JP2010111686A - Tetracyclic compound having lateral halogen substituent group and liquid crystal composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new liquid crystal composition having a wide nematic phase temperature range at the same time having high compatibility with other liquid crystallin compounds at low temperature, a large refractive index anisotropy value and chemical stability. <P>SOLUTION: There are disclosed the compound represented by general formula (1) and the liquid crystal composition comprising the same. Wherein H<SB>1</SB>-H<SB>12</SB>represent each H and at least one of them is substituted with a halogen atom and when either one of H<SB>6</SB>and H<SB>8</SB>is substituted with a halogen, at least one in the remaining H<SB>1</SB>to H<SB>12</SB>is substituted with a halogen, R<SB>1</SB>and Y<SB>1</SB>are each independently a 1-20C alkyl, etc., X<SB>1</SB>, X<SB>2</SB>, X<SB>3</SB>are each independently a covalent bond, 1, 2-ethylene or 1, 4-butylene. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  An object of the present invention is to provide a novel liquid crystal compound exhibiting various physical properties suitable as an electro-optical display material, and a liquid crystal composition having suitable physical properties using the compound. In particular, a novel liquid crystal compound having a wide nematic phase temperature range and a high clearing point, a good phase solubility with other liquid crystal compounds, and a novel liquid crystal composition having a wide driving temperature range using them.

  The liquid crystal display element utilizes the optical anisotropy and dielectric anisotropy of the liquid crystalline compound, but the active matrix driving method utilizing the TFT method has received the most attention because of its high display performance. .

Various characteristics are required for the liquid crystal compound used in the above method,
1) The temperature range of the nematic phase is wide to realize a wide operating temperature range, or the nematic phase temperature range is not reduced when added to a liquid crystal composition, or phase separation such as crystal precipitation in a low temperature region. Difficult to produce,
2) Low viscosity to achieve high speed response
3) having a large refractive index anisotropy;
Is needed.

  In order to realize such required characteristics, liquid crystalline compounds with low viscosity and a very wide nematic phase temperature range, especially high clearing point, are used as the base liquid crystal, and the characteristic refractive index anisotropy here An operation of obtaining a desired characteristic by mixing an appropriate amount of a liquid crystal compound having a value is performed. In order to obtain a liquid crystal composition that can operate in a wide temperature range, a liquid crystal compound having as wide a temperature range as possible, that is, a SN point or melting point as low as possible, a clearing point as high as possible, and a nematic phase temperature range as wide as possible is required. is there.

  Further, the liquid crystal compound is composed of a mixture of several to thirty or more kinds of liquid crystal compounds in order to exhibit characteristics required for individual display elements. For this reason, compatibility with other liquid crystal compounds, particularly recently, since the use environment is widespread, it is required that the low-temperature compatibility is also good. That is, in order to enable use in a wide temperature range, the liquid crystal composition must have a nematic phase, particularly at a low temperature, and there is a demand for a liquid crystal composition that does not precipitate crystals or develop a smectic phase. Yes. Therefore, high compatibility of the liquid crystal compound to be used with other liquid crystal compounds at a low temperature is extremely important.

  Various tetracyclic compounds have already been disclosed with the aim of simultaneously satisfying the above object, that is, a wide nematic phase temperature range, good phase solubility, and a large refractive index anisotropy. For example, JP-A-4-31540 and JP-A-4-356432 correspond to this. JP-A-58-203922 discloses a compound represented by (Chemical Formula 8):

  JP-A-2-237949 discloses compounds represented by (Chemical Formula 9), respectively.

  However, although all showed large refractive index anisotropy, (Chemical Formula 8) had extremely poor phase solubility, and (Chemical Formula 9) had a narrow nematic phase temperature range. Therefore, a novel liquid crystalline compound having further excellent characteristics has been awaited.

  The liquid crystal compound used in the liquid crystal composition must be stable against external environmental factors such as moisture, air, heat and light. In particular, liquid crystal compositions designed for active matrix liquid crystal displays containing integrated nonlinear elements for switching individual image points have extremely high specific resistance (high voltage holding ratio) and good UV stability. I have to. Active matrix liquid crystal displays are suitable for advanced information displays for televisions or computers, as well as advanced information displays in automobiles and aircraft. However, when a liquid crystal compound or liquid crystal composition that does not have a very high specific resistance (high voltage holding ratio) and good UV stability is used, the contrast decreases as the electrical resistance in the liquid crystal panel decreases. The problem of “afterimage phenomenon” occurs. Further, the high electrical resistance of the liquid crystal composition is a very important factor that affects the service life, particularly when driven at a low voltage. For this reason, an extremely high specific resistance value (high voltage holding ratio) and good UV stability are extremely important characteristics required for the liquid crystal compound to be used.

  That is, in order to provide a liquid crystal composition having excellent characteristics, it has a wider nematic phase temperature range, high compatibility with other liquid crystal compounds at low temperatures, high chemical stability, and a large refractive index anisotropy value. There has been a long-awaited need for a novel liquid crystal compound having the above.

JP-A-4-31540 JP-A-4-356432 JP 58-203922 JP-A-2-237949

  The object of the present invention is to provide a novel liquid crystal compound having a wide nematic phase temperature range, high compatibility with other liquid crystal compounds at low temperatures, a large refractive index anisotropy value, and high chemical stability at the same time. It is to provide a liquid crystal composition having excellent characteristics.

  As a result of intensive studies to solve the above-described problems, the present inventors have found a compound having a novel structure and improved characteristics as compared with known liquid crystal compounds. That is, by introducing one or more halogen atoms into a specific portion of the benzene ring in the 4-cyclohexyl terphenyl skeleton or the similar four-ring skeleton, a particularly wide nematic phase temperature range and a significantly improved phase are obtained. The inventors have found that it induces solubility and have completed the present invention. That is, the present invention relates to the general formula (1)

(In the formula, H _{1 to} H ₁₂ represent a hydrogen atom, but at least one of them is replaced by a halogen atom, and when any one of H ₆ or H ₈ is replaced by a halogen atom, it remains. At least one of the above hydrogen atoms is replaced by a halogen atom, R ₁ and Y ₁ each independently represents an alkyl group having 1 to 20 carbon atoms, but one of R ₁ and Y ₁ or Two or more methylene groups may be replaced by any one of an oxygen atom, a sulfur atom, a dihydrosilylene group, a dimethylsilylene group, —CH═CH—, —C≡C—, wherein X ₁ , X ₂ , and X ₃ are Each independently represents a covalent bond, a 1,2-ethylene group or a 1,4-butylene group.).

A preferred embodiment of the compound of the present invention is a tetracyclic compound in which R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms in the general formula (1). is there.

In a more specific embodiment of the compound of the present invention, in the general formula (1), R ₁ and Y ₁ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxyalkyl group, or an alkenyl group, A tetracyclic compound in which H ₁ and H ₄ are replaced by halogen atoms, and H _{2 to} H ₃ and H _{5 to} H ₁₂ are hydrogen atoms.

Another more specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxyalkyl group or an alkenyl group. Yes, it is a tetracyclic compound in which H ₁ is replaced with a halogen atom, and H _{2 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. And H ₅ is substituted with a halogen atom, and H _{1 to} H ₄ and H _{6 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. And H ₂ and H ₄ are substituted with halogen atoms, and H ₁ , H ₃ and H _{5 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. H ₆ and H ₈ are substituted with halogen atoms, and H _{1 to} H ₅ , H ₇ and H _{9 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. And H ₁ and H ₅ are substituted with halogen atoms, and H _{2 to} H ₄ and H _{6 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. And H ₁ and H ₉ are substituted with halogen atoms, and H _{2 to} H ₈ and H _{10 to} H ₁₂ are hydrogen atoms.

Still another specific embodiment of the compound of the present invention is as follows. In the general formula (1), R ₁ and Y ₁ are each independently an alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 20 carbon atoms. And H ₂ and H ₉ are substituted with halogen atoms, and H ₁ , H _{3 to} H ₈ , and H _{10 to} H ₁₂ are hydrogen atoms.

  The present invention also relates to a liquid crystal composition comprising at least one tetracyclic compound represented by the general formula (1).

  The specific mode of the liquid crystal composition of the present invention contains at least one tetracyclic compound represented by the general formula (1) as the first component, and the general formulas (2) and (3) as the second component. ) And (4)

(Wherein R ₂ represents an alkyl group having 1 to 10 carbon atoms, Y ₂ represents a fluorine atom, a chlorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and L ₁ , L ₂ , L ₃ and L ₄ each independently represent a hydrogen atom or a fluorine atom, Z ₁ and Z ₂ each independently represent a 1,2-ethylene group, —CH═CH— or a covalent bond, a represents 1 or 2.) A liquid crystal composition comprising at least one compound selected from the group consisting of:

  In another specific embodiment of the liquid crystal composition of the present invention, the first component contains at least one tetracyclic compound represented by the general formula (1), and the second component contains the general formula (5), (6), (7), (8) and (9)

(In the formula, R ₃ represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl group or alkenyl group is substituted with an oxygen atom. However, two or more methylene groups are not continuously substituted by oxygen atoms, and ring B is 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5- Diyl, ring C represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring D represents 1,4-cyclohexylene or 1,4-phenylene, Z ₃ Represents a 1,2-ethylene group, —COO— or a covalent bond, L ₅ and L ₆ each independently represent a hydrogen atom or a fluorine atom, and b and c each independently represents 0 or 1 .)

