DIFLUOROPHENYL DERIVATIVES, LIQUID-CRYSTAL COMPOUNDS, AND LIQUID-CRYSTAL COMPOSITION

Abstract

Disclosed are liquid crystalline compounds which (i) are characterized in that the compounds have a wide temperature range in which the compounds exhibit a liquid crystal phase, are low in viscosity, and have a negative and high &Dgr;&egr;, (ii) are readily mixed with other various liquid crystal materials even at low temperatures, and (iii) are useful as component of liquid crystal compositions suitable both for TFT type display mode and IPS mode; and liquid crystal composition comprising the liquid crystalline compound; the compounds are expressed by the general formula (1) 1

Description

TECHNICAL FIELD

[0001] The present invention relates to liquid crystalline compounds and liquid crystal compositions. More specifically, the invention relates to novel liquid crystalline compounds simultaneously having butylene group or propylenoxy group, and 2,3-difluorophenyl group in the compounds; to liquid crystal compositions comprising the compound; and further to liquid crystal display devices fabricated by using the liquid crystal composition.

BACKGROUND ART

[0002] Display devices produced by employing optical anisotropy and dielectric anisotropy which are characteristics of liquid crystalline compounds (the term “liquid crystalline compounds” is used in this specification as a general term for the compounds which exhibit a liquid crystal phase and for the compounds which do not exhibit a liquid crystal phase but are useful as component of liquid crystal compositions) have widely been utilized for tabletop calculators, word processors, and TV sets including watches, and the demand for the devices are rising year after year.

[0003] Liquid crystal phase is broadly classified into nematic phase, smectic phase, and cholesteric phase. Among them, nematic phase has most widely been employed for display devices. As display mode applied for liquid crystal display, TN (twisted nematic) display mode, DS (dynamic scattering) display mode, guest-host display mode, and DAP (Deformation of Aligned Phases) display mode have been developed corresponding to electro-optic effects.

[0004] In recent years, coloring of liquid crystal displays has rapidly been advanced, and thin film transistor (TFT) display mode and super twisted nematic (STN) display mode are main streams in TN display mode as display mode. On the other hand, CRT which is a main stream of current television screen is expected to be replaced by liquid crystal displays sooner or later. In order to realize the replacement, liquid crystal displays must have display characteristics comparable to those of CRT.

[0005] In the research and development of liquid crystal displays, one's energies have been devoted to the improvement of response speed, contrast, and viewing angle as important subject. Among them, response speed and contrast became such an extent as equal to those of CRT as a result of repeated improvements in TFT display mode. However, a wide viewing angle comparable to that of CRT has not yet been actualized, whereas some improvements such as an improvement in the orientational direction of liquid crystal molecules and the use of a phase difference plate have been made as to viewing angle.

[0006] Although it is an active matrix mode similar to that of TFT display mode, in-plane-switching (IPS) display mode which is characterized in that comb type electrodes are formed only one side of substrate is lately performed on the stage as a mode for actualizing a wide viewing angle (G. Baur, Freiburger Arbeistagung Flussigkristalle, Abstract No. 22 (1993) and M. Oh-e et al., ASIA DISPLAY '95, 577 (1995)). When liquid crystalline compounds having a negative dielectric anisotropy value (&Dgr;&egr;) was used in IPS display mode, a dramatically wide viewing angle was obtained.

[0007] However, this IPS display mode has such a defect that response speed is considerably low compared with conventional TFT display mode or STN display mode. Then, liquid crystalline compounds having a negative and high &Dgr;&egr; and a low viscosity are have been required in IPS display mode.

[0008] Also, since active matrix driving mode is employed in IPS mode as described above, liquid crystalline compounds having a high voltage holding ratio (V. H. R.) are more preferable.

[0009] Various compounds having a negative dielectric anisotropy value are already known. In Laid-open Japanese Patent Publication No. Hei 2-4724 and Tokuhyo (Laid-open Japanese WO publication) No. Hei 2-503441, compounds having 2,3-difluoro-1,4-phenylene group in their partial structure are disclosed as liquid crystal compound having a negative &Dgr;&egr;.

[0010] It is considered that in the compounds having such partial structure, fluorine atoms substituted at positions 2 and 3 act so as to increase dipole moment in the direction of the minor axis of molecules to make dipole moment of the major axis smaller than the dipole moment in the direction of minor axis, and as the result, the compounds come to have a negative dielectric anisotropy value. However, compounds having such partial structure become slightly narrow in their temperature range exhibiting a liquid crystal phase compared with compounds in which hydrogen atoms of phenylene group are not replaced by fluorine atoms, their miscibility with other liquid crystalline compounds particularly at very low temperatures can hardly be said to be excellent, and sometimes such phenomena that smectic phase is developed and crystals are separated in liquid crystal compositions in a low temperature region are observed.

[0011] Compounds expressed by the following formula (a) are described in Tokuhyo No. Hei 2-503441: 2

[0012] wherein R and R′ represent an alkyl group and alkoxy group, respectively.

[0013] Whereas structural formula of the compounds is described in the publication mentioned above, physical properties and the likes necessary for judging the utility of the compounds as liquid crystalline compound are not described at all therein. Based on the consideration by the present inventors, whereas an improvement in miscibility by the compounds of the formula (a) described above compared with compounds having no 1,2-ethylene group can be surmised since the compounds of the formula (a) have 1,2-ethylene group as bonding group in skeleton structure, their effect can not be said to be sufficient.

DISCLOSURE OF THE INVENTION

[0014] An object of the present invention is to provide liquid crystalline compounds which are wide particularly in temperature range of liquid crystal phase, have a low viscosity, have a negative and large &Dgr;&egr;, and are improved in solubility at low temperatures; to provide liquid crystal compositions comprising the compound; and to provide liquid crystal display devices fabricated by using the liquid crystal composition, thereby to overcome the problems in conventional technologies described above.

[0015] Then, compounds expressed by the general formula (1) and simultaneously having butylene group or propylenoxy group, and 2,3-difluoro-1,4-phenylene group in the structure of compounds were diligently investigated by the present inventors. As the result of the investigation, it has been found out that the compounds are characterized in that they are wide in temperature range exhibiting a liquid crystal phase, are low in viscosity, and have a negative and large &Dgr;&egr;, as well as they are remarkably excellent in miscibility at low temperatures, leading to the accomplishment of the present invention.

[0016] That is, the present invention is summarized as follows:

[0017] [1] A liquid crystalline compound expressed by the general formula (1) 3

[0018] wherein R1 represents an alkyl group having 1 to 15 carbon atoms in which alkyl group, not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X1, X2, and X3 independently represent —(CH2)4—, —(CH2)3O—, —O(CH2)3—, or single bond; Y1 represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

[0019] [2] The liquid crystalline compound recited in paragraph [1] above wherein ring Al represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X1 represents —(CH2)4— or —(CH2)3O—; and either m and n are 0 in the general formula (1).

[0020] [3] The liquid crystalline compound recited in paragraph [1] above wherein ring A1 and ring A2 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; XI represents —(CH2)4— or —(CH2)3O—; X2 represents single bond; and m is 1 and n is 0 in the general formula (1).

[0021] [4] The liquid crystalline compound recited in paragraph [1] above wherein ring A1 and ring A2 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X2 represents —(CH2)4— or —(CH2)3O—; X1 represents single bond; and m is 1 and n is 0 in the general formula (1).

[0022] [5] The liquid crystalline compound recited in paragraph [1] above wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X1 represent —(CH2)4— or —(CH2)3O—; either X2 and X3 represent single bond; and m is 1 and n is 1 in the general formula (1).

[0023] [6] The liquid crystalline compound recited in paragraph [1] above wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X2 represents —(CH2)4— or —(CH2)3O—; either X1 and X3 represent single bond; and m is 1 and n is 1 in the general formula (1).

[0024] [7] The liquid crystalline compound recited in paragraph [1] above wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X3 represents —(CH2)4— or —(CH2)3O—; either X1 and X2 represent single bond; and m is 1 and n is 1 in the general formula (1).

[0025] [8] A liquid crystal composition comprising at least two components and comprising at least one liquid crystalline compound expressed by the general formula (1) 4

[0026] wherein R1 represents an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X1, X2, and X3 independently represent —(CH2)4—, —(CH2)3O—, —O(CH2)3—, or single bond; Y1 represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

[0027] [9] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) 5

[0028] wherein R2 represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y2 represents fluorine atom, chlorine atom, —OCF3, —OCF2H, —CF3, —CF2H, —CFH2, —OCF2CF2H, or —OCF2CFHCF3; L1 and L2 independently represent hydrogen atom or fluorine atom; Z1 and Z2 independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF2O—, —OCF2—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope.

[0029] [10] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) 6

[0030] wherein R3 and R4 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y3 represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z3 represents 1,2-ethylene group, —COO—, or single bond; L3, L4, and L5 independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope.

[0031] [11] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) 7

[0032] wherein R5 and R6 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z4 and Z5 independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡—C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

[0033] [12] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12) 8

[0034] wherein R7 and R8 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K and ring M independently represent trans-1,4-cyclohexylene or 1,4-phenylene; L6 and L7 independently represent hydrogen atom or fluorine atom, but in no case simultaneously represent L6 and L7 hydrogen atom; Z6 and Z7 independently represent —CH2CH2—, —COO—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

[0035] [13] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12) described above.

[0036] [14] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[0037] [15] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[0038] [16] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a fourth component, at least one component selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[0039] [17] A liquid crystal composition comprising at least one optically active compound in addition to the liquid crystal composition recited in any one of paragraphs [8] to [16] above.

[0040] [18] A liquid crystal display device fabricated by using the liquid crystal composition recited in any one of paragraphs [8] to [17] above.

[0041] Liquid crystalline compounds of the present invention expressed by the general formula (1) are two to four rings compounds having butylene group or propylenoxy group, and 2,3-difluorophenyl group at the same time in the molecular structure. As a matter of course, these liquid crystalline compounds are extremely stable physically and chemically under the environment in which liquid crystal display devices are used, and the compounds are characterized in that they are wide in temperature range exhibiting a liquid crystal phase, excellent in solubility in liquid crystal compositions even at low temperatures, and low in viscosity, and have a negative and large &Dgr;&egr;.

[0042] As described in the section of BACKGROUND ART, whereas compounds having 2,3-difluoro-1,4-phenylene group as a partial structure are already disclosed in patent publications, it is a fact discovered for the first time by the present inventors that the compounds simultaneously having 1,4-butylene group or propylenoxy group as bonding group and 2,3-difluoro-1,4-phenylene group exhibit the characteristic described above, and it is difficult to expect such fact from conventional technology.

