Liquid crystal compound having benzothiophene, liquid crystal composition and liquid crystal display device

Abstract

Provided is a liquid crystal compound that has high stability to heat, light and so forth, a high clearing point, low minimum temperature of a liquid crystal phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, a suitable elastic constant and excellent compatibility with other liquid crystal compounds, a liquid crystal composition containing the compound and a liquid crystal display device including the composition. The compound is represented by formula (1). ##STR00001## For example, R.sup.1 is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyl having 2 to 10 carbons; R.sup.2 is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyl having 3 to 10 carbons; ring A.sup.1 is 1,4-cyclohexylene or 1,4-phenylene; ring A.sup.2 is 1,4-cyclohexylene or 1,4-phenylene; Z.sup.1 and Z.sup.2 are a single bond; Z.sup.3 is O or a single bond; and L.sup.1 is F, CF.sub.3 or CF.sub.2H.

Claims

1. A compound, represented by formula (1): ##STR00338## wherein, in formula (1), R.sup.1 and R.sup.2 are independently hydrogen, halogen or alkyl having 1 to 20 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O or S, at least one piece of (CH.sub.2).sub.2 may replace by CHCH, and in the groups, at least one piece of hydrogen may be replaced by halogen; ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, and at least one piece of hydrogen on the rings may be replaced by halogen; Z.sup.1 and Z.sup.2 are independently a single bond or alkylene having 1 to 4 carbons, in the alkylene, at least one piece of CH.sub.2 may be replaced by O or COO, and at least one piece of (CH.sub.2).sub.2 may replace by CH=CH or CC, and in the groups, at least one piece of hydrogen may be replaced by halogen; Z.sup.3 is O or a single bond; L.sup.1 is F, CF.sub.3 or CF.sub.2H; and a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 4 or less, and when a or b is 2 or more, two of arbitrary ring A.sup.1, two of arbitrary ring A.sup.2, two pieces of arbitrary Z.sup.1 or two pieces of arbitrary Z.sup.2 may be identical or different.

2. The compound according to claim 1, represented by formula (1-2): ##STR00339## wherein, in formula (1-2), R.sup.1 and R.sup.2 are independently hydrogen, halogen or alkyl having 1 to 20 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O or S, at least one piece of (CH.sub.2).sub.2 may replace by CHCH, and in the groups, at least one piece of hydrogen may be replaced by halogen; ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, and at least one piece of hydrogen on the rings may be replaced by halogen; Z.sup.1 and Z.sup.2 are independently a single bond or alkylene having 1 to 4 carbons, in the alkylene, at least one piece of CH.sub.2 may be replaced by O or COO, and at least one piece of (CH.sub.2).sub.2 may replace by CHCH or and in the groups, at least one piece of hydrogen may be replaced by halogen; Z.sup.3 is O or a single bond; and a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 4 or less, and when a or b is 2 or more, two of ring A and A.sup.2, and two of Z.sup.1 and Z.sup.2 may be identical or different.

3. The compound according to claim 2, wherein, in formula (1-2), R.sup.1 and R.sup.2 are independently chlorine, fluorine, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkenyl having 2 to 10 carbons, polyfluoroalkyl having 1 to 10 carbons or polyfluoroalkyl having 1 to 9 carbons; ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one piece of hydrogen may be replaced by halogen, or tetrahydropyran-2,5-diyl; Z.sup.1 and Z.sup.2 are independently a single bond, (CH.sub.2).sub.2, CHCH, CFCF, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, (CH.sub.2).sub.4, (CH.sub.2).sub.2CF.sub.2O, (CH.sub.2).sub.2OCF.sub.2-5CF.sub.2O(CH.sub.2).sub.2, OCF.sub.2 (CH.sub.2).sub.2CHCH(CH.sub.2).sub.2 or (CH.sub.2).sub.2CHCH; and a and b are independently 0, 1, 2, 3 or 4, and a sum of a and b is 4 or less.

4. The compound according to claim 2, wherein, in formula (1-2), a sum of a and b is 0, 1, 2 or 3; R.sup.1 and R.sup.2 are independently chlorine, fluorine, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkenyl having 2 to 10 carbons, polyfluoroalkyl having 1 to 10 carbons or polyfluoroalkyl having 1 to 9 carbons; ring A.sup.1 and ring A.sup.2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one piece of hydrogen may be replaced by halogen, tetrahydropyran-2,5-diyl; and Z.sup.1 and Z.sup.2 are independently a single bond, (CH.sub.2).sub.2, CHCH, CFCF, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, (CH.sub.2).sub.4, (CH.sub.2).sub.2CF.sub.2O, (CH.sub.2).sub.2OCF.sub.2CF.sub.2O(CH.sub.2).sub.2, OCF.sub.2 (CH.sub.2).sub.2CHCH(CH.sub.2).sub.2 or (CH.sub.2).sub.2CHCH.

5. The compound according to claim 1, represented by any one of formulas (1-2-1) to (1-2-10): ##STR00340## ##STR00341## wherein, in formulas (1-2-1) to (1-2-10), R.sup.1 and R.sup.2 are independently chlorine, fluorine, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkenyl having 2 to 10 carbons, polyfluoroalkyl having 1 to 10 carbons or polyfluoroalkyl having 1 to 9 carbons; ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one piece of hydrogen is replaced by halogen, or tetrahydropyran-2,5-diyl; and Z.sup.1, Z.sup.2, Z.sup.4 and Z.sup.5 are independently a single bond, (CH.sub.2).sub.2CHCH, CFCF, CC, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, (CH.sub.2).sub.4, (CH.sub.2).sub.2CF.sub.2O, (CH.sub.2).sub.2OCF.sub.2CF.sub.2O(CH.sub.2).sub.2, OCF.sub.2 (CH.sub.2).sub.2CHCH(CH.sub.2).sub.2 or (CH.sub.2).sub.2CHCH.

6. The compound according to claim 5, wherein, in formulas (1-2-1) to (1-2-10), R.sup.1 and R.sup.2 are independently fluorine, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkenyl having 2 to 10 carbons or polyfluoroalkyl having 1 to 9 carbons; ring A.sup.1, ring A.sup.2, ring A.sup.3 and ring A.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one piece of hydrogen may be replaced by halogen, or tetrahydropyran-2,5-diyl; and Z.sup.1, Z.sup.2, Z.sup.4 and Z.sup.5 are independently a single bond, (CH.sub.2).sub.2CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O or OCH.sub.2.