(In the formula, R ₄ represents an alkyl group having 1 to 10 carbon atoms, L ₇ represents a hydrogen atom or a fluorine atom, and d represents 0 or 1.)

(Wherein R ₅ represents an alkyl group having 1 to 10 carbon atoms, ring E and ring F each independently represent 1,4-cyclohexylene or 1,4-phenylene, and Z ₄ and Z ₅ represent Each independently represents —COO— or a covalent bond, Z ₆ represents —COO— or —C≡C—, L ₈ and L ₉ each independently represent a hydrogen atom or a fluorine atom, Y ₃ Represents a fluorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g each independently represent 0 or 1.)

(In the formula, R ₆ and R ₇ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any methylene group thereof is substituted by an oxygen atom. However, two or more methylene groups may not be successively substituted by oxygen atoms, and ring H may be 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl. Ring I represents 1,4-cyclohexylene or 1,4-phenylene, Z ₆ represents —C≡C—, —COO—, a 1,2-ethylene group, —CH═CH—C≡C— or And represents a covalent bond, and Z ₇ represents —COO— or a covalent bond.

(In the formula, R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any methylene group is substituted by an oxygen atom. However, two or more methylene groups may not be substituted with oxygen atoms in succession, ring J may be 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl. Ring K represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which one or more hydrogen atoms on the ring may be substituted with fluorine atoms, and ring L represents 1,4-cyclohexylene or 1,4-phenylene, Z ₈ and Z ₁₀ each independently represent —COO—, 1,2-ethylene group or a covalent bond, and Z ₉ represents —CH═CH—. , -C≡C-, COO- or indicates a covalent bond, h is a liquid crystal composition, characterized in that at least one compound selected from the group consisting of a 0 or 1.).

  In still another specific embodiment of the liquid crystal composition of the present invention, the first component contains at least one tetracyclic compound represented by the general formula (1), and a part of the second component has the general formula ( 2), containing at least one compound selected from the group consisting of (3) and (4), and as the other part of the second component, the general formulas (5), (6), (7), (8) ) And (9). A liquid crystal composition comprising at least one compound selected from the group consisting of (9).

  The present invention also relates to a liquid crystal display element formed using the liquid crystal composition.

  The compound of the present invention (1) has a wide nematic phase temperature range, high compatibility with other liquid crystal compounds at low temperatures, large refractive index anisotropy, and high chemical stability at the same time.

  Furthermore, as shown in the composition examples, the use of the compound of the present invention made it possible to prepare a liquid crystal composition having excellent characteristics, that is, a wider operating temperature range than conventional liquid crystal compositions.

The tetracyclic compound represented by the general formula (1) of the present invention is a tetracyclic compound characterized by having a benzene ring substituted with a halogen atom. Specifically, the following (1-1) to ( 1-8). (In the above formula, R ₁ , Y ₁ , and H _{1 to} H ₁₂ have the same meaning as described above.)

  That is, the tetracyclic compound of the formula (1) includes a tetracyclic compound (1-1) in which all the rings are covalently linked, and includes (1-2) to (1-4) including one 1,2-ethylene bond. ) (1-5) to (1-7) containing one 1,4-butylene bond, and (1-8) containing two 1,2-ethylene bonds.

  More specifically, the following compounds are developed.

In the above formula, Ra ₁ and Ya ₁ are an alkyl group, an alkoxy group, an alkoxyalkyl group, and an alkenyl group, and Hal is a fluorine atom or a chlorine atom.

In the tetracyclic compound of the general formula (1) of the present invention, R ₁ and Y ₁ represent an alkyl group having 1 to 20 carbon atoms, and the methylene group in Y ₁ is an oxygen atom, a sulfur atom, a dihydrosilylene group, or dimethylsilylene. The group, —CH═CH—, —C≡C— may be substituted. Among them, preferred R ₁ and Y ₁ are more specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group , Butoxymethyl group, pentoxymethyl group, hexyloxymethyl group, heptyloxymethyl group, octyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, pentoxyethyl group, hexyloxyethyl group, methoxypropyl group , Ethoxypropyl group, propoxypropyl group, pentoxypropyl group, hexyloxypropyl group, heptyloxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, pentoxybutyl group, methoxypentyl group, ethoxy Pliers Group, propoxypentyl group, pentoxypentyl group, methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, butoxymethoxy group, pentoxymethoxy group, hexyloxymethoxy group, heptyloxymethoxy group, octyloxymethoxy group, methoxyethoxy group Ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, pentoxyethoxy group, hexyloxyethoxy group, methoxypropoxy group, ethoxypropoxy group, propoxypropoxy group, pentoxypropoxy group, hexyloxypropoxy group, heptyloxypropoxy group, Methoxybutoxy group, ethoxybutoxy group, propoxybutoxy group, butoxybutoxy group, pentoxybutoxy group, methoxypentoxy group, ethoxypentoxy group, propoxy Pentoxy group, pentoxypentoxy group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1- Butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptynyl group, 4-heptynyl group, 5-heptynyl group , 6-heptynyl group, 1,5 hexadienyl.

At least one of H _{1 to} H ₁₂ hydrogen atoms on the benzene ring is replaced with a halogen atom, and when either one of H ₆ or H ₈ is replaced with a halogen atom, the remaining H _{1 to} H _At least one of the ₁₂ hydrogen atoms is replaced by a halogen atom. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In consideration of the viscosity, it is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. One or more of H _{1 to} H ₁₂ are replaced with halogen atoms, but the number of halogen atoms to be replaced is preferably 1 to 4, and more preferably 1 to 2 in consideration of viscosity.

  In the tetracyclic compound of the general formula (1), those in which each atom constituting the compound is replaced with an isotope also fall within the scope of the present invention. That is, for example, most of the hydrogen atoms usually have nuclei having a mass number of 1, but it is possible to replace specific positions with deuterium having a mass number of 2.

  The tetracyclic compound of the general formula (1) of the present invention has a wide nematic phase temperature range, high chemical stability, high compatibility with other liquid crystal compounds, and a large refractive index anisotropy value. Is extremely important.

  The tetracyclic compound of the general formula (1) has a remarkably wide nematic phase temperature range as compared with conventional liquid crystal compounds. In particular, the melting point (C—N point) or S—N point is extremely low compared to conventional compounds, and the nematic phase temperature range is also significantly wider than known liquid crystal compounds.

  The tetracyclic compound of the general formula (1) has high solubility in other liquid crystal compounds or liquid crystal compositions, and the liquid crystal composition using the tetracyclic compound of (1) has a low temperature (for example, −20 which is required from a practical aspect). (° C.), the nematic phase is not impaired.

  All of the tetracyclic compounds of the general formula (1) are chemically very stable, and the specific resistance value and the voltage holding ratio of the liquid crystal composition using them are very high. Moreover, the stability to ultraviolet light and heating is extremely high.

  All of the tetracyclic compounds of the present invention (1) exhibit low viscosity, and even when used in a large amount in the liquid crystal composition, the viscosity of the entire liquid crystal composition is not significantly increased. Further, the temperature dependency of the viscosity, in particular, the temperature dependency at a low temperature is extremely small.

  Since the tetracyclic compound of the present invention has excellent characteristics as described above, it can be suitably used not only for TFT but also for other applications. For example, it is also suitable as a liquid crystal compound for TN, a liquid crystal compound for STN, a liquid crystal compound for guest-host mode, a liquid crystal compound for polymer dispersion type liquid crystal display elements, and a liquid crystal compound for dynamic scattering mode.

  The liquid crystal composition according to the present invention preferably contains one or more tetracyclic compounds represented by the general formula (1) in a proportion of 0.1 to 99% by weight in order to develop excellent characteristics. .

  In more detail, the liquid crystal composition provided by the present invention includes, in addition to the first component containing at least one tetracyclic compound represented by the general formula (1), the general formulas (2) to (2) depending on the purpose of the liquid crystal composition. It is completed by mixing a compound arbitrarily selected from the compound group represented by (9).

Preferred examples of the compounds of the general formulas (2) to (4) used in the present invention include the following compounds. (R ₂ has the same meaning as described above.)

  The compounds represented by the general formulas (2) to (4) are compounds having a positive dielectric anisotropy value, have excellent thermal stability and chemical stability, and particularly have a high voltage holding ratio. In addition, it is a very useful compound when preparing a liquid crystal composition for TFT (AM-LCD) that requires high reliability such as a large specific resistance value.

  The amount of the compound represented by the general formulas (2) to (4) is arbitrarily used in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition when preparing a liquid crystal composition for TFT. However, it is preferably 10 to 97% by weight. More preferably, it is 40 to 95% by weight. In that case, a part of the compounds represented by the general formulas (5) to (9) may be contained. The compounds represented by the general formulas (2) to (4) can also be used when preparing a liquid crystal composition for STN display mode or normal TN display mode.