[0043] In the compounds of the present invention, it is possible to optionally adjust desired physical properties by selecting a proper ring structure, bonding group, and lateral structure among molecule constituting elements. Accordingly, novel liquid crystal compositions and liquid crystal display devices having excellent characteristics, specifically

[0044] 1) having a wide temperature range of liquid crystal phase,

[0045] 2) being low in viscosity, and having a negative and large &Dgr;&egr;,

[0046] 3) separating no crystals and developing no smectic phase even at very low temperatures,

[0047] 4) being physically and chemically stable, and being possible to expand the temperature range of their usage, to drive at a low voltage, and to realize a high speed response and high contrast

[0048] can be provided by using the compound of the present invention as component of liquid crystal compositions.

[0049] While any of the compounds of the present invention exhibits preferable physical properties, liquid crystal compositions having physical properties suitable for their use can be produced by using the compound which is expressed by the general formula (1) in which ring A1, ring A2, ring A3, X1, X2, X3, m, and n are properly selected.

[0050] That is, when compounds having a negative and large &Dgr;&egr; are necessary, it is sufficient to suitably select 2,3-difluoro-1,4-phenylene group for any one of ring A1, ring A2, ring A3, and when compounds having a high optical anisotropy value are necessary, it is sufficient to select compounds in which any one of ring A1, ring A2, and ring A3 is 1,4-phenylene group, and every one of X1, X2, and X3 is single bond. When compounds having their temperature range of liquid crystal phase at high temperature side are necessary, it is sufficient to suitably select three rings or four rings compounds, and when compounds having their temperature range of liquid crystal phase at low temperature side are necessary, it is sufficient to suitably select two rings compounds, respectively.

[0051] Compounds in which hydrogen atom on 1,4-phenylene group is replaced by fluorine atom exhibit an excellent solubility at low temperatures.

[0052] Compounds expressed by one of the following general formulas (1-1) to (1-12) can be mentioned as particularly preferable ones among the compounds expressed by the general formula (1): 9

[0053] wherein R1, ring A1, ring A2, ring A3, and Y1 have the same meaning as described above.

[0054] In the compounds described above, while R1 represents an alkoxy group, alkoxyalkyl group, alkenyl group, alkenyloxy group, alkenyloxyalkyl group, or alkyloxyalkenyl group having 1 to 15 carbon atoms, particularly preferable groups among them are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 4-pentynyloxy, methoxy-1-propenyl, methoxy-1-pentenyl, and methoxy-3-pentenyl.

[0055] In the compounds described above, while Y1 represents hydrogen atom, an alkyl group, alkoxy group, alkoxyalkyl group, alkenyl group, alkenyloxy group, alkenyloxyalkyl group, or alkyloxyalkenyl group having 1 to 15 carbon atoms, particularly preferable groups among them are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, and propoxypropyl.

[0056] Liquid crystal compositions of the present invention are described below. Liquid crystal compositions of the present invention preferably comprise at least one compound expressed by the general formula (1) in the ratio of 0.1 to 99.9% by weight to develop excellent characteristics.

[0057] More preferably, the liquid crystal compositions provided by the present invention are completed by mixing compounds selected from the group consisting of the compounds expressed by one of the general formulas (2) to (9) depending on the purposes of the liquid crystal compositions in addition to the first component comprising at least one compound expressed by the general formula (1).

[0058] The present invention recited in the paragraphs [12] and [13] above are concerned with N type (having a negative &Dgr;&egr;) liquid crystal compositions. In the same way as P type (having a positive &Dgr;&egr;) liquid crystal compositions, N type liquid crystal compositions can be driven by various driving modes, for example, by IPS mode (In Plane Switching Mode). The present invention recited in paragraphs [9], [10], [11], [14], [15], and [16] are concerned with P type liquid crystal compositions. It is possible to control elastic constants of liquid crystal compositions and to improve the miscibility of the compositions at low temperatures by adding a N type liquid crystalline compound to P type liquid crystal compositions.

[0059] Following compounds can preferably be mentioned as ones used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (2) to (4): 10

[0060] wherein R2 and Y2 have the same meaning as described above.

[0061] Compounds expressed by one of the general formulas (2) to (4) have a positive dielectric anisotropy value, are remarkably excellent in thermal stability and chemical stability, and are useful when liquid crystal compositions for TFT (AM-LCD) display mode of which a high reliability such as a particularly high voltage holding ratio or large specific resistivity is required are produced.

[0062] When the liquid crystal compositions for TFT display mode are produced, the compounds expressed by one of the general formulas (2) to (4) can be used in the range of 0.1 to 99.9% by weight based on the total amount of liquid crystal composition, and the amount is preferably 10 to 97% by weight and more desirably 40 to 95% by weight. Also, the compositions may further comprise the compound expressed by one of the general formulas (7) to (9) for the purpose of adjusting viscosity. Even when liquid crystal compositions for STN display mode or TN display mode are produced, the compound expressed by one of the general formulas (2) to (4) can be used. In this case, the amount of the compound to be used is preferably less than 50% by weight.

[0063] As the compound used in the liquid crystal compositions of the present invention expressed by the general formula (5) or (6), the following compounds can preferably be mentioned: 11

[0064] wherein R3, R4, and Y3 have the same meaning as described above.

[0065] Compounds expressed by one of the general formula (5) or (6) have a positive and large dielectric anisotropy value, and are used particularly for the purpose of lowering threshold voltage of liquid crystal compositions. Also, they are used for the purpose of adjusting optical anisotropy value, and widening nematic range such as raising clearing point. Further, they are used even for the purpose of improving the steepness of V-T curve of liquid crystal compositions for STN display mode or TN display mode.

[0066] Compounds expressed by the general formula (5) or (6) are useful when liquid crystal compositions particularly for STN display mode or TN display mode are produced.

[0067] When the content of the compound expressed by the general formula (5) or (6) in liquid crystal compositions is increased, threshold voltage of liquid crystal compositions lowers but viscosity increases. Accordingly, it is advantageous to use the compound in a large amount since driving at a low voltage becomes possible, so far as viscosity of liquid crystal compositions satisfies required characteristics.

[0068] When liquid crystal compositions for STN display mode or TN display mode are produced, the amount of the compound expressed by the general formula (5) or (6) to be used is in the range of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, and more desirably 40 to 95% by weight.

[0069] As the compounds used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (7) to (9), the following compounds can preferably be mentioned. 12

[0070] wherein R5 and R6 have the same meaning as described above.

[0071] Compounds expressed by one of the general formulas (7) to (9) have a small absolute value of dielectric anisotropy, and are close to neutral. Compounds expressed by the general formula (7) are used principally for the purpose of adjusting viscosity and adjusting optical anisotropy value of liquid crystal compositions. Compounds expressed by the general formula (8) or (9) are used for the purpose of widening nematic range such as raising clearing point, or for the purpose of adjusting optical anisotropy value.

[0072] When the content of the compound expressed by one of the general formulas (7) to (9) in liquid crystal compositions is increased, threshold voltage of liquid crystal compositions rises but viscosity reduces. Accordingly, it is desirable to use the compound in a large amount so far as threshold voltage of liquid crystal compositions satisfies required characteristics. When liquid crystal compositions for TFT are produced, the amount of the compound expressed by one of the general formulas (7) to (9) to be used is preferably less than 40% by weight and more desirably less than 35% by weight. When liquid crystal compositions for STN display mode or TN display mode are produced, the amount is preferably less than 70% by weight and more desirably less than 60% by weight.

[0073] As the compounds used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (10) to (12), the following compounds can preferably be mentioned: 13

[0074] wherein R7 and R8 have the same meaning as described above.

[0075] Compounds expressed by one of the general formulas (10) to (12) have a negative dielectric anisotropy value. Compounds expressed by the general formula (10) are two rings compounds, and are used principally for the purpose of adjusting threshold voltage, adjusting viscosity, or adjusting optical anisotropy value. Compounds expressed by the general formula (11) are used for the purpose of widening nematic range such as raising clearing point, or for the purpose of adjusting optical anisotropy value. Compounds expressed by the general formula (12) are used for the purpose of widening nematic range as well as for the purpose of lowering threshold voltage and for the purpose of increasing optical anisotropy value.

[0076] Compounds expressed by one of the general formulas (10) to (12) are used principally for N type (having a negative dielectric anisotropy &Dgr;&egr;) liquid crystal compositions. When the amount of the compound to be used is increased, threshold voltage of liquid crystal compositions lowers but viscosity increases. Accordingly, it is desirable to use the compound in a small amount so far as threshold voltage of liquid crystal compositions is satisfied. However, since these compounds have an absolute value of dielectric anisotropy value of lower than 5, when the amount of the compound used is less than 40% by weight, driving at a low voltage sometimes becomes impossible.

[0077] The amount of the compound expressed by one of the general formulas (10) to (12) to be used in liquid crystal compositions is preferably more than 40% by weight when liquid crystal compositions for N type TFT are produced and the amount is more desirably 50 to 95% by weight.

[0078] Further, for the purpose of control the elastic constants of liquid crystal compositions and regulating voltage-transmittance curve (V-T curve), the compound expressed by one of the general formulas (10) to (12) is sometimes added to P type (having positive dielectric anisotropy &Dgr;&egr;) liquid crystal compositions. In such case, the amount of the compound expressed by one of the general formulas (10) to (12) to be used in liquid crystal compositions is preferably less than 30% by weight.

[0079] With the exception of such specific cases as liquid crystal compositions for OCB (Optically Compensated Birefringence) mode and the likes, an optically active compound is usually added to the liquid crystal compositions of the present invention for the purpose of inducing helical structure of liquid crystal composition to adjust required twist angle and to prevent reverse twist. While any known optically active compounds used for such purposes can be added in the liquid crystal compositions of the present invention, the following optically active compounds can be mentioned as preferable examples: 14

[0080] These optically active compounds are usually added to liquid crystal compositions of the present invention to adjust their pitch of twist. The twist pitch is preferably adjusted in the range of 40 to 200 &mgr;m in the case of liquid crystal compositions for TFT or TN, and preferably adjusted in the range of 6 to 20 &mgr;m in the case of liquid crystal compositions for STN. In the case for bistable TN mode, it is preferable to adjust the pitch in the range of 1.5 to 4 &mgr;m. Further, two or more kind of optically active compounds may be added for the purpose of adjusting the dependency of the pitch length on temperature.

[0081] Liquid crystal compositions of the present invention can be produced by methods which are conventional by themselves. Generally, a method in which various components are dissolved one another at a high temperature has been adopted.

[0082] Further, the liquid crystal compositions of the present invention can be used as ones for guest-host (GH) mode by adding a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type, and tetrazine type thereto. Alternatively, the liquid crystal compositions can be used as NCAP which is prepared by the microencapsulation of a nematic liquid crystal, or as liquid crystal compositions for polymer dispersed liquid crystal display devices (PDLCD) represented by polymer net work liquid crystal display devices (PNLCD) prepared by forming a polymer of three-dimensional reticulated structure in a liquid crystal. Still further, the liquid crystal compositions of the present invention can be used as ones for electrically controlled birefringence (ECB) mode or dynamic scattering (DS) mode.