7. The compound according to claim 6, represented by any one of formulas (1-2-4), (1-2-7) and (1-2-9): ##STR00342##

8. The compound according to claim 6, represented by any one of formulas (1-2-1), (1-2-5), (1-2-8) and (1-2-10), wherein, R.sup.1 is alkoxy having 1 to 6 carbons: ##STR00343##

9. A liquid crystal composition, containing at least one compound according to claim 1.

10. The liquid crystal composition according to claim 9, further containing at least one compound selected from the group of compounds represented by formulas (6) to (12): ##STR00344## wherein in formulas (6) to (12), R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of hydrogen may be replaced by fluorine; R.sup.14 is alkyl having 1 to 10 carbons, in the alkyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of hydrogen may be replaced by fluorine; R.sup.15 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of hydrogen may be replaced by fluorine; S.sup.11 is hydrogen or methyl; X is CF.sub.2, O or CHF; ring D.sup.1, ring D.sup.2, ring D.sup.3 and ring D.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one piece of hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; ring D.sup.5 and ring D.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z.sup.15, Z.sup.16, Z.sup.17 and Z.sup.18 are independently a single bond, CH.sub.2CH.sub.2, OCO, CH.sub.2O, OCF.sub.2 or OCF.sub.2CH.sub.2CH.sub.2; L.sup.15 and L.sup.16 are independently fluorine or chlorine; and j, k, m, n, p, q, r and s are independently 0 or 1, a sum of k, m, n and p is 1 or 2, and a sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

11. The liquid crystal composition according to claim 9, further containing at least one compound selected from the group of compounds represented by formulas (13) to (15): ##STR00345## wherein in formulas (13) to (15), R.sup.16 and R.sup.17 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of hydrogen may be replaced by fluorine; ring E.sup.1, ring E.sup.2, ring E.sup.3 and ring E.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; and Z.sup.19, Z.sup.20 and Z.sup.21 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC or COO.

12. The liquid crystal composition according to claim 9, further containing at least one compound selected from the group of compounds represented by formulas (2) to (4): ##STR00346## wherein in formulas (2) to (4), R.sup.11 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of hydrogen may be replaced by fluorine, and at least one piece of CH.sub.2 may be replaced by O; X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3; ring B.sup.1, ring B.sup.2 and ring B.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one piece of hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z.sup.11, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC, COO, CF.sub.2O, OCF.sub.2, CH.sub.2O or (CH.sub.2).sub.4; and L.sup.11 and L.sup.12 are independently hydrogen or fluorine.

13. The liquid crystal composition according to claim 9, further containing at least one optically active compound and/or at least one polymerizable compound.

14. The liquid crystal composition according to claim 9, further containing at least one antioxidant and/or at least one ultraviolet light absorbent.

15. A liquid crystal display device, including the liquid crystal composition according to claim 9.

16. A liquid crystal display device, wherein the liquid crystal composition according to claim 9 is encapsulated.

Description

EXAMPLES

(1) The invention will be described in greater detail by way of Examples. However, the invention is not limited by the Examples.

(2) 1-1. Example of Compound (1)

(3) Compound (1) was prepared according to procedures described below. The thus prepared compound was identified by methods such as an NMR analysis. Physical properties of the compound were measured by methods described below.

(4) NMR Analysis

(5) As a measuring apparatus, DRX-500 (made by Bruker BioSpin Corporation) was used. In .sup.1H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl.sub.3, and measurement was carried out under conditions of room temperature, 500 MHz and 16 times of accumulation. Tetramethylsilane was used as an internal standard. In .sup.19F-NMR measurement, CFCl.sub.3 was used as an internal standard, and measurement was carried out under conditions of 24 times of accumulation. In explaining nuclear magnetic resonance spectra obtained, s, d, t, q, quin, sex and m stand for a singlet, a doublet, a triplet, a quartet, a quintet, a sextet and a multiplet, and br being broad, respectively.

(6) Sample for Measurement

(7) Upon measuring phase structure and a transition temperature, a liquid crystal compound itself was used as a sample. Upon measuring physical properties such as maximum temperature of a nematic phase, viscosity, optical anisotropy and dielectric anisotropy, a composition prepared by mixing the compound with a base liquid crystal was used as a sample.

(8) When the sample prepared by mixing the compound with the base liquid crystal was used, measurement was carried out according to a method described below. The sample was prepared by mixing 15% by weight of the compound and 85% by weight of the base liquid crystal. Then, an extrapolated value was calculated from a measured value of the sample, according to an extrapolation method, represented by an equation below, and the value was described: [extrapolated value]=(100[measured value of a sample][% by weight of a base liquid crystal][measured value of the base liquid crystal])/[% by weight of a compound].

(9) When crystals (or a smectic phase) precipitated at 25 C. even at the ratio of the compound to the base liquid crystal, a ratio of the compound to the base liquid crystal was changed in the order of (10% by weight:90% by weight), (5% by weight:95% by weight) and (1% by weight:99% by weight), and physical properties of the sample at a ratio at which no crystals (or no smectic phase) precipitated at 25 C. were measured. In addition, unless otherwise noted, the ratio of the compound to base liquid crystal was 15% by weight:85% by weight.

(10) As the base liquid crystal, base liquid crystal (i) described below was used. A proportion of the components of base liquid crystal (i) are expressed in terms of weight percent (% by weight).

(11) ##STR00067##
Measuring Method

(12) Physical properties were measured according to methods described below. Most of the measuring methods are applied as described in the Standard of Japan Electronics and Information Technology Industries Association (hereinafter abbreviated as JEITA) (JEITA ED-2521A) discussed and established by JEITA, or modified thereon. No TFT was attached to a TN device used for measurement.

(13) (1) Phase Structure

(14) A sample was placed on a hot plate in a melting point apparatus (FP52 Hot Stage made by Mettler-Toledo International Inc.) equipped with a polarizing microscope, and a state of a phase and a change thereof were observed with the polarizing microscope while the sample was heated at a rate of 3 C. per minute, and a kind of the phase was specified.

(15) (2) Transition Temperature ( C.)

(16) A sample was heated and then cooled at a rate of 3 C. per minute using a differential scanning calorimeter, DSC-7 System or Diamond DSC System, made by PerkinElmer, Inc., and a starting point of an endothermic peak or an exothermic peak caused by a phase change of the sample was determined by extrapolation, and thus a transition temperature was determined. Temperature at which a compound undergoes transition from a solid to a liquid crystal phase such as the smectic phase and the nematic phase may be occasionally abbreviated as minimum temperature of the liquid crystal phase. Temperature at which the compound undergoes transition from the liquid crystal phase to liquid may be occasionally abbreviated as clearing point.