Preferred examples of the compounds represented by the general formulas (5) to (7) of the present invention include the following compounds. (R _{3 to} R ₅ have the same meaning as described above.)

  The compounds of the general formulas (5) to (7) have a positive dielectric anisotropy value and a large value, and are used particularly for the purpose of reducing the threshold voltage. It is also used for the purpose of expanding the nematic range such as viscosity adjustment, refractive index anisotropy value adjustment, and clearing point increase. Furthermore, it is also used for the purpose of improving the steepness.

Preferred examples of the compounds of the general formulas (8) and (9) of the present invention include the following compounds. (R _{6 to} R ₉ have the same meaning as described above.)

  The compounds of the general formulas (8) and (9) are positive compounds having a negative or small dielectric anisotropy value. The compound of the general formula (8) is mainly used for the purpose of decreasing the viscosity and / or adjusting the refractive index anisotropy value. The compound of the general formula (9) is used for the purpose of expanding the nematic range such as increasing the clearing point and adjusting the refractive index anisotropy value.

  The compounds of the general formulas (5) to (9) are extremely useful compounds, particularly when adjusting liquid crystal compositions for STN display mode and normal TN display mode.

  The amount of the compounds of the general formulas (5) to (9) can be arbitrarily used in the range of 1 to 99% by weight when preparing a liquid crystal composition for a normal TN display mode and STN display mode. 10 to 97% by weight is preferred. More preferably, it is 40 to 95% by weight. In this case, some of the compounds (2) to (4) may be used.

  The liquid crystal composition of the present invention is prepared by a conventional method. In general, a method is used in which various components are dissolved together at a high temperature. However, after the liquid crystal is dissolved and mixed in an organic solvent, the solvent may be distilled off under reduced pressure.

  The liquid crystal material of the present invention is optimized 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. Usually, a chiral dopant or the like is added to induce the helical structure of the liquid crystal to adjust the necessary twist angle and prevent reverse twist.

  In addition, the liquid crystal composition of the present invention is obtained by adding a dichroic dye such as merocyanine series, styryl series, azo series, azomethine series, azoxy series, quinophthalone series, anthraquinone series, and tetrazine series to a guest host (GH) mode. It can also be used as a liquid crystal composition for a battery. Or for NCAP produced by encapsulating nematic liquid crystal and polymer dispersed liquid crystal display device (PDLCD) represented by polymer network liquid crystal display device (PNLCD) in which 3D stitch polymer is created in the liquid crystal It can also be used as a liquid crystal composition. In addition, it can be used as a liquid crystal composition for a birefringence control (ECB) mode or a dynamic scattering (DS) mode.

  The tetracyclic compound represented by the general formula (1) of the present invention can be produced by making full use of ordinary organic synthetic chemical techniques. That is, it can be produced by combining known reactions described in new experimental chemistry courses, organic synthesis, organic reactions, and other books and magazines.

For example, according to the representative example shown below, it can be manufactured without problems. In the following, R ₁ , Y ₁ , X ₁ , X ₂ , X ₃ , H _{1 to} H ₁₂ have the same meaning as described above, G ₁ represents a bromine atom or iodine atom, and g and p are 0 to 1 or more. The natural number of.

That is, according to the method of Suzuki et al. (Synth. Commun., 11 , 513 (1981)), the boric acid derivative (10) and the halide (11) are subjected to a cross-coupling reaction in the presence of a catalyst such as palladium or nickel. The tetracyclic compound of the general formula (1) can be produced as a cross-coupling adduct.

Further, instead of (10), Grignard reagent (12) according to the conventional method, silicon compound (13) according to the method of Tetsunaka et al. (Tetrahedron, 50 , 8301 (1994)), and silicon compound according to the method of Japanese Patent Application No. 7-141117 The tetracyclic compound of (1) can also be produced by carrying out a cross coupling reaction using (14).

  (10) (12) (13) and (14) can be produced according to the methods described in JP-A-60-97925, JP-B-59-35901, etc. It can be produced by performing a simple reaction. That is, alkyl halide and trialkyl borate were sequentially acted on halide (15) and then treated with acid (10), magnesium was acted on, and (12) was treated with alkyl lithium and alkyltrichlorosilicon was acted on. (14) is obtained by treating tetraalkoxy silicon after treating with (13) alkyllithium.

When Y ₁ is an alkenyl group or an alkynyl group, it is preferable to introduce Y ₁ by the following production method. That is, according to the method described in JP-B-7-2653 and the like (16), carbon addition and Wittig reaction are performed in a conventional manner, and in (1), Y ₁ is an alkenyl group. By converting to acetylene derivative (18) by alkylation and then alkylating, in (1), Y ₁ is an alkynyl group can be produced.

  Hereinafter, the production method and use examples of the compound of the present invention will be described in detail by way of examples. In each example, C represents a crystal, N represents a nematic phase, S represents a smectic phase, I represents an isotropic liquid, and all units of phase transition temperature are ° C.

Example 1
4- (4-Methoxymethylcyclohexyl) -2′-fluoro-4 ″ -methylterphenyl (in the formula (1), R ₁ is a methoxymethyl group, X ₁ , X ₂ and X ₃ are covalent bonds, and Y ₁ is methyl. A group, a compound in which H _{1 to} H ₄ and H _{6 to} H ₁₂ are replaced with a hydrogen atom and H ₅ is replaced with a fluorine atom, and a method for producing compound number a-1).

  To a mixture of 4-bromotoluene (743 mmol) and THF (500 ml), 500 ml (equivalent to 780 mmol) of a hexane solution of n-butyllithium was added dropwise at −78 ° C. over 1.6 hours, followed by stirring at the same temperature for 1.5 hours. To this solution was added dropwise a 200 ml THF solution of triisopropyl borate (1486 mmol), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1000 ml of toluene to obtain 4-methylphenylboric acid (545 mmol) as a white solid.

4-methylphenylboric acid (73.6 mmol), 1-bromo-3-fluorobenzene (66.2 mmol), potassium carbonate (147 mmol), 0.5% palladium on carbon 0.5 g, toluene 100 ml, ethanol 100 ml, water 6.0 ml Was refluxed for 5 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/9) and recrystallized (recrystallization solvent: ethanol) to give colorless plate-like 3-fluoro-4′-methyl. Biphenyl (13.6 mmol) was obtained.

  To a mixture of 4- (4-methoxymethylcyclohexyl) -1-iodobenzene (297 mmol) and THF 250 ml, 200 ml of n-butyllithium hexane solution (corresponding to 312 mmol) was added dropwise at −78 ° C. for 3.0 hours at the same temperature. Stir for 2 hours. To this solution was added dropwise a solution of triisopropyl borate (594 mmol) in THF (100 ml), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 270 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed with water three times, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was washed with heptane to obtain 4- (4-methoxymethylcyclohexyl) phenylboric acid (60.1 mol) as a white solid.

  3-Fluoro-4′-methylbiphenyl (13.4 mmol), iodic acid (6.71 mmol), iodine (8.08 mmol), acetic acid (10 ml), water (1.2 ml), carbon tetrachloride (1.2 ml) The mixture was refluxed for 24 hours. After allowing to cool, the reaction solution was extracted twice with heptane and washed twice with water. This was washed with 50 ml of a 4% aqueous sodium thiosulfate solution, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/9) and recrystallized twice (recrystallization solvent: ethanol) to give a pale yellowish green crystal 3-fluoro-4 -Iodo-4'-methylbiphenyl (3.39 mmol) was obtained.

4- (4-Methoxymethylcyclohexyl) phenyl boric acid (8.42 mmol), 3-fluoro-4-iodo-4′-methylbiphenyl (3.36 mmol), potassium carbonate (16.8 mmol), 5% palladium on carbon. A mixture of 1 g, 14 ml of toluene, 14 ml of ethanol and 0.7 ml of water was refluxed for 6 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography (eluent: toluene) and recrystallization (recrystallization solvent: ethanol / toluene = 4/3) to obtain the title compound (2.58 mmol) as colorless crystals. Various spectral data of this one well supported its structure as follows.
1H-NMR: δ (ppm): 7.21-7.59 (m, 11H), 3.36 (s, 3H), 3.26 (d, 2H), 2.37-2.49 (brs, 1H), 2.41 (s, 3H), 1.07-2.10 (m, 9H)
GC-MS: 388 (M +)
Moreover, this compound showed liquid crystallinity and the phase transition temperature was as follows.
CN point: 156.4 ° C, NI point: 315.7 ° C.

Example 2
4- (4-methoxymethylcyclohexyl) -2 ′, 5′-difluoro-4 ″ -methylterphenyl (wherein R ₁ is a methoxymethyl group, X ₁ , X ₂ and X ₃ are covalent bonds, Y ₁ is a methyl group, H _{1 to} H ₄ , H ₆ , H ₇ , H _{9 to} H ₁₂ are hydrogen atoms, and H ₅ and H ₈ are substituted with fluorine atoms, a production method of compound number b-1).

  To a mixture of 4-bromotoluene (743 mmol) and THF (500 ml), 500 ml (equivalent to 780 mmol) of a hexane solution of n-butyllithium was added dropwise at −78 ° C. over 1.6 hours, followed by stirring at the same temperature for 1.5 hours. To this solution was added dropwise a 200 ml THF solution of triisopropyl borate (1486 mmol), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1000 ml of toluene to obtain 4-methylphenylboric acid (545 mmol) as a white solid.