[0083] [Methods for producing compounds]

[0084] Compounds of the present invention expressed by the general formula (1) can readily be produced by using ordinary chemical procedures of organic synthesis. For instance, the compounds can readily be synthesized by selecting proper known reactions described in reference books such as Organic Synthesis, Organic Reactions, and Shin-Jikken Kagaku Kouza (Course of New Chemical Experiment), and magazines, and using the reactions in combination.

[0085] When butylene group is introduced at the position of a bonding group (X1, X2, and X3), the compounds can be produced, for instance, by the following reaction paths.

[0086] In the following, MSG1 and MSG2 independently represent a mesogen (a residue of organic compounds); Hal represents Cl, Br, or I; ring A represents trans-1,4-cyclohexylene group, 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group; and Y1 have the same meaning as described above.

[0087] That is, 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium halide (12) and aldehyde derivative (11) are subjected to the Wittig reaction in an ether type solvent such as tetrahydrofuran (hereinafter abbreviated to THF) and diethyl ether in the presence of a base such as sodium methylate, potassium-t-butoxide (t-BuOK), and butyl lithium to obtain compound (13). Subsequently, aldehyde derivative (14) can be obtained by subjecting compound (13) to hydrogen reduction in a mixed solvent of toluene/Solmix in the presence of a metal catalyst such as palladium/carbon and Raney nickel, and then reacting with a mineral acid such as hydrochloric acid and sulfuric acid, or an organic acid such as formic acid and p-toluenesulfonic acid.

[0088] Further, in the same way as that wherein compound (13) is obtained from compound (11), compound (16) can be obtained by subjecting compound (14) and compound (15) to the Wittig reaction, and aldehyde derivative (17) can be produced by reacting it with the same acid as described above. Subsequently, derivative (19) having butylene group can be produced by reacting Grignard reagent (18) with compound (17) to conduct Grignard reaction, reacting it with the same acid as described above to dehydrate, and further subjecting to hydrogen reduction by using the same metal catalyst as described above. 15

[0089] When propylenoxy group having ether bond is introduced at the position of a bonding group (X1, X2, and X3), the compounds can be produced, for instance, by the following reaction paths.

[0090] Aldehyde derivative (14) is reacted with lithium aluminum hydride in a solvent such as toluene, THF, and diethyl ether to reduce thereby to obtain alcohol derivative (20). This alcohol derivative (20) is reacted with hydrobromic acid to produce compound (21). Compound (23) having ether bond can be produced by reacting compound (21) with compound (22) in the presence of sodium hydride. 16

[0091] When 2,3-difluoro-1,4-phenylene group is introduced to aring structure portion, the compounds can be produced, for instance, by the following reaction paths.

[0092] a) The case wherein the introduction portion is located at position 4 relative to MSG1 of benzene derivative:

[0093] Compound (25) can be obtained by reacting difluorobenzene derivative (24) with n-butyl lithium or sec-butyl lithium in an ether type solvent such as THF and diethyl ether, reacting with zinc chloride, and then reacting with 2,3-difluoro-1-bromobenzene in the presence of a metal catalyst of palladium (0).

[0094] b) The case wherein it is introduced cyclohexanone derivative having MSG1 at position 4:

[0095] Compound (28) can be produced by reacting compound (26) with Grignard reagent (27) to conduct the Grignard reaction, dehydrating by the same procedure as described above, and then subjecting to hydrogen reduction. 17

[0096] Compounds in which ring A1, ring A2, and ring A3 are silacyclohexane rings can be produced according to the method disclosed in Laid-open Japanese Patent Publication No. Hei 7-70148, Laid-open Japanese Patent Publication No. 7-112990, and Laid-open Japanese Patent Publication Nol Hei 7-149770.

[0097] Compounds of the present invention expressed by the general formula (1) can be produced by selecting and using proper reactions described above.

[0098] Any of the liquid crystalline compounds of the present invention expressed by the general formula (1) thus obtained has such characteristics that the temperature range in which the compound exhibits a liquid crystal phase is wide, viscosity is low, and &Dgr;&egr; is negative and large, and the compound is readily mixed with other various liquid crystal materials even at low temperatures. Accordingly, the compound is remarkably excellent as constituent of nematic liquid crystal compositions suitable for TFT type display mode and IPS mode.

BEST MODE FOR CARRYING OUT THE INVENTION

[0099] Now, the present invention will be described in more detail with reference to Examples. However, it should be understood that the scope of the present invention is by no means restricted by such specific Examples. In the Examples, the structure of compounds was confirmed by nuclear magnetic resonance spectrum (hereinafter abbreviated to 1H-NMR) and mass spectrum (hereinafter abbreviated to MS). In the data of 1H-NMR in the Examples, t indicates triplet, q: quartet, M: multiplet, and J: coupling constant. In the data of MS, M+ indicates molecular ion peak. Further, C indicates crystal, SA: smectic phase A, SB: smectic phase B, N: nematic phase, and Iso: isotropic liquid phase, and the unit of every phase transition temperature is ° C.

EXAMPLE 1

[0100] Preparation of 2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the general formula (1) wherein R1 is pentyl group, ring A1 and ring A2 are trans-1,4-cyclohexylene group, X1 is butylene group, X2 is single bond, Y1 is propyl group, m is 1, n is 0 (Compound No. 20)]

[0101] First step

[0102] Under nitrogen gas stream, 52.3 g (2150 mmol) of magnesium was added in 100 ml of THF, and a solution of 378 g (1960 mmol) of 2,3-difluoro-1-bromobenzene in 4.0 l of THF was added by drops thereto so that the reaction temperature was maintained at about 50° C. Further, after stirred at room temperature for 1 hour, a solution of 500 g (1630 mmol) of 4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexanone in 5.0 l of THF was added by drops to the solution and stirred at 50 to 60° C. for 2 hours, and then 1.0 l of saturated aqueous ammonium chloride solution was added to the solution to terminate the reaction. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and then it was extracted with 2.0 l of toluene. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was removed by filtration, 23.7 g of p-toluenesulfonic acid monohydrate was added to the filtrate and heated to reflux for 4 hours. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 436 g of a crude 1,2-difluoro-3-(4-(4-(trans-4-pentylcyclohexyl)-butyl)cyclohexene-1-yl)benzene.

[0103] Second step

[0104] In 4.0 l of mixed solvent of toluene/Solmix (1/1) was dissolved 436 g (1080 mmol) of the crude product obtained by the procedures described above, 21.8 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm2 for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) and recrystallized from heptane twice to obtain 114 g of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene.

[0105] Third step

[0106] Under nitrogen gas stream, a solution prepared by dissolving 30.0 g (74.1 mmol) of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene in 300 ml of THF was cooled down to −70° C., 88.9 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and stirred at the same temperature for further 2 hours. Subsequently, a suspension prepared by adding 9.98 g (88.9 mmol) of t-BuOK to 100 ml of THF was added by drops to the reaction liquid while being maintained at the same temperature, and stirred at the same temperature for further 1 hour. To the reaction liquid was added by drops a solution of 15.1 g (88.9 mmol) of propyliodide in 150 ml of THF while being maintained at the same temperature and stirred at the same temperature for 5 hours. The reaction was terminated by adding 200 ml of water to the reaction mixture, and the solvent was distilled off under a reduced pressure. Concentrated residue was extracted with 500 ml of toluene, and the organic layer was washed with 200 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain a crude 2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene. This crude product was recrystallized from heptane thrice to obtain 5.40 g (yield 2.82%) of the subject compound.

[0107] Phase transition temperature: C 40.2 SB 90.9 N 98.0 Iso

[0108] 1H-NMR: &dgr;: (ppm): 0.50˜2.10 (m, 45H), 2.59 (t, 1H, J=7.3 Hz), 6.70˜7.10 (m, 2H)

[0109] MS: m/e=446 (M+)

EXAMPLE 2

[0110] Preparation of 1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the general formula (1) wherein R1 is pentyl group, either ring A1 and ring A2 are trans-1,4-cyclohexylene group, X1 is butylene group, X2 is single bond, Y1 is ethoxy group, m is 1, and n is 0 (Compound No. 23)]

[0111] First step

[0112] Under nitrogen gas stream, a solution of 60.0 g (148 mmol) of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)-cyclohexyl)benzene in 600 ml of THF was cooled down to −70° C., 178 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and stirred at the same temperature for 2 hours. Subsequently, a solution of 30.8 g (296 mmol) of trimethyl borate in 300 ml of THF was added by drops thereto while being at the same temperature, and stirred at the same temperature for further 2 hours. After the reaction temperature was gradually raised up to room temperature, 88.9 g (1480 mmol) of acetic acid was added, 134 g (1180 mmol) of 30% hydrogen peroxide was added by drops, and then stirred at room temperature for 3 hours. The reaction was terminated by adding 300 ml of saturated aqueous sodium thiosulfate solution to the reaction mixture, and the solvent was distilled off under a reduced pressure.

[0113] Concentrated residue was extracted with 500 ml of toluene and 100 ml of diethyl ether, the organic layer was washed with 150 ml of saturated aqueous sodium thiosulfate solution twice and with 200 ml of water thrice, and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was recrystallized from toluene to obtain 40.0 g of 2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)phenol.

[0114] Second step

[0115] In 400 ml of N,N-dimethyl formamide (hereinafter abbreviated to DMF), was dissolved 40.0 g (95.1 mmol) of 2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)phenol, and heated on a water bath up to 50° C. Oily 55% sodium hydride in an amount of 4.97 g (114 mmol) was added thereto, stirred at the same temperature for 10 minutes, and a solution of 15.5 g (142 mmol) of ethyl bromide in 150 ml of DMF was added by drops. After finishing of the dropping, the reaction temperature was raised up to 80° C., and stirred at the same temperature for 5 hours. After cooled down to room temperature, the reaction was terminated by adding 500 ml of water to the reaction mixture, and it was extracted with 1.0 l of toluene. The organic layer was washed with 500 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain a crude 1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)-butyl)cyclohexyl)benzene. This crude product was recrystallized from heptane twice and from mixed solvent of heptane/ethanol (6/1) once to obtain 10.3 g (yield 15.5%) of the subject compound.