(17) A crystal was expressed as C. When kinds of the crystals were distinguishable, each of the crystals was expressed as C.sub.1 or C.sub.2. The smectic phase or the nematic phase was expressed as S or N. When smectic A phase, smectic B phase, smectic C phase or smectic F phase was distinguishable among the smectic phases, the phases were expressed as S.sub.A, S.sub.B, S.sub.C or S.sub.F, respectively. A liquid (isotropic) was expressed as I. A transition temperature was expressed as C 50.0 N 100.0 I, for example. The expression indicates that a transition temperature from the crystals to the nematic phase is 50.0 C., and a transition temperature from the nematic phase to the liquid is 100.0 C.

(18) (3) Compatibility at Low Temperature:

(19) Samples in which the base liquid crystal and the compound were mixed for proportions of the compounds to be 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight and 1% by weight were prepared, and put in glass vials. After the glass vials were kept in freezers at 10 C. or 20 C. fora predetermined period of time, whether or not crystals (or a smectic phase) precipitated was observed.

(20) (4) Maximum Temperature of Nematic Phase (T.sub.NI or NI; C.)

(21) A sample was placed on a hot plate in a melting point apparatus equipped with a polarizing microscope, and heated at a rate of 1 C. per minute. Temperature when part of the sample began to change from a nematic phase to an isotropic liquid was measured. A maximum temperature of the nematic phase may be occasionally abbreviated as maximum temperature. When the sample was a mixture of a compound and the base liquid crystal, the maximum temperature was expressed in terms of a symbol TNI. When the sample was a mixture of a compound and component B and so forth, the maximum temperature was expressed in terms of a symbol NI.

(22) (5) Minimum Temperature of Nematic Phase (T.sub.C; C.)

(23) Samples each having a nematic phase were kept in freezers at temperatures of 0 C., 10 C., 20 C., 30 C. and 40 C. for 10 days, and then liquid crystal phases were observed. For example, when the sample was maintained in the nematic phase at 20 C. and changed to crystals or a smectic phase at 30 C., Tc was expressed as T.sub.c20 C. A minimum temperature of the nematic phase may be occasionally abbreviated as minimum temperature.

(24) (6) Viscosity (Bulk Viscosity; ; Measured at 20 C.; mPa.Math.s)

(25) A cone-plate (E-type) rotational viscometer was used for measurement.

(26) (7) Viscosity (Rotational Viscosity; 1; Measured at 25 C.; mPa.Math.s)

(27) Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 20 micrometers. Voltage was applied stepwise to the device in the range of 30 V to 50 V at an increment of 1 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. In dielectric anisotropy required for the calculation, a value measured according to items of dielectric anisotropy described below was used.

(28) (8) Optical Anisotropy (Refractive Index Anisotropy; Measured at 25 C.; n)

(29) Measurement was carried out by an Abbe refractometer with a polarizing plate mounted on an ocular, using light at a wavelength of 589 nanometers. A surface of a main prism was rubbed in one direction, and then a sample was added dropwise onto the main prism. A refractive index (n) was measured when a direction of polarized light was parallel to a direction of rubbing. A refractive index (n) was measured when the direction of polarized light was perpendicular to the direction of rubbing. A value of optical anisotropy (n) was calculated from an equation: n=n n.

(30) (9) Dielectric Anisotropy (; Measured at 25 C.)

(31) A value of dielectric anisotropy was calculated from an equation: =. A dielectric constant ( and ) was measured as described below.

(32) (1) Measurement of dielectric constant (): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, the glass substrate was heated at 150 C. for 1 hour. A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 4 micrometers, and the device was sealed with an ultraviolet-curable adhesive. Sine waves (0.5V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured.

(33) (2) Measurement of dielectric constant (): A polyimide solution was applied to a well-cleaned glass substrate. After calcining the glass substrate, rubbing treatment was applied to the alignment film obtained. A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured.

(34) (10) Elastic Constant (K.sub.11 and K.sub.33; Measured at 25 C.; pN)

(35) For measurement, Elastic Constant Measurement System Model EC-1 made by TOYO Corporation was used. A sample was put in a vertical alignment device in which a distance (cell gap) between two glass substrates was 20 micrometers. An electric charge of 20 V to 0 V was applied to the device, and electrostatic capacity and applied voltage were measured. Values of electrostatic capacity (C) and applied voltage (V) were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku in Japanese; Nikkan Kogyo Shimbun, Ltd.), and a value of elastic constant was obtained from equation (2.100).

(36) (11) Threshold Voltage (Vth; Measured at 25 C.; V)

(37) For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally black mode VA device in which a distance (cell gap) between two glass substrates was 4 micrometers and a rubbing direction was anti-parallel, and the device was sealed with an ultraviolet-curable adhesive. A voltage (60 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 20 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of a voltage at 10% transmittance.

(38) (12) Voltage Holding Ratio (VHR-1; Measured at 25 C.; %)

(39) A TN device used for measurement has a polyimide alignment film, and a distance (cell gap) between two glass substrates is 5 micrometers. A sample was put in the device, and then the device was sealed with an ultraviolet-curable adhesive. A pulse voltage (60 microseconds at 5 V) was applied to the TN device and the device was charged. A decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is a percentage of area A to area B.

(40) (13) Voltage Holding Ratio (VHR-2; Measured at 80 C.; %)

(41) A TN device used for measurement had a polyimide alignment film, and a distance (cell gap) between two glass substrates is 5 micrometers. A sample was put in the device, and then the device was sealed with an ultraviolet-curable adhesive. A pulse voltage (60 microseconds at 5 V) was applied to the TN device and the device was charged. A decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is a percentage of area A to area B.

(42) Raw Material

(43) Solmix A-11 (registered trademark) is a mixture of ethanol (85.5% by weight), methanol (13.4% by weight) and isopropanol (1.1% by weight), and was purchased from Japan Alcohol Trading Co., Ltd.

Example 1

Synthesis of Compound (No. 18)

(44) ##STR00068##
First Step

(45) Under a nitrogen atmosphere, compound (S-1) (40 g) and THF (300 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, sec-butyl lithium (1 M; n-hexane, a cyclohexane solution; 313 mL) was added dropwise, and further the resulting mixture was stirred for 2 hours. Subsequently, sulfur powder (11.8 g) was added thereto and stirred for 2 hours while returning the resulting mixture to 25 C. Then, bromoacetaldehyde diethyl acetal (84 g) was added thereto, and subjected to reflux for 2 hours. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene. An organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and a residue was purified by silica gel chromatography (toluene) to obtain compound (S-2) (31 g).