  4-methylphenylboric acid (46.0 mmol), 1,4-dibromo-2,5-difluorobenzene (91.9 mmol), potassium carbonate (92.0 mmol), 1.0% of 5% palladium on carbon, 120 ml of toluene, ethanol A mixture of 120 ml and 6.0 ml of water was refluxed for 6 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: n-heptane) and recrystallization (recrystallization solvent: ethanol) to give colorless needle-shaped 4-bromo-2,5-difluoro-4′-methyl. Biphenyl (16.0 mmol) was obtained.

  To a mixture of 4-bromo-2,5-difluoro-4′-methylbiphenyl (7.06 mmol) and THF 20 ml, 5.0 ml of n-butyllithium hexane solution (corresponding to 7.85 mmol) was added dropwise at −78 ° C. for 10 minutes. The mixture was stirred at the same temperature for 3.2 hours. To this solution was added dropwise a solution of triisopropyl borate (15.2 mmol) in THF (10 ml), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 9 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with toluene, washed with water three times and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 10 ml of toluene to obtain 2,5-difluoro-4′-methylbiphenyl-4-boric acid (5.48 mmol) as a white solid.

2,5-difluoro-4′-methylbiphenyl-4-boric acid (5.24 mmol), 4- (4-methoxymethylcyclohexyl) -1-iodobenzene (5.24 mmol), potassium carbonate (10.5 mmol), 5 A mixture of 0.1 g% palladium on carbon, 12 ml toluene, 12 ml ethanol, and 0.6 ml water was refluxed for 7 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/1) and recrystallized (recrystallization solvent: ethanol / toluene = 2/1) to give the title compound as colorless crystals ( 3.99 mmol) was obtained. Various spectral data of this one well supported its structure as follows.
1H-NMR: δ (ppm): 7.11-7.52 (m, 10H), 3.35 (s, 3H), 3.25 (d, 2H), 2.01-2.54 (brs, 1H), 2.40 (s, 3H), 1.06-1.90 (m, 9H)
GC-MS: 406 (M +)
Moreover, this compound showed liquid crystallinity and the phase transition temperature was as follows.
CN point: 120.4 degreeC, NI point: 276.3 degreeC.

Example 3
4- (4-propylcyclohexyl) -3-fluoro-4 "-ethylterphenyl (in the formula (1), R ₁ is a propyl group, X ₁ , X ₂ and X ₃ are covalent bonds, Y ₁ is an ethyl group, H ₂ to H ₁₂ are hydrogen atoms, the compound H ₁ is replaced by a fluorine atom, compound No. c-1) production method of.

To a mixture of 4-bromo-4′-ethylbiphenyl (748 mmol) and THF 500 ml, 500 ml of n-butyllithium hexane solution (corresponding to 785 mmol) was dropped at −78 ° C. for 1.5 hours, and the mixture was stirred at the same temperature for 2.0 hours. A solution of trimethyl borate (1496 mmol) in 150 ml of THF was added dropwise to the solution, and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1600 ml of toluene and 500 ml of acetone to obtain 4′-ethylbiphenyl-4-boric acid (572 mmol) as a white solid.

  Mixture of 4′-ethylbiphenyl-4-boric acid (177 mmol), 1-bromo-3-fluorobenzene (195 mmol), potassium carbonate (354 mmol), 3.0 g of 5% palladium on carbon, 260 ml of toluene, 260 ml of ethanol, 13 ml of water Was refluxed for 7 hours. After allowing to cool, 500 ml of toluene was added to the reaction solution to make it uniform, followed by filtration and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) and recrystallized (recrystallization solvent: ethanol / toluene = 5/2) to give colorless plate-like 3-fluoro-4 "-ethylterphenyl. (121 mmol) was obtained.

  A cyclohexane solution of sec-butyllithium (corresponding to 23.9 mol) was added dropwise to a mixture of 3-fluoro-4 "-ethylterphenyl (21.7 mol) and 100 ml of THF while maintaining -78 ° C, and the mixture was stirred at the same temperature for 40 minutes. While maintaining at −78 ° C., 10 ml of a solution of 4-propylcyclohexanone (26.0 mol) in THF was added and the mixture was gradually returned to room temperature while stirring, and then stirred overnight, and 30 ml of 7.3% hydrochloric acid was added and stirred for 30 minutes. The reaction solution was extracted twice with toluene, washed 4 times with water and dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) to give 4- (1-hydroxy) as a colorless solid. -4-Propylcyclohexyl) -3-fluoro-4 "-ethylterphenyl (17.2 mmol) was obtained.

  A mixture of 4- (1-hydroxy-4-propylcyclohexyl) -3-fluoro-4 "-ethylterphenyl (24.5 mmol), Amberlyst 15E (0.5 g) from Organo, 250 ml of toluene is produced. The mixture was heated to reflux for 6.5 hours while dehydrating water, allowed to cool, and the reaction mixture was filtered. Propyl-1-cyclohexenyl) -3-fluoro-4 "-ethylterphenyl (24.0 mmol) was obtained.

4- (4-propyl-1-cyclohexenyl) -3-fluoro-4 "-ethylterphenyl (24.0 mmol) was added with 500 ml of toluene and 20 g of Raney nickel and stirred for 12 hours in a hydrogen atmosphere. Hydrogen absorption stopped. The catalyst was removed by filtration from the reaction system, the solvent was distilled off, the residue was purified by column chromatography (eluent: toluene), and recrystallized (recrystallization solvent: ethanol / toluene = 3/1). The title compound (11.0 mmol) was obtained in the form of colorless crystals, and various spectral data of this product supported the structure as follows.
1H-NMR: δ (ppm): 7.22-7.63 (m, 11H), 2.90-3.10 (brs, 1H), 2.71 (q, 2H), 0.80-2. 10 (m, 19H)
GC-MS: 400 (M +)
Moreover, this compound showed liquid crystallinity and the phase transition temperature was as follows.
C-C point: 98.2 ° C, C-S point: 156.2 ° C, S-N point: 188.6 ° C, N-I point: 317.9 ° C.

Example 4
4- (4-propylcyclohexyl) -2,5, -difluoro-4 "-ethylterphenyl (in the formula (1), R1 is a propyl group, X ₁ , X ₂ and X ₃ are covalent bonds, and Y ₁ is an ethyl group) , H ₂ , H ₃ , H _{5 to} H ₁₂ are hydrogen atoms, and H ₁ and H ₄ are replaced with fluorine atoms, a production method of compound number d-1).

  To a mixture of 4-bromo-4′-ethylbiphenyl (748 mmol) and THF 500 ml, 500 ml of n-butyllithium hexane solution (corresponding to 785 mmol) was dropped at −78 ° C. for 1.5 hours, and the mixture was stirred at the same temperature for 2.0 hours. A solution of trimethyl borate (1496 mmol) in 150 ml of THF was added dropwise to the solution, and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1600 ml of toluene and 500 ml of acetone to obtain 4′-ethylbiphenyl-4-boric acid (572 mmol) as a white solid.

  4′-ethylbiphenyl-4-boric acid (123 mmol), 1,4-dibromo-2,5-difluorobenzene (184 mmol), potassium carbonate (245 mmol), 5% palladium-carbon 3.0 g, toluene 240 ml, ethanol 240 ml, A mixture of 12 ml of water was refluxed for 7.3 hours. After allowing to cool, 300 ml of toluene was added to the reaction solution to make it uniform, followed by filtration and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: heptane) and recrystallization (recrystallization solvent: ethanol / toluene = 15/4) to give colorless plate-like 4-bromo-2,5-difluoro- 4 "-ethyl terphenyl (41.3 mmol) was obtained.

  A hexane solution (corresponding to 23.6 mol) of n-butyllithium was added dropwise to a mixture of 4-bromo-2,5-difluoro-4 "-ethylterphenyl (21.4 mol) and THF 130 ml while maintaining -78 ° C for 3 hours. The mixture was stirred at the same temperature, and a solution of 4-propylcyclohexanone (25.7 mol) in 10 ml of THF was added while maintaining at -78 ° C., and the mixture was gradually returned to room temperature while stirring and stirred overnight, and 67 ml of 7.3% hydrochloric acid was added. After stirring for 30 minutes, the reaction solution was extracted twice with toluene, washed four times with water and dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) to give a colorless solid. 4- (1-hydroxy-4-propylcyclohexyl) -2,5-difluoro-4 "-ethylterphenyl (15.3 mmol) It was.

  A mixture of 4- (1-hydroxy-4-propylcyclohexyl) -2,5-difluoro-4 "-ethylterphenyl (16.1 mmol), Amberlyst 15E (0.35 g) manufactured by Organo Corporation, and 250 ml of toluene, The resulting water was heated to reflux for 6.0 hours while dehydrating, allowed to cool, the reaction mixture was filtered, the solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) to give a colorless solid 4- ( 4-Propyl-1-cyclohexenyl) -2,5-difluoro-4 "-ethylterphenyl (15.3 mmol) was obtained.