[0116] Phase transition temperature: C 79.2 SA 94.5 N 125.5 Iso

[0117] 1H-NMR: &dgr;: (ppm): 0.50˜2.05 (m, 41H), 2.73 (t, 1H, J=7.3 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50˜7.00 (m, 2H)

[0118] MS: m/e =448 (M+)

EXAMPLE 3

[0119] Preparation of 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene [Compound expressed by the general formula (1) wherein R1 is propyl group, either ring A1 and ring A2 are trans-1,4-cyclohexylene group, X1 is a covalent bond, X2 is butylene group, Y1 is ethoxy group, m is 1, and n is 0 (Compound No. 94)]

[0120] First step

[0121] Under nitrogen gas stream, a mixture of 1330 g (2930 mmol) of 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide with 6.0 l of THF was cooled down to −30° C., and 303 g (2700 mmol) of t-BuOK was added thereto and stirred for 1 hour. To this mixture was added by drops a solution of 500 g (2250 mmol) of 4-(trans-4-propylcyclohexyl)cyclohexanone in 3.0 l of THF while being maintained at a temperature lower than −30° C. After finishing of the adding, the reaction temperature was gradually raised up to room temperature and they were stirred for further 5 hours. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of toluene/ethyl acetate=9/1) to obtain 652 g of a crude 2-(2-(4-(trans-4-propylcyclohexyl)-cyclohexylidene)-ethyl-1,3-dioxane.

[0122] Second step

[0123] In 6.5 l of mixed solvent of toluene/Solmix (1/1) was dissolved 652 g (2030 mmol) of the crude product obtained by the procedures described above, 32.6 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm2 for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: toluene) and recrystallized from heptane to obtain 366 g of 2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)-1,3-dioxane.

[0124] Third step

[0125] In 3.0 l of toluene was dissolved 300 g (930 mmol) of the 2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)-1,3-dioxane obtained by the procedures described above, 428 g (9300 mmol) of formic acid was added thereto, and they were heated to reflux for 4 hours. The reaction mixture was washed with 600 ml of saturated aqueous sodium bicarbonate solution twice and with 1.0 l of water five times, and the solvent was distilled off under a reduced pressure to obtain 240 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propanal.

[0126] Fourth step

[0127] Under nitrogen gas stream, a mixture of 405 g (1180 mmol) of methoxymethyltriphenyl-phosphonium chloride with 4.0 ml of THF was cooled down to −30° C., 122 g (1090 mmol) of t-BuOK was added thereto, and they were stirred for 1 hour. To this mixture was added by drops a solution of 240 g (907 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-propanal in 2.4 l of THF while being maintained at a temperature lower than −30° C. After finishing of the dropping, the reaction temperature was gradually raised up to room temperature, and the mixture was stirred for further 5 hours. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 152 g of a crude 1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butene.

[0128] Fifth step

[0129] In 500 ml of toluene was dissolved 50.0 g (171 ml ) of the crude 1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butene obtained by the procedures in the fourth step, 78.7 g (1710 mmol) of formic acid was added thereto, and then they were heated to reflux for 4 hours. The reaction mixture was washed with 300 ml of saturated aqueous sodium bicarbonate solution twice and with 500 ml of water five times, and the solvent was distilled off under a reduced pressure to obtain 45.1 g of a crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal.

[0130] Sixth step

[0131] Under nitrogen gas stream, a solution of 30.7 g (194 mmol) of 1-ethoxy-2,3-difluorobenzene in 300 ml of THF was cooled down to −70° C., 194 ml of sec-butyl lithium (1.0M cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and they were stirred at the same temperature for 2 hours. To this reaction mixture was added by drops a solution of 45.1 g (162 mmol) of the crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal obtained by the reaction in the fifth step in 450 ml of THF while being maintained at the same temperature, and stirred for 2 hours. Subsequently, they were raised up to −50° C. and stirred for 2 hours. The reaction mixture was added to 200 ml of water to terminate the reaction, the solvent was distilled off under a reduced pressure, the residue was extracted with 500 ml of toluene, and the organic layer was washed with 100 ml of water thrice, and then dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was removed by filtration, 2.83 g of p-toluenesulfonic acid monohydrate was added to the filtrate, and heated to reflux for 4 hours. The organic layer was washed with 200 ml of water thrice and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain 50.2 g of a crude 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-butenyl)benzene.

[0132] Seventh step

[0133] In 500 ml of mixed solvent of toluene/Solmix (1/1) was dissolved 50.2 g (120 mmol) of the crude product obtained by the procedures described above, 15.1 g of 5% by weight-palladium/carbon catalyst was added thereto, and they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm2 for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene. This crude product was recrystallized from heptane twice to obtain 24.3 g (yield 9.90%) of the subject compound.

[0134] Phase transition temperature: C 44.4 SA 107.2 N 129.0 Iso

[0135] 1H-NMR: &dgr;: (ppm): 0.45˜2.10 (m, 36H), 2.58 (t, 2H, J=7.0 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50˜7.00 (m, 2H)

[0136] MS: m/e =420 (M+)

EXAMPLE 4

[0137] Preparation of 3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether [Compound expressed by the general formula (1) wherein R1 is propyl group, either ring A1 and ring A2 are trans-1,4-cyclohexylene group, ring A3 is 2,3-difluoro-1,4-phenylene group, either X1 and X3 are single bond, X2 is propyloxylene group, Y1 is pentyl group, m is 1, and n is 1 (Compound No. 237)]

[0138] First step

[0139] Under nitrogen gas stream, a solution of 400 g (1510 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-propanal obtained in the same manner as in the third step in Example 1 in 2.0 a of THF was added by drops to a mixture which was prepared by adding 43.0 g (1130 mmol) of lithium aluminum hydride to 400 ml of THF cooled down to a temperature lower than 5° C., while being maintained at the same temperature. After finishing of the adding, they were stirred at room temperature for 6 hours. This reaction mixture was gradually added to 500 ml of 2N aqueous sodium hydroxide solution and stirred at 50° C. for 30 minutes. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was extracted with 2.0 l of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under a reduced pressure to obtain 341 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-propanol.

[0140] Second step

[0141] To 350 ml of xylene were added 341 g (1280 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanol obtained by the procedures described above and 881 g (5120 mmol) of 47% hydrobromic acid, water was removed by azeotropic distillation, and then the mixture was stirred at 150° C. for 2 hours. To the reaction mixture was added 1.0 l of toluene, and it was washed with 300 ml of saturated aqueous sodium carbonate solution twice and with 400 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 156 g of a crude 1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propane.

[0142] Third step

[0143] Under nitrogen gas stream, 29.8 g (683 mmol) of 55% sodium hydride was added to 100 ml of DMF and cooled with water, a solution of 74.0 g (569 mmol) of 2,3-difluorophenol in 700 ml of DMF was added by drops thereto, and they were stirred for 1 25 hour. To the reaction mixture was added by drops a solution of 156 g (474 mmol) of the crude 1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propane in 400 ml of mixed solvent of DMF/toluene (3/1), and then they were stirred at 80° C. for 3 hours. The reaction mixture was added to 500 ml of water to terminate the reaction, and the organic layer was separated, washed with 500 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) and recrystallized from heptane to obtain 101 g of 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluorophenyl ether.

[0144] Fourth step

[0145] Under nitrogen gas stream, 101 g (267 mmol) of the 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluorophenyl ether obtained by the procedures described above was dissolved in 1.0 l of THF and cooled down to −70° C. To this solution was added by drops 320 ml of sec-butyl lithium (1.0M, cyclohexane solution) while being maintained at the same temperature, and stirred at the same temperature for 2 hours. To the reaction mixture was added by drops 640 ml of zinc chloride (0.5M, THF solution), and stirred at the same temperature for 1 hour, the reaction temperature was gradually raised up to room temperature, and they were stirred for 1 hour. To the reaction mixture was added 1.00 g of tetrakis-(triphenylphosphine)palladium (0), and a solution of 61.8 g (15.9 mmol) of 2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops thereto, and heated to reflux for 3 hours. The reaction mixture was added to 1.0 l of water to terminate the reaction, the solvent was distilled off under a reduced pressure, and the residue was extracted with 3.0 l of toluene. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: toluene) to obtain 55.3 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether.

[0146] Fifth step

[0147] Under nitrogen gas stream, a solution prepared by dissolving 55.3 g (112 mmol) of the 3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether obtained by the procedures described above in 550 ml of THF was cooled down to −70° C., and 134 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hours. To the reaction mixture added by drops a suspension which was prepared by adding 15.0 g (134 mmol) of t-BuOK to 150 ml of THF, while being maintained at the same temperature, and stirred at the same temperature for further 1 hour. To the reaction mixture was added by drops a solution of 26.5 g (134 mmol) of pentyliodide in 300 ml of THF while being maintained at the same temperature and stirred at the same temperature for 5 hours. The reaction mixture was added to 300 ml of water to terminate the reaction, and the solvent was distilled off under a reduced pressure. The residue was extracted with 700 ml of toluene, and the organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 3-(trans-4-(trans-4-propylcyclohexyl)-propyl 2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether. This crude product was recrystallized from heptane twice and from mixed solvent of heptane/ethanol (4/1) once to obtain 10.2 to g (yield 1.21%) of the subject compound.

[0148] MS: m/e =560 (M+)

EXAMPLE 5

[0149] Preparation of 1-ethoxy-2,3-difluoro-4-(2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)-benzene [Compound expressed by the general formula (1) wherein R1 is propyl group, either ring A1 and ring A2 are trans-1,4-cyclohexylene group, ring A3 is 2,3-difluoro-1,4-phenylene group, either X1 and X3 are single bond, X2 is butylene group, Y1 is ethoxy group, m is 1, and n is 1 (Compound No. 238)]

[0150] First step

[0151] Under nitrogen gas stream, 8.05 g (331 mmol) of magnesium was added to 20.0 ml of THF, and a solution of 58.1 g (301 mmol) of 2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops thereto so that the reaction temperature was maintained at about 50° C. and then stirred at room temperature for 1 hour. To the reaction solution was added by drops a solution of 70.0 g (251 mmol) of the crude 4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butanal obtained by the same manner as in the fifth step of Example 1 in 700 ml of THF, stirred at 50 to 60° C. for 2 hours, and then 200 ml of saturated aqueous ammonium chloride solution was added thereto to terminate the reaction. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and then the residue was extracted with 700 ml of toluene. The organic layer was washed with 400 ml of water thrice and then dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was filtered off, 3.56 g of p-toluenesulfonic acid monohydrate was added to the filtrate, and heated to reflux for 4 hours. The organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 63.5 g of a crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-butenyl)benzene.

[0152] Second step

[0153] To 600 ml of mixed solvent of toluene/Solmix (1/1) was dissolved 63.5 g (170 mmol) of the crude product obtained by the procedures described above, 3.18 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm2 for 6 hours. After the catalyst was removed from the reaction mixture by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 60.0 g of a crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene.

