (3-hexynyl) cyclohexane Compound No. 116 4- (4- ( 2- (3-Fluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-hexynyl) cyclohexane Compound No. 117 4- (4- (2- (3,5-difluoro-4-methylphenyl) ethynyl) Phenyl) -1- (2-hexynyl) cyclohexane Compound No. 118 4- (4- (2- (4-methoxyphenyl) ethynyl)
Phenyl) -1- (2-hexynyl) cyclohexane Compound No. 119 4- (4- (2- (4-ethylphenyl) ethynyl) phenyl) -1- (4-hexynyl) cyclohexane

Compound No. 120 4- (4- (2- (4-propylphenyl) ethynyl)
Phenyl) -1- (2-hexynyl) cyclohexane Compound No. 121 4- (4- (2- (3-fluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-hexynyl) cyclohexane Compound No. 122 4- (4- (2- (3,5-difluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-hexynyl) cyclohexane Compound No. 123 4- (4- (2- (4-propoxyphenyl) ethynyl) Phenyl) -1- (2-hexynyl) cyclohexane Compound No. 124 4- (4- (2- (4-methylphenyl) ethynyl) phenyl) -1- (2-heptynyl) cyclohexane Compound No. 125 4- (4- ( 2- (3-Fluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-heptynyl) cyclohex Sun compound number 126 4- (4- (2- (3,5-difluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-heptynyl) cyclohexane compound number 127 4- (4- (2- (4 -Methoxyphenyl) ethynyl)
Phenyl) -1- (4-heptynyl) cyclohexane compound number 128 4- (4- (2- (4-ethylphenyl) ethynyl) phenyl) -1- (2-heptynyl) cyclohexane compound number 129 4- (4- ( 2- (4-propylphenyl) ethynyl)
Phenyl) -1- (2-heptynyl) cyclohexane

Compound No. 130 4- (4- (2- (3-fluoro-4-propylphenyl) ethynyl) phenyl) -1- (2-heptynyl) cyclohexane Compound No. 131 4- (4- (2- (4 -Methylphenyl) ethynyl) phenyl) -1- (2-octynyl) cyclohexane Compound No. 132 4- (4- (2- (3-fluoro-4-methylphenyl) ethynyl) phenyl) -1- (2-octynyl) Cyclohexane compound number 133 4- (4- (2- (3,5-difluoro-4-methylphenyl) ethynyl) phenyl) -1- (4-octynyl) cyclohexane compound number 134 4- (4- (2- (4 -Ethylphenyl) ethynyl) phenyl) -1- (2-octynyl) cyclohexane Compound No. 135 4- (4- (2- (4 Propylphenyl) ethynyl)
Phenyl) -1- (2-octynyl) cyclohexane Compound No. 136 4- (2- (4- (4-methylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 137 4- (2- ( 3-Fluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 138 4- (2- (3,5-difluoro-4- (4-methylphenyl) phenyl) Ethynyl) -1- (2-butynyl)
Benzene compound No. 139 4- (2- (4- (4-methoxyphenyl) phenyl)
Ethynyl) -1- (2-butynyl) benzene

Compound No. 140 4- (2- (4- (4-ethylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 141 4- (2- (4- (4-propylphenyl)) Phenyl)
Ethynyl) -1- (2-butynyl) benzene Compound No. 142 4- (2- (3-Fluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 143 4- (2- (3,5-difluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 144 4- (2- (4- (4-propoxyphenyl) phenyl) Ethynyl) -1- (2-butynyl) benzene Compound No. 145 4- (2- (4- (4-pentylphenyl) phenyl)
Ethynyl) -1- (2-butynyl) benzene Compound No. 146 4- (2- (3-Fluoro-4- (4-pentylphenyl) phenyl) ethynyl) -1- (2-butynyl) benzene Compound No. 147 4- (2- (4- (4-hexylphenyl) phenyl)
Ethynyl) -1- (2-butynyl) benzene Compound No. 148 4- (2- (4- (4-methylphenyl) phenyl) ethynyl) -1- (5-octynyl) benzene Compound No. 149 4- (2- ( 3-fluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene

Compound No. 150 4- (2- (3,5-difluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 151 4- (2- (4- (4-methoxyphenyl) phenyl)
Ethynyl) -1- (2-pentynyl) benzene compound number 152 4- (2- (4- (4-ethylphenyl) phenyl) ethynyl) -1- (3-pentynyl) benzene compound number 153 4- (2- ( 4- (4-propylphenyl) phenyl)
Ethynyl) -1- (2-pentynyl) benzene Compound No. 154 4- (2- (4- (3-fluoro-4-propylphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 155 4- (2- (3-Fluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 156 4- (2- (3,5-difluoro-4- (4-propyl) Phenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 157 4- (2- (4- (4-propoxyphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene Compound No. 158 4- (2- (4- (4-pentylphenyl) phenyl)
Ethynyl) -1- (2-pentynyl) benzene Compound No. 159 4- (2- (3-Fluoro-4- (4-pentylphenyl) phenyl) ethynyl) -1- (2-pentynyl) benzene

Compound No. 160 4- (2- (4- (4-hexylphenyl) phenyl)
Ethynyl) -1- (3-pentynyl) benzene Compound No. 161 4- (2- (4- (4-methylphenyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 162 4- (2- ( 3-Fluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-hexynyl) benzene Compound No. 163 4- (2- (3,5-difluoro-4- (4-methylphenyl) phenyl) Ethynyl) -1- (2-hexynyl) benzene Compound No. 164 4- (2- (4- (4-methoxyphenyl) phenyl)
Ethynyl) -1- (2-hexynyl) benzene compound number 165 4- (2- (4- (4-ethylphenyl) phenyl) ethynyl) -1- (2-hexynyl) benzene compound number 166 4- (2- ( 4- (4-propylphenyl) phenyl)
Ethynyl) -1- (2-hexynyl) benzene compound number 167 4- (2- (3-fluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (2-hexynyl) benzene compound number 168 4- (2- (3,5-difluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (4-hexynyl) benzene Compound No. 169 4- (2- (4- (4-propoxyphenyl) phenyl) Ethynyl) -1- (2-hexynyl) benzene

Compound No. 170 4- (2- (4- (4-methylphenyl) phenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 171 4- (2- (3-fluoro-4- (4 -Methylphenyl) phenyl) ethynyl) -1- (2-heptynyl) benzene Compound No. 172 4- (2- (3,5-difluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2- Heptinyl) benzene Compound No. 173 4- (2- (4- (4-methoxyphenyl) phenyl)
Ethynyl) -1- (2-heptynyl) benzene compound number 174 4- (2- (4- (4-ethylphenyl) phenyl) ethynyl) -1- (2-heptynyl) benzene compound number 175 4- (2- ( 4- (4-propylphenyl) phenyl)
Ethynyl) -1- (4-heptynyl) benzene compound number 176 4- (2- (3-fluoro-4- (4-propylphenyl) phenyl) ethynyl) -1- (2-heptynyl) benzene compound number 177 4 (2- (4- (4-methylphenyl) phenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 178 4- (2- (3-fluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-Octynyl) benzene Compound No. 179 4- (2- (3,5-difluoro-4- (4-methylphenyl) phenyl) ethynyl) -1- (2-octynyl) benzene

Compound No. 180 4- (2- (4- (4-ethylphenyl) phenyl) ethynyl) -1- (2-octynyl) benzene Compound No. 181 4- (2-((4-4-propylphenyl)) Phenyl)
Ethynyl) -1- (4-octynyl) benzene Compound No. 182 4- (4- (4- (2- (4- (4-propylcyclohexyl) phenyl) ethynylphenyl) -1- (3-pentynyl) cyclohexane Compound No. 183 4- (4- (2- (4- (4-pentylcyclohexyl) phenyl) ethynylphenyl) -1- (3-pentynyl) cyclohexane