4- (4-propyl-1-cyclohexenyl) -2,5-difluoro-4 "-ethylterphenyl (15.3 mmol) was added with 400 ml of toluene and 15 g of Raney nickel and stirred for 21 hours in a hydrogen atmosphere. After confirming that the catalyst had stopped, the catalyst was removed by filtration from the reaction system, the solvent was distilled off, the residue was purified by column chromatography (eluent: toluene), and recrystallized (recrystallization solvent: ethanol / toluene = 20 / 3) was repeated 4 times to obtain the title compound (3.50 mmol) as colorless crystals, and various spectral data of this product supported the structure as follows.
1H-NMR: δ (ppm): 6.91-7.71 (m, 10H), 2.90-3.10 (brs, 1H), 2.70 (q, 2H), 0.80-2. 10 (m, 19H)
GC-MS: 418 (M +)
Moreover, this compound showed liquid crystallinity and the phase transition temperature was as follows.
C-C point: 117.5 ° C, C-N point: 122.2 ° C, N-I point: 286.6 ° C.

Example 5
4- (4-pentylcyclohexyl) -2,6-difluoro-4 "-ethylterphenyl (in the formula (1), R ₁ is a pentyl group, X ₁ , X ₂ and X ₃ are covalent bonds, Y 1 is an ethyl group, A method for producing compound No. (d-25), wherein H ₁ , H ₃ , H ₅ , H ₆ , H ₇ and H ₈ are replaced with hydrogen atoms, and H ₂ and H ₄ are replaced with fluorine atoms.

  To a mixture of magnesium (600 mmol) and THF 1300 ml, 1-bromo-3,5-difluorobenzene (500 mmol) was added dropwise at room temperature and stirred at the same temperature for 30 minutes to obtain a Grignard reagent. To this solution, a mixture of 4-pentylcyclohexanone (600 mmol) and 200 ml of THF was added dropwise and stirred overnight at the same temperature. After adding 600 ml of 1N hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain (1-hydroxy-4-pentylcyclohexyl) -3,5-difluorobenzene (550 mmol). No particular purification was performed.

  A mixture of (1-hydroxy-4-pentylcyclohexyl) -3,5-difluorobenzene (300 mmol), Amberlyst (4.0 g) and 1000 ml of toluene was refluxed for 6 hours. After standing to cool, Amberlyst was filtered off, the solvent was distilled off, and the residue was purified by column chromatography (eluent: heptane) to give (4-pentyl-1-cyclohexenyl) -3,5-difluorobenzene (170 mmol). )

  A mixture of (4-pentyl-1-cyclohexenyl) -3,5-difluorobenzene (89 mmol), Raney nickel (3.5 g), and 500 ml of Solmix was subjected to a hydrogenation reaction at room temperature and normal pressure for 10 hours. When the hydrogen did not decrease and the reaction did not proceed any more, the catalyst was changed from Raney nickel to palladium carbon (2.4 g) and stirred for 8 hours. Palladium carbon was filtered off and the solvent was distilled off. The residue was purified by column chromatography (eluent: heptane) to obtain (4-pentyl-cyclohexyl) -3,5-difluorobenzene (81 mmol).

  To a mixture of (4-pentyl-cyclohexyl) -3,5-difluorobenzene (10 mmol) and 150 ml of THF, 7.5 ml (corresponding to 12 mmol) of n-butyllithium in hexane was added dropwise while keeping the temperature at −70 ° C. or less, and the same temperature was maintained for 30 minutes. And stirred. While maintaining at −70 ° C. or lower, iodine (30 mmol) was added and stirred for 1.5 hours, and then gradually returned to room temperature and stirred for 2 hours. After adding 12 ml of 1N hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted once with toluene and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: heptane) to give (4-pentyl-cyclohexyl) -3,5-difluoro-4-iodobenzene (8.3 mmol).

(4-Pentyl-cyclohexyl) -3,5-difluoro-4-iodobenzene (5 mmol), 4-ethyl-biphenyl-4-boric acid (6 mmol), sodium carbonate (18 mmol), tetrakistriphenylphosphinopalladium (0. 6 mmol), 50 ml of toluene and 50 ml of water were refluxed for 11 hours. After allowing to cool, the organic phase was separated and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: heptane) and recrystallization (recrystallization solvent: heptane) twice to obtain the title compound (3 mmol). Various spectral data of this one well supported its structure as follows.
1H-NMR: δ (ppm): 6.65-7.85 (m, 10H), 2.20-2.95 (m, 2H), 0.78-2.10 (m, 24H)
Moreover, this compound showed liquid crystallinity and the transition temperature was as follows.
C-N point: Decomposes at 143.3 ° C and 230 ° C or higher.

Example 6
4- (4-pentylcyclohexyl) -3 ′, 5′-difluoro-4 ″ -ethylterphenyl (in the formula (1), R ₁ is a propyl group, X ₁ , X ₂ and X ₃ are covalent bonds, and Y ₁ is A method for producing an ethyl group, a compound in which H _{1 to} H ₅ , H ₇ and H _{9 to} H ₁₂ are replaced with a hydrogen atom, and H ₆ and H ₈ are replaced with a fluorine atom, Compound No. d-43).

  To a mixture of 1-bromo-3,5-difluorobenzene (743 mmol) and THF 500 ml was added dropwise hexane solution 500 ml (equivalent to 780 mmol) of n-butyllithium at −78 ° C. for 1.6 hours and stirred at the same temperature for 1.5 hours. . To this solution was added dropwise a 200 ml THF solution of triisopropyl borate (1486 mmol), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1000 ml of toluene to obtain 3,5-difluorophenylboric acid (520 mmol) as a white solid.

  3,5-difluorophenylboric acid (73.6 mmol), 1-bromo-4-iodobenzene (77.5 mmol), potassium carbonate (147 mmol), 0.5% palladium carbon 0.5 g, toluene 100 ml, ethanol 100 ml, water 6 0.0 ml of the mixture was refluxed for 5 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/9) and recrystallized (recrystallization solvent: ethanol) to give 4-bromo-3 ′, 5 ′ as a colorless solid. -Difluorobiphenyl (45.0 mmol) was obtained.

  4-Bromo-3 ′, 5′-difluorobiphenyl (44.0 mmol), iodic acid (22.0 mmol), iodine (26.6 mmol), acetic acid (33 ml), water (4.0 ml), carbon tetrachloride (4 0.0 ml) was refluxed for 24 hours. After allowing to cool, the reaction solution was extracted twice with heptane and washed twice with water. This was washed with 160 ml of a 4% aqueous sodium thiosulfate solution, washed three times with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/9) and recrystallized twice (recrystallization solvent: ethanol) to give pale yellowish green crystals 4-bromo-3 ', 5'-Difluoro-4'-iodobiphenyl (10.6 mmol) was obtained.

  To a mixture of 1-bromo-4-ethylbenzene (743 mmol) and THF 500 ml, 500 ml (equivalent to 780 mmol) of a hexane solution of n-butyllithium was added dropwise at −78 ° C. for 1.6 hours, followed by stirring at the same temperature for 1.5 hours. To this solution was added dropwise a 200 ml THF solution of triisopropyl borate (1486 mmol), and the mixture was gradually warmed to room temperature and stirred overnight. After adding 750 ml of 7.3% hydrochloric acid and stirring for 30 minutes, the reaction solution was extracted twice with diethyl ether, washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from about 1000 ml of toluene to obtain 4-ethylphenylboric acid (515 mmol) as a white solid.

  4-ethylphenylboric acid (9.50 mmol), 4-bromo-3 ′, 5′-difluoro-4′-iodobiphenyl (10.0 mmol), potassium carbonate (19.0 mmol), 0.07 g of 5% palladium on carbon , Toluene 13 ml, ethanol 13 ml, water 0.8 ml was refluxed for 5 hours. After cooling, the reaction solution was filtered and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene / n-heptane = 1/9) and recrystallized (recrystallization solvent: ethanol) to give 4-bromo-3 ′, 5 ′ as a colorless solid. -Difluoro-4 "-ethylterphenyl (7.05 mmol) was obtained.

  A hexane solution of n-butyllithium (equivalent to 7.72 mol) was added dropwise to a mixture of 4-bromo-3 ′, 5′-difluoro-4 ”-ethylterphenyl (7.00 mol) and 44 ml of THF while maintaining −78 ° C. The mixture was stirred for 3 hours at the same temperature, and a solution of 4-pentylcyclohexanone (8.40 mol) in 10 ml of THF was added while maintaining -78 ° C, and the mixture was gradually returned to room temperature while stirring and stirred overnight. After stirring for 30 minutes, the reaction solution was extracted twice with toluene, washed four times with water and dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) to be colorless. Solid 4- (1-hydroxy-4-pentylcyclohexyl) -3 ′, 5′-difluoro-4 ″ -ethylterphenyl (5.10 mmol) It was.