[0154] Third step

[0155] Under nitrogen gas stream, 60.0 g (159 mmol) of the crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butyl)benzene was dissolved in 600 ml of THF, cooled down to −70° C., and 191 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hours. To the reaction mixture was added by drops a solution of 60.7 g (239 mmol) of iodine in 600 ml of THF while being maintained at the same temperature, the reaction temperature was gradually raised up to room temperature, and then they were stirred for 30 minutes. The reaction mixture was added to 300 ml of saturated aqueous sodium thiosulfate solution to terminate the reaction, and the solvent was distilled off under a reduced pressure. The residue was extracted with 700 ml of toluene, and the organic layer was washed with 300 ml of saturated aqueous sodium thiosulfate solution twice and 200 ml of saturated aqueous sodium carbonate solution once, and 300 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 72.5 g of a crude 2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)butyl)benzene.

[0156] Fourth step

[0157] Under nitrogen gas stream, a solution prepared by dissolving 9.46 g (59.8 mmol) of 2,3-difluoro-1-ethoxybenzene in 100 ml of THF was cooled down to −70° C., and 59.8 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hors. To the reaction mixture was added by drops 120 ml of zinc chloride (0.5M, THF solution), stirred at the same temperature for 1 hour, the reaction temperature was gradually raised up to room temperature, and they were stirred for further 1 hour. To the reaction mixture was added 1.00 g of tetrakis(triphenylphosphine)palladium (0), and a solution of 25.0 g (49.8 mmol) of the crude 2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-butyl)benzene in 250 ml of THF was added by drops thereto and heated to reflux for 3 hours. The reaction mixture was added to 200 ml of water to terminate the reaction, the solvent was distilled off under a reduced pressure, and the concentrated residue was extracted with 500 ml of toluene. The organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 1-ethoxy-2,3-difluoro-4-(2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)benzene. This crude product was recrystallized from heptane once and from mixed solvent of heptane/ethanol (5/1) once to obtain 13.1 g (yield 28.3%) of the subject compound.

[0158] Phase transition temperature: C 89.5 N 193.2 Iso

[0159] 1H-NMR: &dgr;: (ppm): 0.40˜2.10 (m, 36H), 2.70 (t, 2H, J=6.9 Hz), 4.17 (q, 2H, J=7.2 Hz), 6.60˜7.20 (m, 4H)

[0160] MS: m/e =532 (M+)