Example 6 (Use Example 1) 4- (4-propylcyclohexyl) benzonitrile
30% 4- (4-pentylcyclohexyl) benzonitrile
40% 4- (4-heptylcyclohexyl) benzonitrile
A liquid crystal composition B1 consisting of 30% was prepared. The nematic liquid crystal composition B1 has a clearing point of 52.3 ° C., a viscosity at 20 ° C. of 21.7 mPa · s, and a refractive index anisotropy value of 0.119.
Met. 85 parts by weight of this liquid crystal composition B1 and 15 parts of the compound 4- (2- (4-propylphenyl) ethynyl) -1- (3-pentynyl) benzene (Compound No. 18) of the present invention obtained in Example 1 A liquid crystal composition A1 consisting of 1 part by weight was prepared. The clearing point of this liquid crystal composition A1 is 53.0.
The viscosity at 20 ° C is 20.9 mPa · s,
Both were almost the same as those of the liquid crystal composition B1, but the refractive index anisotropy value was greatly increased to 0.158.
Further, the composition A1 was left in a freezer at -20 ° C for 60 days, but no precipitation of crystals was observed.

Example 7 (Comparative Example 1) Mol. Cryst. Liq. Cryst. , 48 , 1
According to the method of No. 75 (1978), a butadiyne compound in which both terminal alkyl groups were propyl groups was produced among the compounds represented by the general formula (11).

[0102]

Embedded image

A liquid crystal composition A2 comprising 85 parts by weight of the liquid crystal composition B1 and 15 parts by weight of the butadiyne compound was prepared. Each of the liquid crystal composition A2 and the liquid crystal composition A1 prepared in Example 6 was heated at 100 ° C. for 2 hours, and then the clearing point was measured. The clearing point of the liquid crystal composition A2 decreased by 7 ° C. from 76.5 ° C. before heating to 69.5 ° C. after heating. On the other hand, the clearing point of the liquid crystal composition A1 after heating is 5
The decrease was 2.7 ° C., which was only 0.3 ° C., and it was found that the compound represented by the general formula (1) has extremely high heat resistance stability.

Example 8 (Use Example 2) 4- (4-propylcyclohexyl) benzonitrile 24% 4- (4-pentylcyclohexyl) benzonitrile 36% 4- (4-heptylcyclohexyl) benzonitrile 25% 4- ( A liquid crystal composition B2 consisting of 15% of 4- (4-propylcyclohexyl) phenyl) benzonitrile was prepared. The clearing point of B2 is 7
The anisotropy value of dielectric constant was 11.0, the anisotropy value of refractive index was 0.137, and the viscosity at 20 ° C. was 27 mPa · s. 85 parts by weight of this liquid crystal composition B2 and 15 parts of the compound 4- (2- (4-methoxyphenyl) ethynyl) -1- (3-pentynyl) benzene (Compound No. 16) of the present invention obtained in the examples. Liquid crystal composition A3 comprising 1 part by weight
Was prepared. The clearing point of this liquid crystal composition A3 is 70.0.
C., the dielectric anisotropy value is 10.7, and the refractive index anisotropy value is 0.
The viscosity at 164 and 20 ° C. was 32.5 mPa · s. Example 9 (Use Example 3) 85 parts by weight of B2 and the compound 4 of the present invention obtained in the example.
-(2- (4-propylphenyl) ethynyl) -1-
15 of (3-pentynyl) benzene (Compound No. 18)
A liquid crystal composition A4 consisting of 10 parts by weight was prepared. This liquid crystal composition A4 has a clearing point of 65.6 ° C. and a dielectric anisotropy value of 1
The value was 0.4 and the refractive index anisotropy value was 0.158.

Example 10 (Use Example 4) 85 parts by weight of the liquid crystal composition B2 and the compound of the present invention 4- (2- (4-pentylphenyl) ethynyl) -1- (3- Pentynyl) benzene (Compound No. 2
A liquid crystal composition A5 consisting of 15 parts by weight of 2) was prepared.
The liquid crystal composition A5 had a clearing point of 66.6 ° C., a dielectric anisotropy value of 10.3, a refractive index anisotropy value of 0.155, and a viscosity at 20 ° C. of 40.1 mPa · s. Example 11 (Use Example 5) 95 parts by weight of B2 and the compound 4 of the present invention obtained in the example.
A liquid crystal composition A6 consisting of 5 parts by weight of-(2- (4- (4-propylcyclohexyl) phenyl) ethynyl) -1- (3-pentynyl) benzene (Compound No. 63) was prepared. The clearing point of this liquid crystal composition A6 is 76.7 ° C.,
Dielectric constant anisotropy value is 10.7, refractive index anisotropy value is 0.14
The viscosities at 6 and 20 ° C. were 34.4 mPa · s. In addition, a liquid crystal composition having the following composition was prepared, and its physical property values were measured. However, the abbreviations of the compounds are indicated according to the rules in the table below.