(46) Second Step

(47) Under a nitrogen atmosphere, compound (S-2) (31 g), polyphosphoric acid (150 g) and toluene (250 mL) were put in a reaction vessel, and subjected to reflux under heating for 3 hours. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene. An organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and a residue was purified by silica gel chromatography (toluene:heptane=2:3 in a volume ratio) to obtain compound (S-3) (12.9 g).

(48) Third Step

(49) Under a nitrogen atmosphere, compound (S-3) (6 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, LDA (1 M; n-hexane, a THF solution; 37 mL) was added dropwise, and further the resulting mixture was stirred for 2 hours. Subsequently, compound (S-4) (6 g) was added thereto and stirred for 2 hours while returning the resulting mixture to 25 C. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene. An organic layer was washed with water, and dried over anhydrous magnesium sulfate to obtain compound (S-5). After then, a dehydration under adding p-toluenesulfonic acid thereto was performed according to a publicly known method described in the above scheme and to give compound (S-6), and a hydrogenation reaction and purification were performed with palladium carbon to obtain compound (No. 18). (1.7 g). In addition, if referring to Example described in WO 2009150966 A or the like, the dehydration and the hydrogenation reaction performed herein are easy to be implemented.

(50) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.32 (d, 1H), 7.03 (t, 1H), 6.91 (d, 1H), 4.17 (q, 2H), 2.78 (tt, 1H), 2.12 (dd, 2H), 1.88 (dd, 2H), 1.60-1.20 (m, 10H), 0.91 (t, 3H).

(51) Physical properties of compound (No. 18) were as described below. Transition temperature: C 68.4 N 86.0 I. T.sub.NI=83.9 C.; n=0.153; =3.12; =31.2 mPa.Math.s.

Example 2

(52) Synthesis of Compound (No. 41)

(53) In Example 1, compound (No. 41) was obtained by using compound (S-7) in place of compound (S-4).

(54) ##STR00069##

(55) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.32 (d, 1H), 7.02 (t, 1H), 6.99 (d, 1H), 4.16 (q, 2H), 2.75 (tt, 1H), 2.13 (dd, 2H), 1.85 (d, 2H), 1.74 (t, 4H), 1.60-1.20 (m, 18H), 0.88 (t, 3H).

(56) Physical properties of compound (No. 41) were as described below. Transition temperature: C 95.3 N 260.7 I. T.sub.NI=210.6 C.; n=0.167; =3.29; =53.4 mPa.Math.s.

Example 3

(57) Synthesis of Compound (No. 43)

(58) ##STR00070##
First Step

(59) Under a nitrogen atmosphere, compound (S-3) (3 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, lithium diisopropylamide (1 M; an n-hexane solution; 18.34 mL) was added dropwise in a temperature range of 74 C. to 70 C., and further the resulting mixture was stirred for 2 hours. Subsequently, a THF (10 mL) solution of triisobutyl borate (4.02 g) was added thereto in a temperature range of 75 C. to 70 C., and stirred for 8 hours while returning the resulting mixture to 25 C. A reaction mixture was poured into hydrochloric acid aqueous solution, and the resulting reaction mixture was subjected to extraction with ethyl acetate. A combined organic layer was washed with water, saturated aqueous solution of sodium hydrogencarbonate and water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure to obtain compound (S-8) (1.9 g).

(60) Second Step

(61) Then, compound (S-8) (1.3 g) and compound (S-9) (1.8 g) were dissolved in toluene, and water, ethanol, Pd(PPh.sub.3).sub.4 (0.6 g), TBAB (0.17 g) and potassium carbonate (2.2 g) were added thereto, and the resulting mixture was refluxed under heating for 6 hours. After completion of the reaction, the resulting mixture was subjected to extraction with toluene, and washed with water, and then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a light brown solid. The resulting solid was formed into a solution, and subjected to silica gel column chromatography (heptane:toluene=3:2 in a volume ratio) and recrystallization (ethanol) to obtain compound (No. 43) as a colorless crystal (1.5 g).

(62) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.73 (d, 2H), 7.64 (d, 2H), 7.55 (d, 2H), 7.48 (d, 1H), 7.44 (d, 1H), 7.27 (d, 2H), 7.07 (t, 1H), 4.20 (q, 2H), 2.63 (t, 2H), 1.69 (sex, 2H), 1.47 (t, 3H), 0.98 (t, 3H).

(63) Physical properties of compound (No. 43) were as described below. Transition temperature: C 205.9 S 265.6 N 295.5 I. T.sub.NI=224.6 C.; n=0.587; =5.47; =109.6 mPa.Math.s. In addition, the sample for measurement was prepared from 1% by weight of compound (No. 43) and 99% by weight of base liquid crystal (i).

Example 4

(64) Synthesis of Compound (No. 9)

(65) In Example 3, compound (No. 9) was obtained by using compound (S-10) in place of compound (S-9).

(66) ##STR00071##

(67) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.59 (d, 2H), 7.43 (d, 1H), 7.41 (d, 1H), 7.23 (d, 2H), 7.07 (t, 1H), 4.20 (q, 2H), 2.62 (t, 2H), 1.67 (sex, 2H), 1.47 (t, 3H), 0.97 (t, 3H).

(68) Physical properties of compound (No. 9) were as described below. Transition temperature: C 89.5 N 99.4 I. T.sub.NI=101.9 C.; n=0.287; =3.83; =38.8 mPa.Math.s.

Example 5

Synthesis of Compound (No. 25)

(69) ##STR00072##
First Step

(70) Under a nitrogen atmosphere, compound (S-3) (3 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, lithium diisopropylamide (1 M; n-hexane solution; 16.82 mL) was added dropwise in a temperature range of 74 C. to 70 C., and further the resulting mixture was stirred for 2 hours. Subsequently, a THF (10 mL) solution of compound (S-11) (4.99 g) was added dropwise thereto in a temperature range of 75 C. to 70 C., and stirred for 8 hours while returning the resulting mixture to 25 C. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene, and washed with water, and then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a light brown solid. The resulting material was subjected to silica gel column chromatography (heptane:toluene=3:1 in a volume ratio) and recrystallization (ethanol) to obtain compound (No. 25) as a colorless crystal (3.15 g).