[0161] Following the methods of Example 1 to 5, the following compounds can be prepared: 1 R1 18 19 20 m n Y1 1 C3H7 21 0 0 C5H11 2 C5H11 22 0 0 C7H15 3 C7H15 23 0 0 C3H7 4 C3H7 24 0 0 OC2H5 5 C5H11O 25 0 0 OC4H9 6 C5H11 26 0 0 OC2H5 7 C3H7 27 0 0 C3H7 8 C5H11 28 0 0 C7H15 9 C7H15 29 0 0 C5H11 10 30 31 0 0 OC4H9 11 C5H11 32 0 0 OC2H5 12 C7H15 33 0 0 OCH3 13 C3H7 34 0 0 C7H15 14 C5H11 35 0 0 C5H11 15 C7H15 36 0 0 C3H7 16 C3H7 37 0 0 OC2H5 17 C5H11 38 0 0 OC4H9 18 C3H7O 39 0 0 OC5H11 19 C3H7 40 41 1 0 C5H11 20 C5H11 42 43 1 0 C3H7 C 40.2 SB 90.9 N 98.0 Iso 21 C3H7O 44 45 1 0 C7H15 22 C3H7 46 47 1 0 OC4H9 23 C5H11 48 49 1 0 OC2H5 C 79.2 SA 94.5 N 125.5 Iso 24 C7H15 50 51 1 0 OCH3 25 C3H7 52 53 1 0 C7H15 26 C5H11 54 55 1 0 C5H11 27 C7H15 56 57 1 0 C3H7 28 C3H7 58 59 1 0 OC4H9 29 C5H11 60 61 1 0 OC2H5 30 C5H11O 62 63 1 0 OCH3 31 C3H7 64 65 1 0 C5H11 32 C5H11 66 67 1 0 C3H7 33 68 69 70 1 0 CH3 34 C3H7 71 72 1 0 OC4H9 35 C5H11 73 74 1 0 OC2H5 36 C7H15 75 76 1 0 OC3H7 37 C3H7 77 78 1 0 C3H7 38 C5H11 79 80 1 0 C5H11 39 C2H5 81 82 1 0 C5H11 40 C3H7 83 84 1 0 OC4H9 41 C5H11 85 86 1 0 OC2H5 42 C6H13O 87 88 1 0 OCH3 43 C3H7 89 90 1 0 C5H11 44 C5H11 91 92 1 0 C3H7 45 C2H5O 93 94 1 0 C7H15 46 C3H7 95 96 1 0 OC2H5 47 C5H11 97 98 1 0 OC4H9 48 C7H15 99 100 1 0 OCH3 49 C3H7 101 102 1 0 C3H7 50 C5H11 103 104 1 0 C5H11 51 105 106 107 1 0 C2H5 52 C3H7 108 109 1 0 OC4H9 53 C5H11 110 111 1 0 OC3H7 54 C7H15 112 113 1 0 OC2H5 55 C5H11 114 115 1 0 C3H7 56 C3H7 116 117 1 0 C5H11 57 C5H11O 118 119 1 0 C3H7 58 C3H7 120 121 1 0 OC2H5 59 C5H11 122 123 1 0 OC4H9 60 124 125 126 1 0 OC3H7 61 C3H7 127 128 1 0 C7H15 62 C5H11 129 130 1 0 C3H7 63 C7H15 131 132 1 0 C5H11 64 C3H7 133 134 1 0 OC2H5 65 C5H11 135 136 1 0 OC4H9 66 137 138 139 1 0 OCH3 67 C3H7 140 141 1 0 C5H11 68 C5H11 142 143 1 0 C3H7 69 C7H15 144 145 1 0 C2H5 70 C3H7 146 147 1 0 OC2H9 71 C5H11 148 149 1 0 OC3H7 72 C7H15 150 151 1 0 OC4H9 73 C3H7 152 153 1 0 C3H7 74 C5H11 154 155 1 0 C5H11 75 C5H11 156 157 1 0 C3H7 76 C3H7 158 159 1 0 OC2H5 77 C3H7 160 161 1 0 OC3H7 78 C7H15 162 163 1 0 OC3H7 79 C3H7 164 165 1 0 C5H11 80 C5H11 166 167 1 0 C3H7 81 C7H15 168 169 1 0 C5H11 82 C3H7 170 171 1 0 OC2H5 83 C5H11 172 173 1 0 OC4H9 84 174 175 176 1 0 OC2H5 85 C3H7 177 178 1 0 C3H7 86 C5H11 179 180 1 0 C5H11 87 C5H11 181 182 1 0 C3H7 88 C3H7 183 184 1 0 OC2H5 89 C5H11 185 186 1 0 OC4H9 90 C7H15 187 188 1 0 OC2H5 91 C3H7 189 190 1 0 C3H7 92 C5H11 191 192 1 0 C3H7 93 193 194 195 1 0 C5H11 94 C3H7 196 197 1 0 OC2H5 C 44.4 SA 107.2 N 129.0 Iso 95 C5H11 198 199 1 0 OC4H9 96 C5H11 200 201 1 0 OC2H5 97 C3H7 202 203 1 0 C3H7 98 C5H11O 204 205 1 0 C5H11 99 C7H15 206 207 1 0 C7H15 100 C3H7 208 209 1 0 OC4H9 101 C5H11 210 211 1 0 OC2H5 102 C5H11 212 213 1 0 OC3H7 103 C3H7 214 215 1 0 C5H11 104 C5H11 216 217 1 0 C3H7 105 C7H15 218 219 1 0 CH3 106 C3H7 220 221 1 0 OC2H5 107 C5H11 222 223 1 0 OC4H9 108 C2H5O 224 225 1 0 OCH3 109 C3H7 226 227 1 0 C3H7 110 C5H11 228 229 1 0 C5H11 111 C5H11 230 231 1 0 C3H7 112 C3H7O 232 233 1 0 OC4H9 113 C5H11 234 235 1 0 OC2H5 114 C7H15 236 237 1 0 OCH3 115 C3H7 238 239 1 0 C7H15 116 C5H11 240 241 1 0 C3H7 117 242 243 244 1 0 C5H11 118 C3H7 245 246 1 0 OC2H5 119 C5H11O 247 248 1 0 OC4H9 120 C5H11 249 250 1 0 OC3H7 121 C3H7 251 252 1 0 C5H11 122 C5H11 253 254 1 0 C3H7 123 C7H15 255 256 1 0 C2H5 124 257 258 259 1 0 OC2H5 125 C5H11 260 261 1 0 OC4H9 126 C7H15 262 263 1 0 OC3H7 127 C3H7 264 265 1 0 C4H9 128 C5H11 266 267 1 0 C3H7 129 C5H11O 268 269 1 0 C5H11 130 C5H11 270 271 1 0 OC4H9 131 C5H11 272 273 1 0 OC2H5 132 C7H15 274 275 1 0 OCH3 133 C3H7 276 277 1 0 C3H7 134 C5H11 278 279 1 0 C2H5 135 C7H15 280 281 1 0 C5H11 136 C3H7 282 283 1 0 OC2H5 137 C5H11 284 285 1 0 OC4H9 138 C5H11 286 287 1 0 OC3H7 139 C3H7 288 289 1 0 C5H11 140 290 291 292 1 0 C3H7 141 C3H7O 293 294 1 0 C7H15 142 C3H7 295 296 1 0 OC2H5 143 C5H11 297 298 1 0 OC3H7 144 C7H15 299 300 1 0 OC4H9 145 C3H7 301 302 303 1 1 C5H11 146 C5H11 304 305 306 1 1 C3H7 147 C3H7O 307 308 309 1 1 C7H15 148 C3H7 310 311 312 1 1 OC4H9 149 C5H11 313 314 315 1 1 OC2H5 150 316 317 318 319 1 1 OCH3 151 C3H7 320 321 322 1 1 C7H15 152 C5H11 323 324 325 1 1 C5H11 153 C7H15 326 327 328 1 1 C3H7 154 C3H7 329 330 331 1 1 OC4H9 155 C5H11 332 333 334 1 1 OC2H5 156 C7H15 335 336 337 1 1 OCH3 157 C3H7 338 339 340 1 1 C2H5 158 C5H11 341 342 343 1 1 C3H7 159 C5H11O 344 345 346 1 1 C5H11 160 C3H7 347 348 349 1 1 OC2H5 161 C5H11 350 351 352 1 1 OC4H9 162 C7H15 353 354 355 1 1 OC3H7 163 C3H7 356 357 358 1 1 C3H7 164 C5H11 359 360 361 1 1 C5H11 165 C3H7 362 363 364 1 1 C7H15 166 365 366 367 368 1 1 OCH3 167 C5H11 369 370 371 1 1 OC2H5 168 C7H15 372 373 374 1 1 OC3H7 169 C3H7 375 376 377 1 1 C7H15 170 C5H11 378 379 380 1 1 C5H11 171 C7H15 381 382 383 1 1 C3H7 172 C3H7 384 385 386 1 1 OC4H9 173 C5H11O 387 388 389 1 1 OC2H5 174 C7H15 390 391 392 1 1 OC3H7 175 C3H7O 393 394 395 1 1 C2H5 176 C5H11 396 397 398 1 1 C3H7 177 C5H11 399 400 401 1 1 C5H11 178 C3H7 402 403 404 1 1 OC2H5 179 C5H11 405 406 407 1 1 OC3H7 180 C3H7O 408 409 410 1 1 OC4H9 181 C3H7 411 412 413 1 1 C3H7 182 C5H11 414 415 416 1 1 C7H15 183 417 418 419 420 1 1 C5H11 184 C3H7O 421 422 423 1 1 OCH3 185 C5H11 424 425 426 1 1 OC2H5 186 C7H15 427 428 429 1 1 OC3H7 187 C3H7 430 431 432 1 1 C7H15 188 C5H11 433 434 435 1 1 C5H11 189 C7H15 436 437 438 1 1 C3H7 190 C3H7 439 440 441 1 1 OC4H9 191 C5H11 442 443 444 1 1 OC2H5 192 C7H15 445 446 447 1 1 OC3H7 193 C3H7 448 449 450 1 1 C2H5 194 C5H11O 451 452 453 1 1 C3H7 195 C5H11 454 455 456 1 1 C5H11 196 C3H7 457 458 459 1 1 OC2H5 197 C5H11 460 461 462 1 1 OC3H7 198 C3H7O 463 464 465 1 1 OC4H9 199 C3H7 466 467 468 1 1 C7H15 200 C5H11 469 470 471 1 1 C3H7 201 472 473 474 475 1 1 C5H11 202 C3H7 476 477 478 1 1 OC3H7 203 C5H11 479 480 481 1 1 OC2H5 204 C7H15 482 483 484 1 1 OC4H9 205 C3H7 485 486 487 1 1 C7H15 206 C5H11O 488 489 490 1 1 C5H11 207 C7H15 491 492 493 1 1 C3H7 208 C3H7 494 495 496 1 1 OC2H5 209 C5H11 497 498 499 1 1 OCH3 210 C7H15 500 501 502 1 1 OC3H7 211 C3H7 503 504 505 1 1 C2H5 212 C5H11 506 507 508 1 1 C3H7 213 C3H7O 509 510 511 1 1 C5H11 214 C5H11 512 513 514 1 1 OC2H5 215 C5H11 515 516 517 1 1 OC4H9 216 C3H7O 518 519 520 1 1 OC3H7 217 C3H7 521 522 523 1 1 C3H7 218 C5H11 524 525 526 1 1 C3H7 219 527 528 529 530 1 1 C5H11 220 C5H11 531 532 533 1 1 OC2H5 221 C5H11 534 535 536 1 1 OC3H7 222 C5H11 537 538 539 1 1 OC4H9 223 C3H7 540 541 542 1 1 C3H7 224 C5H11O 543 544 545 1 1 C5H11 225 C7H15 546 547 548 1 1 C7H15 226 C3H7 549 550 551 1 1 OC4H9 227 C5H11 552 553 554 1 1 OC2H5 228 C5H11 555 556 557 1 1 OC3H7 229 C3H7 558 559 560 1 1 C5H11 230 C5H11O 561 562 563 1 1 C3H7 231 C7H15 564 565 566 1 1 CH3 232 C3H7 567 568 569 1 1 OC2H5 233 C5H11 570 571 572 1 1 OC4H9 234 C2H5O 573 574 575 1 1 OCH3 235 C3H7 576 577 578 1 1 C3H7 236 C5H11 579 580 581 1 1 C3H7 237 C3H7 582 583 584 1 1 C5H11 238 C3H7 585 586 587 1 1 OC2H5 C 89.5 N 193.2 Iso 239 C5H11 588 589 590 1 1 OC3H7 240 591 592 593 594 1 1 OC4H9 241 C3H7 595 596 597 1 1 C3H7 242 C5H11O 598 599 600 1 1 C5H11 243 C7H15 601 602 603 1 1 C7H15 244 C3H7 604 605 606 1 1 OC3H7 245 C5H11 607 608 609 1 1 OC2H5 246 C5H11 610 611 612 1 1 OC4H9 247 C3H7 613 614 615 1 1 C5H11 248 C5H11O 616 617 618 1 1 CH3 249 C7H15 619 620 621 1 1 C3H7 250 C3H7 622 623 624 1 1 OCH3 251 C5H11 625 626 627 1 1 OC2H5 252 C2H5O 628 629 630 1 1 OC4H9 253 C3H7 631 632 633 1 1 C3H7 254 C5H11 634 635 636 1 1 CH3 255 637 638 639 640 1 1 C5H11 256 C3H7 641 642 643 1 1 OC2H5 257 C5H11 644 645 646 1 1 OC3H7 258 C5H11 647 648 649 1 1 OC4H9 259 C3H7 650 651 652 1 1 C3H7 260 C5H11 653 654 655 1 1 C5H11 261 C7H15 656 657 658 1 1 C7H15 262 C3H7 659 660 661 1 1 OC2H5 263 C5H11 662 663 664 1 1 OC3H7 264 C5H11O 665 666 667 1 1 OC4H9 265 C3H7 668 669 670 1 1 C5H11 266 C5H11O 671 672 673 1 1 C3H7 267 C7H15 674 675 676 1 1 C3H7 268 C3H7O 677 678 679 1 1 OCH3 269 C5H11 680 681 682 1 1 OC4H9 270 C2H5 683 684 685 1 1 OC2H5 271 C2H5 686 687 688 1 1 C3H7 272 C5H11 689 690 691 1 1 C3H7 273 692 693 694 695 1 1 C7H15 274 C3H7 696 697 698 1 1 OC2H5 275 C5H11 699 700 701 1 1 OC3H7 276 C7H15 702 703 704 1 1 OC4H9 277 C3H7 705 706 707 1 1 C3H7 278 C5H11 708 709 710 1 1 C5H11 279 C7H15 711 712 713 1 1 CH3 280 C5H11O 714 715 716 1 1 OC2H5 281 C5H11 717 718 719 1 1 OC4H9 282 C3H7 720 721 722 1 1 OC3H7 283 C3H7 723 724 725 1 1 C5H11 284 C5H11O 726 727 728 1 1 C3H7 285 C5H11 729 730 731 1 1 C5H11 286 C3H7O 732 733 734 1 1 OC4H9 287 C3H7 735 736 737 1 1 OCH3 288 C5H11 738 739 740 1 1 OC2H5 289 C3H7 741 0 0 C3H7 290 C5H11 742 0 0 OC2H5 291 C3H7O 743 0 0 OC3H7 292 C3H7 744 0 0 C3H7 293 C5H11 745 0 0 OC2H5 294 C7H15 746 0 0 OCH3 295 C3H7 747 0 0 C7H15 296 C2H5O 748 0 0 C5H11 297 C5H11 749 0 0 OC4H9 298 750 751 0 0 OC4H9 299 C5H11 752 0 0 C3H7 300 C5H11O 753 0 0 OCH3 301 C3H7 754 0 0 OC2H5 302 C5H11 755 0 0 C3H7 303 C3H7 756 0 0 CH3 304 C3H7 757 0 0 C5H11 305 C5H11 758 0 0 OC2H5 306 C7H15O 759 0 0 OC3H7 307 C3H7 760 761 1 0 C5H11 308 C5H11O 762 763 1 0 OC2H5 309 C3H7 764 765 1 0 C3H7 310 766 767 768 1 0 C3H7 311 C5H11 769 770 1 0 OC2H5 312 C7H15 771 772 1 0 C3H7 313 C3H7 773 774 1 0 C7H15 314 C2H5O 775 776 1 0 C5H11 315 C5H11 777 778 1 0 OC4H9 316 C3H7 779 780 1 0 OC2H5 317 C5H11O 781 782 1 0 C3H7 318 C5H11 783 784 1 0 OCH3 319 C3H7 785 786 1 0 OC2H5 320 C5H11 787 788 1 0 C3H7 321 C3H7 789 790 1 0 OC3H7 322 C4H9 791 792 1 0 C5H11 323 C5H11 793 794 1 0 OC2H5 324 C7H15O 795 796 1 0 CH3 325 C5H11 797 798 1 0 OC3H7 326 C3H7 799 800 1 0 OC2H5 327 C5H11 801 802 1 0 C3H7 328 C3H7 803 804 1 0 C3H7 329 C3H7O 805 806 1 0 C7H15 330 C7H15 807 808 1 0 OCH3 331 C3H7 809 810 1 0 OC2H5 332 811 812 813 1 0 C5H11 333 C5H11 814 815 1 0 OCH3 334 C2H5O 816 817 1 0 OC4H9 335 C5H11 818 819 1 0 C3H7 336 C3H7 820 821 1 0 OC4H9 337 C5H11 822 823 1 0 OC2H5 338 C5H11 824 825 1 0 C3H7 339 C3H7 826 827 1 0 C5H11 340 C5H11O 828 829 1 0 CH3 341 C3H7 830 831 1 0 OC2H5 342 C7H15O 832 833 1 0 OC3H7 343 C5H11 834 835 836 1 1 C3H7 344 C2H5O 837 838 839 1 1 OC2H5 345 C3H7 840 841 842 1 1 OC4H9 346 843 844 845 846 1 1 C3H7 347 C5H11O 847 848 849 1 1 OC2H5 348 C7H15 850 851 852 1 1 C5H11 349 C5H11 853 854 855 1 1 C7H15 350 C3H7 856 857 858 1 1 C5H11 351 C5H11 859 860 861 1 1 C3H7 352 C3H7 862 863 864 1 1 OC2H5 353 C5H11O 865 866 867 1 1 C3H7 354 C4H9 868 869 870 1 1 OC3H7 355 C3H7 871 872 873 1 1 OC2H5 356 C5H11 874 875 876 1 1 C3H7 357 C3H7 877 878 879 1 1 OCH3 358 C3H7O 880 881 882 1 1 C5H11 359 C5H11 883 884 885 1 1 OC2H5 360 C7H15O 886 887 888 1 1 CH3 361 C3H7 889 890 1 0 C3H7 362 C5H11O 891 892 1 0 OC2H5 363 C3H7 893 894 895 1 1 C3H7 364 896 897 898 899 1 1 C5H11 365 C5H11 900 901 1 0 OC2H5 366 C7H15 902 903 1 0 C3H7 367 C3H7 904 905 906 1 1 OC2H5 368 C2H5O 907 908 909 1 1 C5H11 369 C5H11 910 911 912 1 1 OC2H5 370 C3H7 913 914 1 0 C7H15 371 C5H11O 915 916 1 0 C3H7 372 C5H11 917 918 919 1 1 OCH3 373 C3H7 920 921 1 0 CH3 374 C5H11 922 923 924 1 1 C3H7 375 C3H7 925 926 1 0 OC3H7 376 C4H9 927 928 929 1 1 C5H11 377 C5H11 930 931 932 1 1 OC2H5 378 C7H15O 933 934 1 0 OC4H9

[0162] As nematic liquid crystal compositions comprising the liquid crystalline compound of the present invention produced by such methods as described above, the following Composition Examples (Use Examples 1 through 30) can be shown. In this connection, compounds in the Composition Examples are designated by abbreviation according to the definition shown in Table 1. Further, when the hydrogen atom of trans-1,4-cyclohexylene in the following partial structure was replaced by deuterium (heavy hydrogen) at positions Q1, Q2, and Q3, it is designated by symbol H [1D, 2D, 3D], and when replaced by deuterium at positions Q5, Q6, and Q7, it is designated by symbol H [5D, 6D, 7D]. In other words, the positions where deuterium substituted are indicated by the numeral in the bracket [ ].