[0106]

[Table 1]

Example 12 (Using Example 6) 5-BTB-2T1 3.0% V2-HB-C 10.0% 1V2-HB-C 10.0% 3-HB-C 14.0% 1O1-HB -C 8.0% 2O1-HB-C 4.0% 3-HHB-C 4.0% 3-HH-4 6.0% 3-HH-2V1 4.0% 1O1-HH-5 8.0 % 2-BTB-O1 10.0% 3-HHB-1 5.0% 3-HHB-3 10.0% V-HHB-1 4.0% T _NI = 78.2 [° C] η ₂₀ = 21 .3 [mPa · s] Δn = 0.130 Δε = 7.4 V _th = 1.92 [V]

Example 13 (Use Example 7) 1O-BTB-2T1 3.0% 5-HBTB-2T1 3.0% 1V2-BEB (F, F) -C 12.0% 2O1-BEB (F)- C 6.0% 3O1-BEB (F) -C 8.0% 3-HB (F) -C 15.0% 3-HH-4 10.0% 1O1-HH-3 4.0% 4-BTB -O2 5.0% 2-BTB-1 1.0% 1-BTB-6 2.0% 4-BTB-4 1.0% 2-HHB (F) -C 10.0% 3-HHB (F ) -C 8.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% T _NI = 73.3 [° C] η ₂₀ = 41.9 [ mPa · s] Δn = 0.154 Δε = 25.6 V _th = 0.93 [V]

Example 14 (Use Example 8) 10-BTB-2T1 8.0% 3-BTB-2T1 8.0% 2-BB-C 8.0% 4-BB-C 7.0% 3-HB -C 17.0% 1O1-HB-C 12.0% 2-HHB-C 4.0% 3-HHB-C 5.0% 2-HHB-1 4.0% 3-HHB-O1 8.0 % 3-HHB-F 11.0% 1O1-HH-3 8.0% T _NI = 80.8 [° C] η ₂₀ = 34.8 [mPa · s] Δn = 0.154 Δε = 10.0 V _th = 1.78 [V]

Example 15 (Using Example 9) 5-BTB-2T1 7.0% 1O-BTB-2T1 7.0% 5-HBTB-2T1 5.0% 3-HB (F) -C 10.0% 1O1-HB-C 10.0% 2-BEB-C 6.0% 5-HEB-F 5.0% 7-HEB-F 5.0% 3-HEB-O4 8.3% 4-HEB-O2 6.2% 5-HEB-O1 6.2% 3-HEB-O2 5.2% 5-HEB-O3 4.1% 3-HBEB-F 5.0% 3-HHEB-F 10.0% T _NI = 65.2 [° C.] η ₂₀ = 42.3 [mPa · s] Δn = 0.120 Δε = 10.9 V _th = 1.78 [V]

Example 16 (Use Example 10) 5-HBTB-2T1 6.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 17.0% 5-HB -C 6.0% 3-HH-4 10.0% 3-HH-5 4.0% 2-HH-5 4.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0 % 3-H2BTB-4 4.0% 3-HB (F) TB-2 5.0% 3-HB (F) TB-3 5.0% 3-HB (F) TB-4 5.0% T _NI = 94.3 [° C] η ₂₀ = 24.7 [mPa · s] Δn = 0.158 V _th = 2.23 [V]