  Mixture of 4- (1-hydroxy-4-pentylcyclohexyl) -3 ′, 5′-difluoro-4 ”-ethylterphenyl (5.00 mmol), Amberlyst 15E (0.12 g) manufactured by Organo, and 80 ml of toluene The mixture was heated to reflux for 6.0 hours while dehydrating the water produced, and the reaction mixture was filtered after standing to cool.The solvent was distilled off, and the residue was purified by column chromatography (eluent: toluene) to give a colorless solid 4 -(4-Pentyl-1-cyclohexenyl) -3 ', 5'-difluoro-4 "-ethylterphenyl (4.75 mmol) was obtained.

  To 4- (4-pentyl-1-cyclohexenyl) -3 ', 5'-difluoro-4 "-ethylterphenyl (4.75 mmol) was added 400 ml of toluene and 15 g of Raney nickel, and the mixture was stirred for 20 hours in a hydrogen atmosphere. After confirming that the absorption stopped, the catalyst was removed by filtration from the reaction system, the solvent was distilled off, the residue was purified by column chromatography (eluent: toluene), and recrystallized (recrystallization solvent: ethanol / toluene = 20/3) was repeated four times to obtain the title compound (1.15 mmol) as colorless crystals, and various spectral data of this product well supported the structure.

Example 7
The compounds of the following formula (1) are produced according to Examples 1 to 6.

Example 8 (Use Example 1)
4- (4-Propylcyclohexyl) benzonitrile 24%
4- (4-pentylcyclohexyl) benzonitrile 36%
4- (4-Heptylcyclohexyl) benzonitrile 25%
4- (4-propylphenyl) benzonitrile 15%
A liquid crystal composition B1 comprising: The clearing point of B1 is 71.7 ° C., the dielectric anisotropy value is 11.0, the refractive index anisotropy value is 0.137, the viscosity at 20 ° C. is 26.7 mPa · s, and the cell thickness is 9.2 μm. The threshold voltage was 1.78V.

5% of B1 was mixed with 5% of the compound 4- (4-methoxymethylcyclohexyl) -2′-fluoro-4 ″ -methylterphenyl (Compound No. a-1) obtained in Example 1 according to the present invention. An A1 was prepared, which had a clearing point of 79.1 ° C. (extrapolated value 219.7 ° C.), a dielectric anisotropy value of 10.9 (extrapolated value 9.0), and a refractive index anisotropy value. Was 0.144 (extrapolated value 0.277), the viscosity at 20 ° C. was 29.3 mPas (extrapolated value 76.8 mPas), and the threshold voltage at a cell thickness of 8.9 μm was 1.75 V. The composition was left in a freezer at −20 ° C. for 60 days, but no precipitation of crystals was observed, and the voltage holding ratio of A1 was measured and found to be 99.6% at 100 ° C.

15% of the compound 4- (4-methoxymethylcyclohexyl) -2 ′, 5′-difluoro-4 ″ -methylterphenyl (Compound No. b-1) obtained in Example 2 was mixed with 85% of B1 Liquid crystal composition A2 was prepared, which had a clearing point of 91.0 ° C. (extrapolated value 200.4 ° C.), a dielectric anisotropy value of 10.6 (extrapolated value 8.3), and a different refractive index. The isotropic value was 0.155 (extrapolated value 0.257), the viscosity at 20 ° C. was 36.9 mPas (extrapolated value 94.7 mPas), and the threshold voltage at a cell thickness of 9.2 μm was 1.93 V. The composition was left in a freezer at −20 ° C. for 60 days, but no crystal deposition was observed, and the voltage holding ratio of A2 was measured to be 99.7% at 100 ° C.

  The liquid crystal composition A3 was prepared by mixing 5% of the compound 4- (4-propylcyclohexyl) -3-fluoro-4 "-ethylterphenyl (Compound No. c-1) obtained in Example 3 with 95% of B1. The clearing point of this was 79.5 ° C. (extrapolated value 227.7 ° C.), the dielectric anisotropy value was 10.7 (extrapolated value 5.0), and the refractive index anisotropy value was 0. 144 (extrapolated value 0.277), the viscosity at 20 ° C. was 28.5 mPas (extrapolated value 64.6 mPas), and the threshold voltage at the cell thickness of 8.7 μm was 1.77 V. The composition was left in a freezer at −20 ° C. for 60 days, but no precipitation of crystals was observed, and the voltage holding ratio of A3 was measured and found to be 99.6% at 100 ° C.

  85% of B1 was mixed with 15% of the compound 4- (4-propylcyclohexyl) -2,5, -difluoro-4 "-ethylterphenyl (Compound No. d-1) obtained in Example 4 according to the present invention. Composition A4 was prepared, which had a clearing point of 93.0 ° C. (extrapolated value 213.7 ° C.), a dielectric anisotropy value of 10.1 (extrapolated value 5.0), and a refractive index anisotropy. The value was 0.155 (extrapolated value 0.257), the viscosity at 20 ° C. was 35.0 mPas (extrapolated value 81.5 mPas), and the threshold voltage at a cell thickness of 8.8 μm was 1.90 V. The composition was left in a freezer at −20 ° C. for 60 days, but no precipitation of crystals was observed, and the voltage holding ratio of A4 was measured and found to be 99.7% at 100 ° C.

Example 9
When the liquid crystal composition prepared by mixing Compound No. d-1 (15%) with B1 (85%) was left in a freezer at −20 ° C., crystals and smectics did not appear for more than 60 days. On the other hand, a liquid crystal composition prepared by mixing the aforementioned B1 (85%) with 4- (4-propylcyclohexyl) -4 "-ethylterphenyl (15%) synthesized according to the method of JP-A-58-203922. The product was also allowed to stand in a freezer at −20 ° C., whereupon crystals precipitated in 1 hour, and 4- (4-propylcyclohexyl) -4 ”-ethylterphenyl (5%) was added to B1 (95%). When the liquid crystal composition prepared by mixing was allowed to stand in a freezer at −20 ° C., crystals were precipitated in 3 days.

Example 10
The nematic temperature range of 4- (4-pentylcyclohexyl) -3'-fluoro-4 "-propylterphenyl described in JP-A-2-237949 is as narrow as 43 ° C. The nematic temperature ranges of -1 and d-1 were as wide as 129.3 ° C and 164.4 ° C, respectively.

  Examples of the nematic liquid crystal composition containing the compound of the present invention can further include the following composition examples. However, the compounds described in the composition examples are shown according to the rules in the following table.

Example 11
1O1-HBB (2F) B-1 (Compound No. a-1) 3.0%
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 5.0%
1V2-BEB (F, F) -C 5.0%
3-HB-C 25.0%
3-HB-O2 4.0%
1-BTB-3 5.0%
2-BTB-1 10.0%
3-HH-4 11.0%
3-HHB-1 9.0%
3-HHB-3 7.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-HB (F) TB-2 6.0%
3-HB (F) TB-3 2.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 90.7 (℃)
η = 18.7 (mPa · s)
Δn = 0.161
Δε = 7.3
_Vth = 2.05 (V)

Example 12
3-HB (2F) BB-2 (Compound No. c-1) 3.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 5.0%
V2-HB-C 12.0%
1V2-HB-C 12.0%
3-HB-C 24.0%
3-HB (F) -C 5.0%
3-HB-O2 5.0%
2-BTB-1 2.0%
3-HH-4 8.0%
3-HHV (F) -F 6.0%
2-HHB-C 3.0%
3-HHB-C 6.0%
3-HB (F) TB-2 5.0%
3-H2BTB-4 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 87.0 (℃)
η = 20.1 (mPa · s)
Δn = 0.144
Δε = 8.7
V _th = 2.00 (V)

Example 13
5-HBB (F, F) B-2 (Compound No. d-43) 3.0%
2O1-BEB (F) -C 5.0%
3O1-BEB (F) -C 15.0%
4O1-BEB (F) -C 13.0%
5O1-BEB (F) -C 13.0%
3-HB (F) -C 3.0%
2-HHB (F) -C 15.0%
3-HHB (F) -C 12.0%
3-HB (F) TB-2 4.0%
3-HB (F) TB-3 4.0%
3-HB (F) TB-4 4.0%
3-HHB-1 5.0%
3-HHB-O1 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 88.6 (℃)
η = 85.2 (mPa · s)
Δn = 0.151
Δε = 31.3
V _th = 0.88 (V)

Example 14
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 10.0%
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%
3-PyB-2 2.0%
4-PyB-2 2.0%
6-PyB-O5 3.0%
6-PyB-O6 3.0%
6-PyB-O7 3.0%
6-PyB-O8 3.0%
3-PyBB-F 6.0%
4-PyBB-F 6.0%
5-PyBB-F 6.0%
3-HB-O2 5.0%
3-HHB-1 6.0%
3-HHB-3 3.0%
2-H2BTB-2 4.0%
2-H2BTB-3 4.0%
3-H2BTB-3 5.0%
3-H2BTB-4 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 94.4 (℃)
η = 41.3 (mPa · s)
Δn = 0.200
Δε = 6.8
V _th = 2.30 (V)

Example 15
1O1-HBB (2F) B-1 (Compound No. a-1) 3.0%
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%
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%
5-HEB-5 5.0%
4-HEB-5 5.0%
1O-BEB-2 4.0%
3-HHB-1 6.0%
3-HHEBB-C 3.0%
3-HBEBB-C 3.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 68.3 (℃)
η = 38.1 (mPa · s)
Δn = 0.121
Δε = 11.2
V _th = 1.33 (V)