(71) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.28 (d, 1H), 7.02 (t, 1H), 6.89 (d, 1H), 4.16 (q, 2H), 2.87 (t, 2H), 1.79 (d, 2H), 1.73 (d, 2H), 1.62 (q, 2H), 1.44 (t, 3H), 1.35-0.79 (m, 10H), 0.88 (t, 3H).

(72) Physical properties of compound (No. 25) were as described below. Transition temperature: C 88.2 I. T.sub.NI=59.9 C.; n=0.133; =3.16; =38.7 mPa.Math.s.

Example 6

(73) Synthesis of Compound (No. 105)

(74) ##STR00073##
First Step

(75) Under a nitrogen atmosphere, compound (S-12) (22.9 g), (S-13) (10.0 g), potassium carbonate (K.sub.2CO.sub.3; 18.5 g) and DMF (150 mL) were put in a reaction vessel, and the resulting mixture was stirred for 2 hours at 100 C. A reaction mixture was cooled to 25 C., and then a precipitate was filtered, and the filtrate was concentrated. A residue was purified by silica gel chromatography (heptane), and further purified by recrystallization from ethanol to obtain compound (S-14) (23.0 g).

(76) Second Step

(77) Under a nitrogen atmosphere, compound (S-14) (10 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, sec-butyl lithium (1 M; n-hexane, a cyclohexane solution; 33 mL) was added dropwise, and further the resulting mixture was stirred for 2 hours. Subsequently, sulfur powder (1.25 g) was added thereto, and stirred for 2 hours while returning the resulting mixture to 25 C. Then, bromoacetaldehyde diethyl acetal (8.89 g) was added thereto, and the resulting material was subjected to reflux for 2 hours. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene. An organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (S-15) (7.8 g).

(78) Third Step

(79) Under a nitrogen atmosphere, compound (S-15) (7.7 g), polyphosphoric acid (20 g) and toluene (150 mL) were put in a reaction vessel, and subjected to reflux under heating for 3 hours. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene. An organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and a residue was purified by silica gel chromatography (toluene:heptane=2:3 in a volume ratio) to obtain compound (S-16) (3.9 g).

(80) Fourth Step

(81) Under a nitrogen atmosphere, compound (S-16) (3.9 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled down to 74 C. Thereto, lithium diisopropylamide (LDA, 1 M; an n-hexane solution; 16.82 mL) was added dropwise in a temperature range of 74 C. to 70 C., and further the resulting mixture was stirred for 2 hours. Subsequently, a THF (10 mL) solution of iodopropane (2.4 g) was added dropwise thereto in a temperature range of 75 C. to 70 C., and stirred for 8 hours while returning the resulting mixture to 25 C. A reaction mixture was poured into water, and the resulting reaction mixture was subjected to extraction with toluene, and washed with water, and then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a light brown solid. The resulting material was subjected to silica gel column chromatography (heptane:toluene=4:1 in a volume ratio) and recrystallization (ethanol) to obtain compound (No. 105) as a colorless crystal (2.7 g).

(82) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.31 (d, 1H), 7.01 (t, 1H), 6.90 (d, 1H), 3.88 (d, 2H), 2.83 (t, 2H), 1.95 (br, 2H), 1.79-1.69 (m, 9H), 1.30 (sex, 2H), 1.2-0.8 (m, 13H), 1.00 (t, 3H), 0.88 (t, 3H).

(83) Physical properties of compound (No. 105) were as described below. Transition temperature: C 74.0 N 171.2 I. T.sub.NI=145 C.; n=0.127; =2.0; =51.4 mPa.Math.s.

Example 7

Synthesis of Compound (No. 8)

(84) In first step and second step in Example 1, compound (S-18) was prepared by using compound (S-17) in place of compound (S-1), and in Example 3, compound (No. 8) was obtained by using compound (S-10) in place of compound (S-9) and using compound (S-18) in place of compound (S-3).

(85) ##STR00074##

(86) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.62 (d, 2H), 7.45 (s, 1H), 7.45 (d, 1H), 7.24 (d, 2H), 7.15 (t, 1H), 2.72 (t, 2H), 2.62 (t, 2H), 1.68 (sex, 2H), 1.67 (sex, 2H), 0.98 (t, 3H), 0.97 (t, 3H).

(87) Physical properties of compound (No. 8) were as described below. Transition temperature: C 56.6 S 62.0 N 66.5 I. T.sub.NI=65.0 C.; n=0.260; =0.7; =40.8 mPa.Math.s.

Example 8

(88) Synthesis of Compound (No. 56)

(89) In Example 3, compound (No. 56) was obtained by using compound (S-19) in place of compound (S-9).

(90) ##STR00075##

(91) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.70 (t, 1H), 7.67 (dd, 1H), 7.54 (d, 2H), 7.48 (d, 1H), 7.43 (dd, 1H), 7.41 (dd, 1H), 7.27 (d, 2H), 7.09 (t, 1H), 4.21 (q, 2H), 2.64 (t, 2H), 1.69 (sex, 2H), 1.47 (t, 3H), 0.98 (t, 3H).

(92) Physical properties of compound (No. 56) were as described below. Transition temperature: C 111.2 N 263.3 I. T.sub.NI=201.7 C.; n=0.364; =3.80; =66.4 mPa.Math.s.

Example 9

(93) Synthesis of Compound (No. 241)

(94) In Example 3, compound (No. 241) was obtained by using compound (S-19) in place of compound (S-9).

(95) ##STR00076##

(96) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.70 (t, 1H), 7.67 (dd, 1H), 7.53 (d, 2H), 7.48 (d, 1H), 7.43 (dd, 1H), 7.40 (dd, 1H), 7.27 (d, 2H), 7.09 (t, 1H), 4.21 (q, 2H), 2.65 (t, 2H), 1.66 (quint, 2H), 1.47 (t, 3H), 1.40-1.30 (m, 4H), 0.91 (t, 3H).

(97) Physical properties of compound (No. 241) were as described below. Transition temperature: C 110.3 N 249.9 I. T.sub.NI=192.7 C.; n=0.357; =3.70; =61.7 mPa.Math.s.

Example 10

(98) Synthesis of Compound (No. 242)

(99) In Example 3, compound (No. 242) was obtained by using compound (S-20) in place of compound (S-9).

(100) ##STR00077##

(101) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.69 (t, 1H), 7.66 (dd, 1H), 7.54 (d, 2H), 7.47 (d, 1H), 7.40 (dd, 1H), 7.37 (dd, 1H), 7.09 (t, 1H), 6.98 (d, 2H), 4.21 (q, 2H), 4.01 (t, 2H), 2.64 (t, 2H), 1.80 (quint, 2H), 1.51 (sex, 2H), 1.48 (t, 3H), 0.99 (t, 3H).