[0163] In the Composition Examples (Use Examples), “%” means % by weight unless otherwise specified, and “part” means part by weight of an optically active compound based on 100 parts by weight of liquid crystal composition.

[0164] Determination of viscosity (&eegr;) was conducted at 20.0C, and determination of each of optical anisotropy (&Dgr;n), dielectric anisotropy (&Dgr;&egr;), threshold voltage (Vth), and twist pitch (P) was conducted at 25.0° C. 2 TABLE 1 R-(A1)-Z1 . . . -Zn-(An)-X 1) Left side terminal group R- Symbol CH2n+1— n- CnH2n+O— nO- CnH2n+1OCmH2m— nOm- CH2═CH— V- CH2=CHCnH2n— Vn- CnH2n+1CH═CHCmH2m— nVm- CnH2n+1CH═CHCmH2mCH═CHCkH2k— nVmVk- 2) Ring structure —(A1)—, —(An)— Symbol 935 B 936 (B)F 937 B(2F,3F) 938 B(F,F) 939 H 940 Py 941 D 942 Ch 3) Bonding group —Z1—, —Zn— Symbol —C2H4— 2 —C4H8— 4 —COO— E —C≡C— T —CH═CH— V —CF2O— CF2O —OCF2— OCF2 4) Right side terminal group -X Symbol —F —F —Cl —CL —CN —C —CF3 —CF3 —OCF3 —OCF3 —OCF2H —OCF2H —CnH2n+1 -n —OCnH2n+1 —On —COOCH3 -EMe —CnH2nCH═CH2 -nV —CmH2mCH═CHCnH2n+1 -mVn —CmH2mCH═CHCnH2nF -mVnF —CH═CF2 —VFF —CnH2nCH═CF2 -nVFF —C≡C—CN -TC 5) Example of designation Example 1 3-H2B(F,F)B(F)—F 943 Example 2 3-HB(F)TB-2 944 Example 3 1V2-BEB(F,F)—C 945 946 Use Example 1 5-H4HB(2F, 3F)-3 (No. 20) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% TNI = 77.0 (° C.) &Dgr;&egr; = −1.5 Use Example 2 5-H4HB(2F, 3F)-O2 (No. 23) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% TNI = 81.8 (° C.) &Dgr;&egr; = −2.1 Use Example 3 3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% TNI = 81.0 (° C.) &Dgr;&egr; = −1.9 Use Example 4 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% TNI = 90.2 (° C.) &Dgr;&egr; = −2.3 Use Example 5 3-HH4B(2F, 3F)-O2 (No. 94) 10.0% 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 6.0% 3-HHB-1 11.0% 3-HHB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% CM33 0.8 part TNI = 90.3 (° C.) &eegr; = 17.8 (mPa·s) &Dgr;n = 0.165 &Dgr;&egr; = 6.5 Vth = 2.18 (V) P = 11.3 &mgr;m Use Example 6 5-H4HB(2F, 3F)-3 (No. 20) 7.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 15.0% 3-H[1D, 2D, 3D]-C 9.0% 3-HB(F)-C 5.0% 2-BTB-1 2.0% 3-HH-4 4.0% 3-HH-VFF 6.0% 2-H[1D, 2D, 3D]HB-C 3.0% 3-HHB-C 6.0% 3-HB(F)TB-2 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0% TNI =87.3 (° C.) &eegr; = 19.9 (mPa·s) &Dgr;n = 0.154 &Dgr;&egr; = 8.5 Vth = 2.05 (V) Use Example 7 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 15.0% 4O1-BEB(F)-C 13.0% 5O1-BEB(F)-C 13.0% 2-HHB(F)-C 15.0% 3-HHB(F)-C 15.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% TNI = 88.4 (° C.) &eegr; = 88.0 (mPa·s) &Dgr;n = 0.149 &Dgr;&egr; = 30.6 Vth = 0.90(V) Use Example 8 3-HH4B(2F, 3F)-O2 (No. 94) 6.0% 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-HHB-3 8.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% TNI = 90.8 (° C.) &eegr; = 36.4 (mPa·s) &Dgr;n = 0.201 &Dgr;&egr; = 6.1 Vth = 2.31 (V) Use Example 9 5-H4HB(2F, 3F)-3 (No. 20) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 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-5 5.0% 4-HEB-5 5.0% 1O-BEB-2 4.0% 3-HHB-1 3.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% TNI = 68.1 (° C.) &eegr; = 40.5 (mPa·s) &Dgr;n = 0.121 &Dgr;&egr; = 11.1 Vth = 1.35 (V9 Use Example 10 5-H4HB(2F, 3F)-3 (No. 20) 4.0% 5-H4HB(2F, 5F)-O2 (No. 23) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 4.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 4.0% 3-HB-C 18.0% 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-1 2.0% 3-HHB-F 2.0% 3-HHB-O1 3.0% 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% TNI = 72.1 (° C.) &eegr; = 23.2 (mPa·s) &Dgr;n = 0.140 &Dgr;&egr; = 7.1 Vth = 1.90 (V) Use Example 11 5-H4HB(2F, 3F)-3 (No. 20) 10.0% 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-HH-EMe 10.0% 3-HB-O2 18.0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0% 2O1-HBEB(F)-C 2.0% 3-HB(F)EB(F)-C 2.0% 3-HBEB(F, F)-C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 3.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0% TNI = 70.0 (° C.) &eegr; = 38.0 (mPa·s) &Dgr;n = 0.112 &Dgr;&egr; = 23.0 Vth = 1.04 (V) Use Example 12 3-HH4B(2F, 3F)-O2 (No. 94) 7.0% 5-BEB(F)-C 5.0% V-HB-C 14.0% 5-PyB-C 6.0% 4-BB-3 10.0% 8-HH-2V 10.0% 5-HH-V 6.0% 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% TNI = 90.1 (° C.) &eegr; = 17.9 (mPa·s) &Dgr;n = 0.115 &Dgr;&egr; = 4.8 Vth = 2.37 (V) Use Example 13 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 5F)-O2 (No. 23) 5.0% 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-O1 2.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 5.0% TNI = 84.7 (° C.) &eegr; = 43.2 (mPa·s) &Dgr;n = 0.140 &Dgr;&egr; = 27.5 Vth = 1.06 (V) Use Example 14 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No. 237) 4.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 4-BEB-C 6.0% 3-HB-C 28.0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% TNI = 65.1 (° C.) &eegr; = 29.1 (mPa·s) &Dgr;n = 0.116 &Dgr;&egr; = 9.2 Vth = 1.43 (V) Use Example 15 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 2-BEB-C 10.0% 5-BB-C 12.0% 7-BB-C 7.0% 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% 3-HHB-3 8.0% TNI = 63.4 (° C.) &eegr; = 21.2 (mPa·s) &Dgr;n = 0.160 &Dgr;&egr; = 6.2 Vth = 1.82 (V) Use Example 16 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 1V2-BEB(F, F)-C 8.0% 3-HB-C 10.0% V2V-HB-C 14.0% V2V-HH-3 14.0% 3-HB-O2 4.0% 3-HHB-1 10.0% 3-HHB-3 5.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% TNI = 98.1 (° C.) &eegr; = 20.8 (mPa·s) &Dgr;n = 0.130 &Dgr;&egr; = 7.2 Vth = 2.18 (V) Use Example 17 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 5-BTB(F)TB-3 10.0% V2-HB-TC 10.0% 3-HB-TC 10.0% 3-HB-C 10.0% 5-HB-C 7.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4 5.0% 3-HHB-3 11.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0% TNI = 92.8 (° C.) &eegr; = 16.7 (mPa·s) &Dgr;n = 0.203 &Dgr;&egr; = 6.3 Vth = 2.15 (V) Use Example 18 5-H4HB(2F, 3F)-3 (No. 20) 10.0% 2-HHB(F)-F 17.0% 3-HHB(F)-F 17.0% 5-HHB(F)-F 16.0% 2-H2HB(F)-F 10.0% 3-H2HB(F)-F 5.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 13.0% CN 0.3 part TNI = 100.8 (° C.) &eegr; = 27.3 (mPa·s) &Dgr;n = 0.094 &Dgr;&egr; = 4.6 Vth = 2.25 (V) p = 81 &mgr;m Use Example 19 5-H4HB(2F, 3F)-O2 (No. 23) 6.0% 7-HB(F)-F 5.0% 5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH[5D, 6D, 7D]-4 3.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HH[5D, 6D, 7D]B(F)-F 10.0% 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 2.0% 3-HHB-O1 5.0% 3-HHB-3 4.0% TNI = 83.9 (° C.) &eegr; = 19.9 (mPa·s) &Dgr;n = 0.091 &Dgr;&egr; = 3.0 Vth = 2.69 (V) Use Example 20 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 7-HB(F, F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 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% TNI = 85.5 (° C.) &eegr; = 27.9 (mPa·s) &Dgr;n = 0.116 &Dgr;&egr; = 5.4 Vth = 2.03 (V) Use Example 21 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 7-HB(F, F)-F 3.0% 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 5.0% 4-HHB(F, F)-F 5.0% 3-HH2B(F, F)-F 10.0% 3-HBB(F, F)-F 12.0% 5-HBB(F, F)-F 12.0% 3-HBCF2OB(F, F)-F 6.0% TNI = 72.1 (° C.) &eegr; = 29.5 (mPa·s) &Dgr;n = 0.087 &Dgr;&egr; = 8.1 Vth = 1.61 (V) Use Example 22 5-H4HB(2F, 3F)-O2 (No. 23) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 3.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 3.0% 7-HB(F, F)-F 5.0% 3-H2HB(F, F)-F 12.0% 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 10.0% 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% TNI = 77.8 (° C.) &eegr; = 37.5 (mPa·s) &Dgr;n = 0.087 &Dgr;&egr; = 12.4 Vth = 1.44 (V) Use Example 23 5-H4HB(2F, 3F)-O2 (No. 23) 7.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No. 237) 3.0% 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL 4.0% 1O1-HH-5 3.0% 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% TNI = 91.2 (° C.) &eegr; = 24.9 (mPa·s) &Dgr;n = 0.125 &Dgr;&egr; = 4.3 Vth = 2.39 (V) Use Example 24 3-HH4B(2F, 3F)-O2 (No. 94) 8.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No. 237) 4.0% 3-HHB(F, F)-F 9.0% 3-H2HB(F, F)-F 8.0% 4-H2HB(F, F)-F 8.0% 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% TNI = 95.6 (° C.) &eegr; = 39.8 (mPa·s) &Dgr;n = 0.116 &Dgr;&egr; = 8.4 Vth = 1.82 (V) Use Example 25 3-HH4B(2F, 3F)-O2 (No. 94) 7.0% 5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F 5.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 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 10.0% 3-HH2B(F)-F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F, F)-OCF2H 4.0% TNI = 85.5 (° C.) &eegr; = 18.0 (mPa·s) &Dgr;n = 0.094 &Dgr;&egr; = 4.1 Vth = 2.45 (V) Use Example 26 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 5-H4HB(F, F)-F 7.0% 5-H4HB-OCF3 5.0% 3-H4HB(F, F)-CF3 8.0% 5-H4HB(F,F)-CF3 10.0% 3-HB-CL 6.0% 5-HB-CL 4.0% 2-H2BB(F)-F 5.0% 3-H2BB(F)-F 10.0% 5-HVHB(F, F)-F 5.0% 3-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0% V-HHB(F)-F 5.0% 3-HHB(F)-F 5.0% 5-HHEB-OCF3 2.0% 3-HBEB(F, F)-F 5.0% 5-HH-V2F 3.0% TNI = 68.2 (° C.) &eegr; = 27.6 (mPa·s) &Dgr;n = 0.094 &Dgr;&egr; = 8.0 Vth = 1.78 (V) Use Example 27 5-H4HB(2F, 3F)-3 (No. 20) 15.0% 3-HEB-O4 23.0% 4-HEB-O2 18.0% 5-HEB-O1 18.0% 3-HEB-O2 14.0% 5-HEB-O2 12.0% TNI = 77.0 (° C.) &Dgr;n = 0.087 &Dgr;&egr; = −1.5 Use Example 28 5-H4HB(2F, 3F)-3 (No. 20) 5.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 15.0% 3-HB-O2 10.0% 3-HB-O4 10.0% 3-HH-4 2.0% 5-HH-2 3.0% 3-HEB-O4 15.0% 4-HEB-O2 12.0% 5-HEB-O1 12.0% 3-HEB-O2 9.0% 5-HEB-O2 7.0% TNI = 81.9 (° C.) &Dgr;n = 0.090 &Dgr;&egr; = −2.6 Use Example 29 3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HB-O2 15.0% 3-HB-O4 10.0% 3-HEB-O4 10.0% 4-HEB-O2 7.0% 5-HEB-O1 7.0% 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HB(2F, 3F)-O2 7.0% 5-HHB(2F, 3F)-O2 5.0% 5-HBB(2F, 3F)-2 5.0% 5-HBB(2F, 3F)-O2 4.0% 5-BB(2F, 3F)B-3 4.0% TNI = 77.2 (° C.) &Dgr;n = 0.105 &Dgr;&egr; = −3.1 Use Example 30 5-H4HB(2F, 3F)-3 (No. 20) 15.0% 5-H4HB(2F, 3F)-O2 (No. 23) 10.0% 3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HH4B(2F, 3F)-B(2F, 3F)-O2 (No. 238) 5.0% 3-H4B(2F, 3F)-O2 (No. 4) 5.0% 3-HB(2F, 3F)-O2 20.0% 5-HHB(2F, 3F)-O2 10.0% 5-HHB(2F, 3F)-1O1 5.0% 5-HBB(2F, 3F)-2 10.0% 5-HBB(2F, 3F)-1O1 5.0% Use Example 31 5-H4HB(2F, 3F)-O2 (No. 23) 10.0% 3-HH4B(2F, 3F)-O2 (No. 94) 10.0% 3-H4B(2F, 3F)B(2F, 3F)-O3 (No. 77) 10.0% 5-HH4HB(2F, 3F)-O2 (No. 220) 5.0% 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% 3-HBB(F, F)-F 14.0% 1O1-HBBH-4 5.0% Use Example 32 3-H4B(2F, 3F)-O2 (No. 4) 7.0% 3-HH3OB(2F, 3F)-3 (No. 91) 4.0% 5-HH4HB(2F, 3F)-O2 (No. 220) 3.0% 5-HB-CL 12.0% 3-HH-4 3.0% 3-HB-O2 17.0% 3-H2HB(F, F)-F 4.0% 3-HHB(F, F)-F 8.0% 3-HBB(F, F)-F 6.0% 2-HHB(F)-F 5.0% 3-HHB(F)-F 5.0% 5-HHB(F)-F 5.0% 2-H2HB(F)-F 2.0% 3-H2HB(F)-F 1.0% 5-H2HB(F)-F 2.0% 3-HHBB(F, F)-F 4.0% 3-HBCF2OB-OCF3 4.0% 5-HBCF2OB(F, F)-CF3 4.0% 3-HHB-O1 4.0% Use Example 33 3-H4B(2F, 3F)-O2 (No. 4) 5.0% 3-HH3OB(2F, 3F)-3 (No. 91) 8.0% 1V2-BEB(F, F)-C 6.0% 3-HB-C 23.0% 2-BTB-1 10.0% 5-HH-VFF 20.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 3.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% Use Example 34 5-H3OB(2F, 3F)-O2 (No. 6) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 15.0% 3-H4B(2F, 3F)B(2F, 3F)-O3 (No. 77) 5.0% 2-HB-C 5.0% 3-HB-C 17.0% 3-HB-O2 5.0% 2-BTB-1 3.0% 3-HHB-1 2.0% 3-HHB-F 4.0% 3-HHB-O1 5.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB(F)-F 7.0% 3-HHB(F)-F 7.0% 5-HHB(F)-F 7.0% 3-HHB(F, F)-F 5.0%