Example 16
3-HB (2F) BB-2 (Compound No. c-1) 4.0%
3-HB-C 21.0%
7-HB-C 3.0%
1O1-HB-C 10.0%
3-HB (F) -C 10.0%
2-PyB-2 2.0%
3-PyB-2 2.0%
4-PyB-2 2.0%
1O1-HH-3 7.0%
2-BTB-O1 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%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 79.1 (° C)
η = 19.0 (mPa · s)
Δn = 0.142
Δε = 8.4
V _th = 1.72 (V)

Example 17
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 5.0%
3-HB (2F) BB-2 (Compound No. c-1) 3.0%
2O1-BEB (F) -C 5.0%
3O1-BEB (F) -C 12.0%
5O1-BEB (F) -C 4.0%
1V2-BEB (F, F) -C 10.0%
3-HHE-1 10.0%
3-HB-O2 21.0%
3-HHEB-F 3.0%
5-HHEB-F 3.0%
3-HBEB-F 4.0%
2O1-HBE (F) -C 2.0%
3-HB (F) EB (F) -C 2.0%
3-HBEB (F, F) -C 2.0%
2-HHB-F 4.0%
3-HHB-O1 4.0%
3-HHB-3 2.0%
3-BEBEB-F 2.0%
3-BEBEB-1 2.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 79.4 (℃)
η = 40.1 (mPa · s)
Δn = 0.122
Δε = 23.7
V _th = 0.97 (V)

Example 18
3-HB (2F) BB-2 (Compound No. c-1) 4.0%
5-BEB (F) -C 5.0%
V-HB-C 11.0%
5-PyB-C 6.0%
4-BB-3 11.0%
3-HH-2V 10.0%
5-HH-V 11.0%
V-HHB-1 7.0%
V2-HHB-1 15.0%
3-HHB-1 5.0%
1V2-HBB-2 10.0%
3-HHEBH-3 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 94.7 (℃)
η = 17.3 (mPa · s)
Δn = 0.121
Δε = 4.8
V _th = 2.36 (V)

Example 19
5-HB (F, F) BB-2 (Compound No. d-25) 4.0%
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-HB-O2 10.0%
3-HH-4 3.0%
3-HHB-F 3.0%
3-HHB-1 8.0%
3-HHB-O1 4.0%
3-HBEB-F 4.0%
3-HHEB-F 7.0%
5-HHEB-F 3.0%
3-H2BTB-2 4.0%
3-H2BTB-3 4.0%
3-H2BTB-4 4.0%
3-HB (F) TB-2 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 92.0 (℃)
η = 41.9 (mPa · s)
Δn = 0.147
Δε = 28.4
V _th = 0.99 (V)

Example 20
3-HB (2F, 5F) BB-2 (Compound No. d-1) 5.0%
2-BEB-C 12.0%
3-BEB-C 4.0%
4-BEB-C 6.0%
3-HB-C 30.0%
3-HEB-O4 12.0%
4-HEB-O2 8.0%
5-HEB-O1 8.0%
3-HEB-O2 6.0%
5-HEB-O2 5.0%
3-HHB-O1 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 63.8 (℃)
η = 29.0 (mPa · s)
Δn = 0.120
Δε = 10.3
V _th = 1.31 (V)

Example 21
1O1-HBB (2F) B-1 (Compound No. a-1) 4.0%
3-HB (2F) BB-2 (Compound No. c-1) 4.0%
2-BEB-C 10.0%
5-BB-C 12.0%
7-BB-C 7.0%
3-HB-C 5.0%
1-BTB-3 7.0%
2-BTB-1 10.0%
1O-BEB-2 10.0%
1O-BEB-5 12.0%
2-HHB-1 4.0%
3-HHB-F 4.0%
3-HHB-1 7.0%
3-HHB-O1 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 70.1 (℃)
η = 24.3 (mPa · s)
Δn = 0.171
Δε = 6.8
V _th = 1.72 (V)

Example 22
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 12.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 6.0%
1V2-BEB (F, F) -C 5.0%
3-HB-C 25.0%
1-BTB-3 5.0%
2-BTB-1 10.0%
3-HH-4 11.0%
3-HHB-1 11.0%
3-HHB-3 9.0%
3-HB-O2 6.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 92.2 (℃)
η = 24.1 (mPa · s)
Δn = 0.220
Δε = 7.0
V _th = 2.12 (V)

Example 23
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 10.0%
5-HB (F, F) BB-2 (Compound No. d-25) 4.0%
2O1-BEB (F) -C 5.0%
3O1-BEB (F) -C 15.0%
4O1-BEB (F) -C 13.0%
5O1-BEB (F) -C 13.0%
3-HB-C 10.0%
2-HHB (F) -C 15.0%
3-HHB (F) -C 3.0%
3-HB (F) TB-2 4.0%
3-HB (F) TB-3 4.0%
3-HB (F) TB-4 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 85.8 (℃)
η = 92.0 (mPa · s)
Δn = 0.162
Δε = 31.2
V _th = 0.84 (V)

Example 24
1O1-HBB (2F) B-1 (Compound No. a-1) 2.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 5.0%
7-HB (F) -F 5.0%
2-HHB (F) -F 17.0%
3-HHB (F) -F 17.0%
5-HHB (F) -F 16.0%
2-H2HB (F) -F 5.0%
3-H2HB (F) -F 5.0%
2-HBB (F) -F 6.0%
3-HBB (F) -F 6.0%
5-HBB (F) -F 13.0%
3-HB-O2 3.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 102.1 (℃)
η = 29.5 (mPa · s)
Δn = 0.102
Δε = 5.0
_Vth = 2.22 (V)

Example 25
1O1-HBB (2F) B-1 (Compound No. a-1) 2.0%
5-HB (F, F) BB-2 (Compound No. d-25) 2.0%
7-HB (F) -F 10.0%
5-H2B (F) -F 5.0%
3-HB-O2 10.0%
3-HH-4 5.0%
2-HHB (F) -F 10.0%
3-HHB (F) -F 10.0%
5-HHB (F) -F 5.0%
3-H2HB (F) -F 5.0%
2-HBB (F) -F 3.0%
3-HBB (F) -F 3.0%
5-HBB (F) -F 6.0%
2-H2BB (F) -F 5.0%
3-H2BB (F) -F 6.0%
3-HHB-1 8.0%
3-HHB-O1 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 84.3 (℃)
η = 19.5 (mPa · s)
Δn = 0.094
Δε = 3.4
V _th = 2.63 (V)

Example 26
3-HB (2F) BB-2 (Compound No. c-1) 2.0%
5-HB (F, F) BB-2 (Compound No. d-25) 2.0%
7-HB (F, F) -F 6.0%
3-HB-O2 7.0%
2-HHB (F) -F 10.0%
3-HHB (F) -F 10.0%
5-HHB (F) -F 3.0%
2-HBB (F) -F 9.0%
3-HBB (F) -F 9.0%
5-HBB (F) -F 16.0%
2-HBB-F 4.0%
3-HBB-F 4.0%
5-HBB-F 3.0%
3-HBB (F, F) -F 5.0%
5-HBB (F, F) -F 10.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 81.4 (℃)
η = 26.0 (mPa · s)
Δn = 0.118
Δε = 5.8
V _th = 1.99 (V)

Example 27
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 4.0%
7-HB (F, F) -F 7.0%
3-H2HB (F, F) -F 12.0%
4-H2HB (F, F) -F 10.0%
5-H2HB (F, F) -F 10.0%
3-HHB (F, F) -F 10.0%
4-HHB (F, F) -F 5.0%
3-HH2B (F, F) -F 15.0%
5-HH2B (F, F) -F 3.0%
3-HBB (F, F) -F 12.0%
5-HBB (F, F) -F 12.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 73.2 (℃)
η = 29.2 (mPa · s)
Δn = 0.090
Δε = 8.6
V _th = 1.59 (V)

Example 28
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 4.0%
7-HB (F, F) -F 8.0%
3-H2HB (F, F) -F 12.0%
4-H2HB (F, F) -F 10.0%
3-HHB (F, F) -F 10.0%
4-HHB (F, F) -F 5.0%
3-HBB (F, F) -F 10.0%
3-HHEB (F, F) -F 3.0%
4-HHEB (F, F) -F 3.0%
5-HHEB (F, F) -F 3.0%
2-HBEB (F, F) -F 3.0%
3-HBEB (F, F) -F 5.0%
5-HBEB (F, F) -F 3.0%
3-HDB (F, F) -F 15.0%
3-HHBB (F, F) -F 6.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 76.5 (℃)
η = 34.7 (mPa · s)
Δn = 0.090
Δε = 12.9
V _th = 1.41 (V)