(102) Physical properties of compound (No. 242) were as described below. Transition temperature: C 128.5 N 281.3 I. T.sub.NI=209.7 C.; n=0.377; =3.86; =76.7 mPa.Math.s.

Example 11

(103) Synthesis of Compound (No. 244)

(104) In Example 3, compound (No. 244) was obtained by using compound (S-21) in place of compound (S-9).

(105) ##STR00078##

(106) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.69 (t, 1H), 7.66 (dd, 1H), 7.47 (d, 1H), 7.40 (dd, 1H), 7.37 (dd, 1H), 7.09 (t, 1H), 4.21 (q, 2H), 4.01 (t, 2H), 2.64 (t, 2H), 1.69 (sex, 2H), 1.47 (t, 3H), 0.98 (t, 3H).

(107) Physical properties of compound (No. 244) were as described below. Transition temperature: C 56.6 N 68.6 I. T.sub.NI=88.4 C.; n=0.250; =3.89; =37.4 mPa.Math.s.

Example 12

(108) Synthesis of Compound (No. 14)

(109) In Example 3, compound (No. 14) was obtained by using compound (S-22) in place of compound (S-9).

(110) ##STR00079##

(111) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.54 (dd, 1H), 7.46 (d, 1H), 7.29 (td, 1H), 7.08 (t, 1H), 6.78 (td, 1H), 4.21 (q, 2H), 4.16 (q, 2H), 1.47 (t, 3H), 1.46 (t, 3H).

(112) Physical properties of compound (No. 14) were as described below. Transition temperature: C 140.4 I. T.sub.NI=154.3 C.; n=0.387; =10.46; n=69.6 mPa.Math.s.

Example 13

Synthesis of Compound (No. 243)

(113) In Example 3, compound (No. 243) was obtained by using compound (S-23) in place of compound (S-9). In addition, compound (S-23) can be prepared according to a method described in Examples in JP 2010-270074 A, or the like.

(114) ##STR00080##

(115) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.54 (dd, 1H), 7.46 (d, 1H), 7.29 (td, 1H), 7.08 (t, 1H), 6.77 (td, 1H), 4.21 (q, 2H), 3.87 (d, 2H), 1.92 (d, 2H), 1.85-1.75 (m, 3H), 1.47 (t, 3H), 1.35-0.91 (m, 10H), 0.88 (t, 3H).

(116) Physical properties of compound (No. 243) were as described below. Transition temperature: C 118.4 N 209.5 I. T.sub.NI=190.3 C.; n=0.267; =3.69; =79.4 mPa.Math.s.

Example 14

Synthesis of Compound (No. 247)

(117) In Example 3, compound (No. 247) was obtained by using compound (S-24) in place of compound (S-9). In addition, compound (S-24) is commercially available.

(118) In Example 3, compound (No. 247) was obtained by using compound (S-24) in place of compound (S-9). In addition, (S-24) is commercially available.

(119) ##STR00081##

(120) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.56 (d, 1H), 7.51 (d, 1H), 7.28 (d, 2H), 7.13 (t, 1H), 6.98 (t, 2H), 4.23 (q, 2H), 1.40 (t, 3H).

(121) Physical properties of compound (No. 247) were as described below. Transition temperature: C 153.6 I. T.sub.NI=111.7 C.; n=0.337; =0.98; =77.5 mPa.Math.s.

Example 15

(122) Synthesis of Compound (No. 249)

(123) In Example 3, compound (No. 249) was obtained by using compound (S-25) in place of compound (S-9).

(124) ##STR00082##

(125) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.69 (t, 1H), 7.67 (dd, 1H), 7.52 (d, 2H), 7.47 (d, 1H), 7.42 (dd, 1H), 7.40 (dd, 1H), 7.27 (d, 2H), 7.08 (t, 1H), 4.21 (q, 2H), 2.66 (t, 2H), 1.65 (quint, 2H), 1.48 (t, 3H), 1.37 (sex, 2H), 0.95 (t, 3H).

(126) Physical properties of compound (No. 249) were as described below. Transition temperature: C 102.24 N 249.2 I. T.sub.NI=194.4 C.; n=0.350; =2.6; =62.2 mPa.Math.s.

(127) Compounds (No. 1) to (No. 240) shown below can be prepared in a manner similar to the synthesis methods described in Examples 1 to 7.

(128) TABLE-US-00001 No. 1 2 3 4 5 6 7 8 0 9 10 11 12 13 14 15 16 17 18 00 19 01 20 02 21 03 22 04 23 05 24 06 25 07 26 08 27 09 28 0 29 30 31 32 33 34 35 36 37 38 0 39 40 41 42 43 44 45 46 47 48 0 49 50 51 52 53 54 55 56 57 58 0 59 60 61 62 63 64 65 66 67 68 0 69 70 71 72 73 74 75 76 77 78 0 79 80 81 82 83 84 85 86 87 88 0 89 90 91 92 93 94 95 96 97 98 0 99 100 101 102 103 104 105 106 107 108 0 109 110 111 112 113 114 115 116 117 118 00 119 01 120 02 121 03 122 04 123 05 124 06 125 07 126 08 127 09 128 0 129 130 131 132 133 134 135 136 137 138 0 139 140 141 142 143 144 145 146 147 148 0 149 150 151 152 153 154 155 156 157 158 0 159 160 161 162 163 164 165 166 167 168 0 169 170 171 172 173 174 175 176 177 178 0 179 180 181 182 183 184 185 186 187 188 0 189 190 191 192 193 194 195 196 197 198 0 199 200 201 202 203 204 205 206 207 208 0 209 210 211 212 213 214 215 216 217 218 00 219 01 220 02 221 03 222 04 223 05 224 06 225 07 226 08 227 09 228 0 229 230 231 232 233 234 235 236 237 238 0 239 240

Comparative Example 1

(129) Comparative compound (C-1) that is similar to the compound described in Examples in Patent literature No. 1 was prepared, in which an ethoxy group in a 6-position moves to a 5-position, and further fluorine is introduced to the 6-position in comparison with compound (No. 9).

Synthesis of Comparative Compound (C-1)

(130) ##STR00323##

(131) In the first step to the third step in Example 1, compounds (S-20) and (S-21) were prepared by using compound (S-19) in place of compound (S-1), and in the first step and the second step in Example 3, compound (C-1) was prepared by using compound (S-21) in place of compound (S-3) and using compound (S-10) in place of compound (S-9).