Example 17 (Use Example 11) 5-BTB-2T1 8.0% 3-PyB (F) -F 8.0% 2-HB-C 10.0% 3-HB-C 10.0% 3-HB (F) -C 6.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 2-HHB-C 3.0% 3- HHB-C 4.0% 2-HHB-1 5.0% 3-HHB-O1 4.0% 3-HHB-F 4.0% 3-HHB-3 14.0% 3-HB (F) TB -2 4.0% 3-HB (F) TB-3 4.0% 3-HB (F) TB-4 4.0% 3-HHEB-F 3.0% 5-HHEB-F 3.0% T _NI = 91.3 [° C.] η ₂₀ = 28.6 [mPa · s] Δn = 0.141 V _th = 1.95 [V]

Example 18 (Use Example 12) 1O-BTB-2T1 9.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 13.0% 4O1-BEB (F) -C 10.0% 3-HB-O2 16.0% 2-HHB (F) -C 13.0% 3-HHB (F) -C 14.0% 3-HB (F) TB-2 7. 0% 3-HB (F) TB-3 7.0% 3-HB (F) TB-4 6.0% T _NI = 86.9 [° C] η ₂₀ = 54.7 [mPa · s] Δn = 0.149 V _th = 1.02 [V]

Example 19 (Use Example 13) 1O-BTB-2T1 2.0% 5-H2B (F) -F 3.0% 7-HB-F 3.0% 7-HB (F) -F 4 0.0% 2-HHB (F) -F 13.0% 3-HHB (F) -F 13.0% 5-HHB (F) -F 13.0% 2-H2HB (F) -F 4.0 % 3-H2HB (F) -F 2.0% 5-H2HB (F) -F 4.0% 2-HBB (F) -F 3.0% 3-HBB (F) -F 3.0% 5 -HBB (F) -F 6.0% 3-HHB-3 8.0% 3-HHEBB-F 3.0% 5-HHEB-F 3.0% 3-HH2B-OCF3 3.0% 3-HHB -OCF3 5.0% 3-H2HB-OCF3 5.0% T _NI = 104.5 [° C] η ₂₀ = 21.5 [mPa · s] Δn = 0.090 Δε = 4.2 V _th = 2.55 [V]

Example 20 (Use Example 14) 3-BTB-2T1 2.0% 5-HBTB-2T1 3.0% 7-HB (F, F) -F 8.0% 3-H2HB (F, F ) -F 12.0% 5-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 6.0% 4-HHB (F, F) -F 6.0% 3 -HH2B (F, F) -F 10.0% 5-HH2B (F, F) -F 10.0% 3-HBB (F, F) -F 10.0% 5-HBB (F, F)- F 12.0% 3-HHEB (F, F) -F 3.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 3.0% 2-HHBB (F, F) -F 2.0% 3-HHBB (F, F) -F 2.0% T _NI = 71.5 [° C] η ₂₀ = 31.0 [mPa · s] Δn = 0.093 Δε = 8.8 _th = 1.54 [V]

Example 21 (Using Example 15) 5-BTB-2T1 4.0% 3-HB-CL 7.0% 7-HB (F, F) -F 10.0% 2-HBB (F)- F 7.5% 3-HBB (F) -F 7.5% 5-HBB (F) -F 15.0% 2-HHB-CL 5.0% 4-HHB-CL 10.0% 5-HHB -CL 5.0% 3-HBB (F, F) -F 10.0% 5-HBB (F, F) -F 9.0% 3-HB (F) VB-2 5.0% 3-HB (F) TB-3 5.0% T _NI = 91.0 [° C] η ₂₀ = 27.2 [mPa · s] Δn = 0.141 Δε = 6.0 V _th = 2.10 [V]

[0117]

The compound of the present invention has a very large Δn. As shown in the examples (use examples), Japanese Patent Laid-Open No. 61-5031, which is said to have the largest Δn at present, Mo
l. Cryst. Liq. Cryst. , 48 , 175
(1978), JP-A-2-207056, and JP-A-2-180840, a large Δ
n. Further, the compound of the present invention exhibits high heat resistance stability as shown in Examples (Comparative Examples), and has sufficient chemical stability for use in practical liquid crystal compositions. In addition, the compound of the present invention exhibits excellent compatibility with liquid crystal compositions as shown in Examples (Examples of use), and can be suitably used for practical compositions. The general formula (1) of the present invention having such excellent characteristics
By using the compound represented by, a liquid crystal composition having favorable physical properties and high chemical stability can be obtained, and an excellent liquid crystal display device can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/192 C07C 43/192 43/215 43/215 43/225 7419-4H 43/225 D 255 / 46 255/46 255/50 255/50 255/54 255/54 C09K 19/18 C09K 19/18 19/30 19/30 19/42 19/42 19/44 19/44 19/46 19/46 G02F 1/13 500 G02F 1/13 500