Example 29
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 4.0%
5-HB (F, F) BB-2 (Compound No. d-25) 2.0%
3-HB-CL 10.0%
5-HB-CL 4.0%
7-HB-CL 4.0%
3-HB-O2 2.0%
1O1-HH-5 5.0%
2-HBB (F) -F 8.0%
3-HBB (F) -F 8.0%
5-HBB (F) -F 14.0%
4-HHB-CL 8.0%
3-H2HB (F) -CL 4.0%
3-HBB (F, F) -F 10.0%
5-H2BB (F, F) -F 9.0%
3-HB (F) VB-2 4.0%
3-HB (F) VB-3 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 91.0 (℃)
η = 22.1 (mPa · s)
Δn = 0.135
Δε = 5.0
V _th = 2.29 (V)

Example 30
3-HB (2F, 5F) BB-2 (Compound No. d-1) 5.0%
7-HB (F, F) -F 5.0%
3-HHB (F, F) -F 9.0%
3-H2HB (F, F) -F 8.0%
4-H2HB (F, F) -F 6.0%
3-HBB (F, F) -F 21.0%
5-HBB (F, F) -F 20.0%
3-H2BB (F, F) -F 10.0%
5-HHBB (F, F) -F 3.0%
5-HHEBB-F 2.0%
3-HH2BB (F, F) -F 3.0%
1O1-HBBH-4 4.0%
1O1-HBBH-5 4.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 98.5 (℃)
η = 35.1 (mPa · s)
Δn = 0.120
Δε = 8.5
V _th = 1.70 (V)

Example 31
5-HBB (F, F) B-2 (Compound No. d-43) 2.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 2.0%
5-HB-F 12.0%
6-HB-F 9.0%
7-HB-F 7.0%
7-HB (F) -F 3.0%
2-HHB-OCF3 7.0%
3-HHB-OCF3 11.0%
4-HHB-OCF3 7.0%
5-HHB-OCF3 5.0%
3-HH2B-OCF3 4.0%
5-HH2B-OCF3 4.0%
3-HHB (F, F) -OCF3 5.0%
3-HBB (F) -F 10.0%
5-HBB (F) -F 3.0%
3-HH2B (F) -F 3.0%
3-HB (F) BH-3 3.0%
5-HBBH-3 3.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 87.3 (℃)
η = 14.8 (mPa · s)
Δn = 0.091
Δε = 4.6
V _th = 2.38 (V)

Example 32
3-HB (2F) BB-2 (Compound No. c-1) 2.0%
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 2.0%
5-H4HB (F, F) -F 7.0%
5-H4HB-OCF3 15.0%
3-H4HB (F, F) -CF3 8.0%
5-H4HB (F, F) -CF3 10.0%
3-HB-CL 6.0%
5-HB-CL 7.0%
2-H2BB (F) -F 5.0%
3-H2BB (F) -F 3.0%
5-HVHB (F, F) -F 5.0%
3-HHB-OCF3 5.0%
3-H2HB-OCF3 5.0%
V-HHB (F) -F 5.0%
3-HChB (F) -F 5.0%
5-HHEB-OCF3 2.0%
3-HBEB (F, F) -F 5.0%
5-HHV2-F 3.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 74.6 (℃)
η = 24.3 (mPa · s)
Δn = 0.093
Δε = 8.1
V _th = 1.77 (V)

Example 33
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 4.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 6.0%
2-HHB (F) -F 2.0%
3-HHB (F) -F 2.0%
5-HHB (F) -F 2.0%
2-HBB (F) -F 6.0%
3-HBB (F) -F 6.0%
5-HBB (F) -F 10.0%
2-H2BB (F) -F 9.0%
3-H2BB (F) -F 9.0%
7-HB (F, F) -F 7.0%
3-HBB (F, F) -F 25.0%
5-HBB (F, F) -F 7.0%
1O1-HBBH-4 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 96.8 (℃)
η = 36.6 (mPa · s)
Δn = 0.145
Δε = 7.1
V _th = 2.01 (V)

Example 34
1O1-HBB (2F) B-1 (Compound No. a-1) 2.0%
1O1-HBB (2F, 5F) B-1 (Compound No. b-1) 4.0%
3-HB (2F, 5F) BB-2 (Compound No. d-1) 6.0%
5-HB (F, F) BB-2 (Compound No. d-25) 2.0%
7-HB (F, F) -F 15.0%
3-H2HB (F, F) -F 12.0%
4-H2HB (F, F) -F 10.0%
3-HHB (F, F) -F 10.0%
4-HHB (F, F) -F 5.0%
5-HH2B (F, F) -F 10.0%
3-HBB (F, F) -F 12.0%
5-HBB (F, F) -F 12.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 75.7 (℃)
η = 30.1 (mPa · s)
Δn = 0.087
Δε = 8.0
V _th = 1.70 (V)

Example 35
3-HB (2F) BB-2 (Compound No. c-1) 2.0%
5-HBB (F, F) B-2 (Compound No. d-43) 2.0%
2-HHB (F) -F 3.0%
3-HHB (F) -F 2.0%
5-HHB (F) -F 2.0%
2-HBB (F) -F 6.0%
3-HBB (F) -F 6.0%
5-HBB (F) -F 10.0%
2-H2BB (F) -F 9.0%
3-H2BB (F) -F 9.0%
3-HBB (F, F) -F 25.0%
5-HBB (F, F) -F 19.0%
1O1-HBBH-4 5.0%
Various physical properties of this liquid crystal composition were as follows.
T _NI = 93.2 (℃)
η = 35.0 (mPa · s)
Δn = 0.135
Δε = 7.4
V _h = 1 _t . 93 (V)

Claims (6)

General formula (1)

(In the formula, among the hydrogen atoms of H _{1 to} H ₁₂ , H ₁ and H ₂ , or H ₅ and H ₆ are replaced by fluorine atoms. R ₁ and Y ₁ are each independently an alkyl group having 1 to 1 carbon atoms. 20 represents an alkyl group, and one or two or more methylene groups in R ₁ and Y ₁ may be replaced by any one of an oxygen atom and —CH═CH— X ₁ , X ₂ , X ₃ Represents a covalent bond.)   A liquid crystal composition comprising at least one tetracyclic compound according to claim 1. The first component contains at least one tetracyclic compound according to claim 1, and the second component contains general formulas (2), (3) and (4).

(Wherein R ₂ represents an alkyl group having 1 to 10 carbon atoms, Y ₂ represents a fluorine atom, a chlorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and L ₁ , L ₂ , L ₃ and L ₄ each independently represent a hydrogen atom or a fluorine atom, Z ₁ and Z ₂ each independently represent a 1,2-ethylene group, —CH═CH— or a covalent bond, a represents 1 or 2.) A liquid crystal composition comprising at least one compound selected from the group consisting of: The first component contains at least one tetracyclic compound according to claim 1, and the second component contains general formulas (5), (6), (7), (8) and (9).

(In the formula, R ₃ represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl group or alkenyl group is substituted with an oxygen atom. However, two or more methylene groups are not continuously substituted by oxygen atoms, and ring B is 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5- Diyl, ring C represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring D represents 1,4-cyclohexylene or 1,4-phenylene, Z ₃ Represents a 1,2-ethylene group, —COO— or a covalent bond, L ₅ and L ₆ each independently represent a hydrogen atom or a fluorine atom, and b and c each independently represents 0 or 1 .)

(In the formula, R ₄ represents an alkyl group having 1 to 10 carbon atoms, L ₇ represents a hydrogen atom or a fluorine atom, and d represents 0 or 1.)

(Wherein R ₅ represents an alkyl group having 1 to 10 carbon atoms, ring E and ring F each independently represent 1,4-cyclohexylene or 1,4-phenylene, and Z ₄ and Z ₅ represent Each independently represents —COO— or a covalent bond, Z ₆ represents —COO— or —C≡C—, L ₈ and L ₉ each independently represent a hydrogen atom or a fluorine atom, Y ₃ Represents a fluorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H or CFH ₂ , and e, f and g each independently represent 0 or 1.)

(In the formula, R ₆ and R ₇ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any methylene group thereof is substituted by an oxygen atom. However, two or more methylene groups may not be successively substituted by oxygen atoms, and ring H may be 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl. Ring I represents 1,4-cyclohexylene or 1,4-phenylene, Z ₆ represents —C≡C—, —COO—, a 1,2-ethylene group, —CH═CH—C≡C— or And represents a covalent bond, and Z ₇ represents —COO— or a covalent bond.

(In the formula, R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In any case, any methylene group is substituted by an oxygen atom. However, two or more methylene groups may not be substituted with oxygen atoms in succession, ring J may be 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl. Ring K represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl in which one or more hydrogen atoms on the ring may be substituted with fluorine atoms, and ring L represents 1,4-cyclohexylene or 1,4-phenylene, Z ₈ and Z ₁₀ each independently represent —COO—, 1,2-ethylene group or a covalent bond, and Z ₉ represents —CH═CH—. , -C≡C-, COO- or indicates a covalent bond, h is the liquid crystal composition characterized in that at least one compound selected from the group consisting of a 0 or 1.). The group consisting of at least one tetracyclic compound according to claim 1 as a first component and a group consisting of general formulas (2), (3) and (4) according to claim 3 as part of a second component At least one compound selected from the group consisting of general formulas (5), (6), (7), (8) and (9) according to claim 13 as the other part of the second component A liquid crystal composition comprising at least one compound selected from the group. The liquid crystal display device fabricated by using the liquid crystal composition according to any one of claims 2-5.