(132) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.58 (d, 2H), 7.37 (d, 1H), 7.24 (d, 2H), 7.05 (d, 1H), 4.16 (q, 2H), 2.62 (t, 2H), 1.67 (sex, 2H), 1.50 (t, 3H), 0.96 (t, 3H).

(133) Physical properties of compound (C-1) were as described below. Transition temperature: C 86.5 I. T.sub.NI=41.0 C.; n=0.214; =3.0; =112.7 mPa.Math.s.

(134) In comparison compound (C-1) with compound (No. 9) of the invention, compound (No. 9) of the invention exhibited larger negative dielectric anisotropy (=3.83), higher maximum temperature (T.sub.NI=101), smaller viscosity (=38.8) and larger optical anisotropy (n=0.287).

(135) 1-2. Example of Composition (1)

(136) Liquid crystal composition (1) of the invention will be described in detail by way of Examples. The compounds in Examples were represented using symbols according to definitions in a table described below. In Table 1, the configuration of 1,4-cyclohexylene is trans. A parenthesized number next to a symbolized compound in Examples corresponds to the number of the compound. A symbol () means any other liquid crystal compound. A proportion (percentage) of the liquid crystal compound is expressed in terms of weight percent (% by weight) based on the total weight of the liquid crystal composition. Values of the physical properties of the composition are summarized in a last part. The physical properties were measured according to the methods described above, and measured values are directly described without extrapolation.

(137) TABLE-US-00002 TABLE 1 Method for Description of Compounds using Symbols R(A.sub.1)Z.sub.1 . . . Z.sub.n(A.sub.n)R 1) Left-terminal Group R- Symbol C.sub.nH.sub.2n+1 n- C.sub.nH.sub.2n+1O nO C.sub.mH.sub.2m+1OC.sub.nH.sub.2n mOn- CH.sub.2CH V C.sub.nH.sub.2n+1CHCH nV CH.sub.2CHC.sub.nH.sub.2n Vn- C.sub.mH.sub.2m+1CHCHC.sub.nH.sub.2n mVn- CF.sub.2CH VFF CF.sub.2CHC.sub.nH.sub.2n VFFn- 2) Right-terminal Group -R Symbol C.sub.nH.sub.2n+1 -n OC.sub.nH.sub.2n+1 On COOCH.sub.3 -Eme CHCH.sub.2 V CHCHC.sub.nH.sub.2n+1 Vn C.sub.nH.sub.2nCHCH.sub.2 -nV C.sub.mH.sub.2mCHCHC.sub.nH.sub.2n+1 -mVn CHCF.sub.2 VFF F F Cl CL OCF.sub.3 OCF3 OCF.sub.2H OCF2H CF.sub.3 CF3 OCHCHCF.sub.3 OVCF3 CN C 3) Bonding Group -Z.sub.n- Symbol C.sub.nH.sub.2n n COO E CHCH V CH.sub.2O 1O OCH.sub.2 O1 CF.sub.2O X OCF.sub.2 x CC T 4) Ring Structure -A.sub.n- Symbol H B B(F) B(2F) B(F,F) B(2F,5F) 0 B(2F,3F) Py G Dh dh bt(7F) 5) Examples of Description

Example 16

(138) TABLE-US-00003 2O-bt(7F)H-3 (No. 18) 5% 3-HB-O2 (13-5) 10% 5-HB-CL (2-2) 13% 3-HBB(F,F)-F (3-24) 7% 3-PyB(F)-F (3-81) 10% 5-PyB(F)-F (3-81) 10% 3-PyBB-F (3-80) 10% 4-PyBB-F (3-80) 8% 5-PyBB-F (3-80) 7% 5-HBB(F)B-2 (15-5) 10% 5-HBB(F)B-3 (15-5) 10%

(139) NI=96.5 C.; =38.8 mPa.Math.s; n=0.186; =7.2.

Example 17

(140) TABLE-US-00004 2O-bt(7F)2H-3 (No. 25) 4% 2-HB-C (5-1) 5% 3-HB-C (5-1) 11% 3-HB-O2 (13-5) 14% 2-BTB-1 (13-10) 3% 3-HHB-F (3-1) 4% 3-HHB-1 (14-1) 8% 3-HHB-O1 (14-1) 5% 3-HHB-3 (14-1) 14% 3-HHEB-F (3-10) 4% 5-HHEB-F (3-10) 3% 2-HHB(F)-F (3-2) 7% 3-HHB(F)-F (3-2) 6% 5-HHB(F)-F (3-2) 7% 3-HHB(F,F)-F (3-3) 5%

Example 18

(141) TABLE-US-00005 2O-bt(7F)2H-3 (No. 25) 5% 7-HB(F,F)-F (2-3) 3% 3-HB-O2 (13-5) 7% 2-HHB(F)-F (3-2) 9% 3-HHB(F)-F (3-2) 9% 5-HHB(F)-F (3-2) 9% 2-HBB(F)-F (3-23) 9% 3-HBB(F)-F (3-23) 9% 5-HBB(F)-F (3-23) 14% 2-HBB-F (3-22) 4% 3-HBB-F (3-22) 4% 5-HBB-F (3-22) 3% 3-HBB(F,F)-F (3-24) 6% 5-HBB(F,F)-F (3-24) 9%

(142) NI=83.4 C.; =25.4 mPa.Math.s; n=0.117; =5.4.

Example 19

(143) TABLE-US-00006 3-HH1Obt(7F)-3 (No. 105) 5% 5-HB-CL (2-2) 13% 3-HH-4 (13-1) 12% 3-HH-5 (13-1) 4% 3-HHB-F (3-1) 4% 3-HHB-CL (3-1) 3% 4-HHB-CL (3-1) 4% 3-HHB(F)-F (3-2) 10% 4-HHB(F)-F (3-2) 8% 5-HHB(F)-F (3-2) 8% 7-HHB(F)-F (3-2) 8% 5-HBB(F)-F (3-23) 3% 1O1-HBBH-5 (15-1) 3% 3-HHBB(F,F)-F (4-6) 3% 4-HHBB(F,F)-F (4-6) 3% 5-HHBB(F,F)-F (4-6) 3% 3-HH2BB(F,F)-F (4-15) 3% 4-HH2BB(F,F)-F (4-15) 3%

(144) NI=120.2 C.; =21.6 mPa.Math.s; n=0.094; =3.5.