[0165] As will be understood from the Examples described above, the compounds of the present invention, that is, any two to four rings compounds having butylene group or propylenoxy group, and 2,3-difluorophenyl group at the same time have the following characteristics:

[0166] 1) The compounds are wide in temperature range of exhibiting a liquid crystal phase, and are extremely high in capability of developing nematic phase.

[0167] 2) Improvement in response speed in IPS mode is noticed with the compounds, since the compounds have a negative and high &Dgr;&egr;.

[0168] 3) A low viscosity, low threshold voltage, and improvement in response speed are noticed with the compounds.

[0169] 4) Separation of crystals or development of smectic phase is not observed with the compounds even at very low temperatures, and stabilized nematic liquid crystal compositions can be produced from the compounds.

INDUSTRIAL APPLICABILITY

[0170] Compounds of the present invention exhibit the characteristics described in 1) to 4) above, are stable against outside environment, and can provide novel liquid crystal compositions and liquid crystal display devices by which realization of expansion of temperature range of use, driving at a low voltage, and a high speed response is possible.

Claims

1. A liquid crystalline compound expressed by the general formula (1)

947

wherein R1 represents an alkyl group having 1 to 15 carbon atoms in which alkyl group, not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X1, X2, and X3 independently represent —(CH2)4—, —(CH2)3O—, —O(CH2)3—, or single bond; Y1 represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

2. The liquid crystalline compound according to claim 1 wherein ring A1 represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X1 represents —(CH2)4— or —(CH2)3O—; and either m and n are 0 in the general formula (1).

3. The liquid crystalline compound according to claim 1 wherein ring A1 and ring A2 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X1 represents —(CH2)4— or —(CH2)3O—; X2 represents single bond; and m is 1 and n is 0 in the general formula (1).

4. The liquid crystalline compound according to claim 1 wherein ring A1 and ring A2 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X2 represents —(CH2)4— or —(CH2)3O—; X1 represents single bond; and m is 1 and n is 0 in the general formula (1).

5. The liquid crystalline compound according to claim 1 wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; XI represent —(CH2)4— or —(CH2)3O—; either X2 and X3 represent single bond; and m is 1 and n is 1 in the general formula (1).

6. The liquid crystalline compound according to claim 1 wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X2 represents —(CH2)4— or —(CH2)3O—; either X1 and X3 represent single bond; and m is 1 and n is 1 in the general formula (1).

7. The liquid crystalline compound according to claim 1 wherein ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X3 represents —(CH2)4— or —(CH2)3O—; either X1 and X2 represent single bond; and m is 1 and n is 1 in the general formula (1).

8. A liquid crystal composition comprising at least two components and comprising at least one liquid crystalline compound expressed by the general formula (1)

948

wherein R′ represents an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A1, ring A2, and ring A3 independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X1, X2, and X3 independently represent —(CH2)4—, —(CH2 )3O—, —O(CH2)3—, or single bond; Y1 represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

9. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

949

wherein R2 represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y2 represents fluorine atom, chlorine atom, —OCF3, —OCF2H, —CF3, —CF2H, —CFH2, —OCF2CF2H, or —OCF2CFHCF3; L1 and L2 independently represent hydrogen atom or fluorine atom; Z1 and Z2 independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF2O—, —OCF2—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope.

10. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

950

wherein R3 and R4 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y3 represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z3 represents 1,2-ethylene group, —COO—, or single bond; L3, L4, and L5 independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope.

11. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

951

wherein R5 and R6 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one or hydrogen atom may be replaced by fluorine atom; Z4 and Z5 independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡HC—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

12. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

952

wherein R7 and R8 independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K and ring M independently represent trans-1,4-cyclohexylene or 1,4-phenylene; L6 and L7 independently represent hydrogen atom or fluorine atom, but in no case simultaneously represent L6 and L7 hydrogen atom; Z6 and Z7 independently represent —CH2CH2—, —COO—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

13. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12) described above.

14. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

15. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

16. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1 to 7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a fourth component, at least one component selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

17. A liquid crystal composition comprising at least one optically active compound in addition to the liquid crystal composition defined in any one of claims 8 to 16.

18. A liquid crystal display device fabricated by using the liquid crystal composition defined in any one of claims 8 to 17.