Claims (11)

[Claims] 1. A compound of the general formula (1) (In the formula, R1 represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, a cyano group, or a halogen atom, R2 represents an alkyl group having 1 to 5 carbon atoms, and one methylene group (- CH2-) may be replaced by an oxygen atom,
X1 and X2 each independently represent a hydrogen atom or a halogen atom, and A and B are each independently a single bond, 1,4
-A phenylene ring or a 1,4-cyclohexylene ring, which may be substituted with a halogen atom, and p represents 1 to 5). 2. The liquid crystal compound according to claim 1, wherein both A and B are single bonds. 3. The liquid crystal compound according to claim 1, wherein A is a 1,4-cyclohexylene ring. 4. The liquid crystal compound according to claim 1, wherein A is a 1,4-phenylene ring. 5. The liquid crystal compound according to claim 1, wherein B is a 1,4-cyclohexylene ring. 6. A liquid crystal composition comprising at least two components, which contains at least one liquid crystal compound according to claim 1. 7. A first component containing at least one kind of the liquid crystalline compound according to claim 1, and a second component represented by the general formulas (2), (3), and (4): (In the formula, R3 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, Y represents a fluorine atom or a chlorine atom, and Q
1 and Q2 each independently represent a hydrogen atom or a fluorine atom, r represents 1 or 2, and Z1 and Z2 each independently represent -CH2CH2- or a single bond). A liquid crystal composition comprising a compound of a type. 8. A first component containing at least one compound of claim 1 and a second component represented by the general formulas (5), (6), (7), (8) and (9). [Chemical 3] (In the formula, R4 represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in any of them, an arbitrary methylene group (-CH2-) is an oxygen atom (-O-).
May be substituted by, but two or more methylene groups are not continuously replaced by oxygen atoms, and Z3 is -C
H2CH2-, -COO-, or a single bond, Q3 and Q4 each independently represent a hydrogen atom or a fluorine atom, and (E) represents a cyclohexane ring, a benzene ring, or 1,
Represents a 3-dioxane ring, s represents 0 or 1, R5 represents an alkyl group having 1 to 10 carbon atoms, Q5 represents a hydrogen atom or a fluorine atom, k represents 0 or 1, and R6 represents a carbon number. 1 to 10 alkyl groups, (G) represents a cyclohexane ring or a benzene ring, Q6 and Q7 each independently represent a hydrogen atom or a fluorine atom, and Z4 represents -COO-.
Or a single bond, h represents 0 or 1, R7 and R8 each independently represent an alkyl group, an alkoxy group or an alkoxymethyl group having 1 to 10 carbon atoms, and (H) is a cyclohexane ring or a pyrimidine ring. , Or represents a benzene ring,
(J) represents a cyclohexane ring or a benzene ring, Z5
Represents -C≡C-, -COO-, -CH2CH2-, or a covalent bond: R9 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R10 represents an alkyl group or alkoxy group having 1 to 10 carbon atoms. , Or an alkoxymethyl group,
(K) represents a cyclohexane ring or a pyrimidine ring,
(L) and (M) each independently represent a cyclohexane ring or a benzene ring, Z6 is -COO-, -CH2CH.
2-or a single bond, Z7 is -C≡C-, -COO
-Or a single bond, and Q8 represents a hydrogen atom or a fluorine atom), and at least one compound selected from the group consisting of the following. 9. A liquid crystal display device comprising a liquid crystal composition containing at least one liquid crystal compound according to claim 1 and comprising at least two components. 10. A liquid crystal display device using the liquid crystal composition according to claim 6. 11. A compound represented by the general formula (34): (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, one methylene group (-CH2-) in R2 may be replaced by an oxygen atom, X represents a halogen atom, and p represents 1 to 1). The compound represented by 5).