Example 20

(145) TABLE-US-00007 2O-bt(7F)BB-3 (No. 43) 1% 2O-bt(7F)HVH-3 (No. 73) 2% 3-HHB(F,F)-F (3-3) 9% 3-H2HB(F,F)-F (3-15) 7% 4-H2HB(F,F)-F (3-15) 8% 5-H2HB(F,F)-F (3-15) 8% 3-HBB(F,F)-F (3-24) 20% 5-HBB(F,F)-F (3-24) 20% 3-H2BB(F,F)-F (3-27) 9% 5-HHBB(F,F)-F (4-6) 3% 5-HHEBB-F (4-17) 2% 3-HH2BB(F,F)-F (4-15) 3% 1O1-HBBH-4 (15-1) 4% 1O1-HBBH-5 (15-1) 4%

Example 21

(146) TABLE-US-00008 3-bt(7F)B-3 (No. 8) 4% 5-HB-F (2-2) 12% 6-HB-F (2-2) 9% 7-HB-F (2-2) 7% 2-HHB-OCF3 (3-1) 7% 3-HHB-OCF3 (3-1) 7% 4-HHB-OCF3 (3-1) 7% 5-HHB-OCF3 (3-1) 5% 3-HH2B-OCF3 (5-36) 4% 5-HH2B-OCF3 (5-36) 4% 3-HHB(F,F)-OCF2H (5-30) 3% 3-HHB(F,F)-OCF3 (5-30) 5% 3-HH2B(F)-F (5-37) 3% 3-HBB(F)-F (5-32) 8% 5-HBB(F)-F (5-32) 9% 5-HBBH-3 (15-1) 3% 3-HB(F)BH-3 (15-2) 3%

(147) NI=84.5 C.; =15.1 mPa.Math.s; n=0.097; =4.1.

Example 22

(148) TABLE-US-00009 2O-bt(7F)B-3 (No. 9) 5% 5-HB-CL (2-2) 11% 3-HH-4 (13-1) 8% 3-HHB-1 (14-1) 5% 3-HHB(F,F)-F (3-3) 7% 3-HBB(F,F)-F (3-24) 20% 5-HBB(F,F)-F (3-24) 14% 3-HHEB(F,F)-F (3-12) 9% 4-HHEB(F,F)-F (3-12) 3% 5-HHEB(F,F)-F (3-12) 3% 2-HBEB(F,F) F (3-39) 3% 3-HBEB(F,F)-F (3-39) 4% 5-HBEB(F,F)-F (3-39) 3% 3-HHBB(F,F)-F (4-6) 5%

(149) NI=80.3 C.; =21.9 mPa.Math.s; n=0.112; =8.0.

Example 23

(150) TABLE-US-00010 2O-B(2F,3F)bt(7F)-3 (No. 35) 5% 3-HB-CL (2-2) 6% 5-HB-CL (2-2) 4% 3-HHB-OCF3 (3-1) 5% 3-H2HB-OCF3 (3-13) 5% 5-H4HB-OCF3 (3-13) 13% V-HHB(F)-F (3-3) 5% 3-HHB(F)-F (3-3) 4% 5-HHB(F)-F (3-3) 5% 3-H4HB(F,F)-CF3 (3-21) 8% 5-H4HB(F,F)-CF3 (3-21) 9% 5-H2HB(F,F)-F (3-15) 5% 5-H4HB(F,F)-F (3-21) 7% 2-H2BB(F)-F (3-14) 4% 3-H2BB(F)-F (3-14) 10% 3-HBEB(F,F)-F (3-39) 5%

Example 24

(151) TABLE-US-00011 2O-bt(7F)B(2F,3F)-O2 (No. 14) 5% 5-HB-CL (2-2) 17% 7-HB(F,F)-F (2-4) 3% 3-HH-4 (13-1) 10% 3-HH-5 (13-1) 3% 3-HB-O2 (13-5) 12% 3-HHB-1 (14-1) 8% 3-HHB-O1 (14-1) 5% 2-HHB(F)-F (3-2) 7% 3-HHB(F)-F (3-2) 7% 5-HHB(F)-F (3-2) 7% 3-HHB(F,F)-F (3-3) 6% 3-H2HB(F,F)-F (3-15) 5% 4-H2HB(F,F)-F (3-15) 5%

Example 25

(152) TABLE-US-00012 2O-bt(7F)1OB(2F,3F)-O2 (No. 32) 5% 5-HB-CL (2-2) 3% 7-HB(F)-F (2-3) 6% 3-HH-4 (13-1) 8% 3-HH-EMe (13-2) 22% 3-HHEB-F (3-10) 8% 5-HHEB-F (3-10) 8% 3-HHEB(F,F)-F (3-12) 10% 4-HHEB(F,F)-F (3-12) 4% 4-HGB(F,F)-F (3-103) 4% 5-HGB(F,F)-F (3-103) 6% 2-H2GB(F,F)-F (3-106) 4% 3-H2GB(F,F)-F (3-106) 5% 5-GHB(F,F)-F (3-109) 7%

Example 26

(153) TABLE-US-00013 3-Dhbt(7F)-3 (No. 37) 4% 1V2-BEB(F,F)-C (5-15) 6% 3-HB-C (5-1) 15% 2-BTB-l (13-10) 10% 5-HH-VFF (13-1) 29% 3-HHB-1 (14-1) 4% VFF-HHB-1 (14-1) 8% VFF2-HHB-1 (14-1) 11% 3-H2BTB-2 (14-17) 5% 3-H2BTB-3 (14-17) 4% 3-H2BTB-4 (14-17) 4%

Example 27

(154) TABLE-US-00014 2O-bt(7F)xH-3 (No. 30) 5% 3-GB(F)B(F,F)XB(F,F)-F (4-57) 5% 3-BB(F)B(F,F)XB(F,F)-F (4-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (4-47) 5% 5-BB(F)B(F,F)XB(F,F)-F (4-47) 3% 3-HH-V (13-1) 41% 3-HH-V1 (13-1) 6% 3-HHEH-5 (14-13) 3% 3-HHB-1 (14-1) 4% V-HHB-1 (14-1) 4% V2-BB(F)B-1 (14-6) 5% 1V2-BB-F (2-1) 3% 3-BB(F,F)XB(F,F)-F (3-97) 10% 3-HHBB(F,F)-F (4-6) 3%

Example 28

(155) TABLE-US-00015 2O-bt(7F)dh-3 (No. 24) 5% 3-GB(F)B(F,F)XB(F,F)-F (4-57) 5% 3-BB(F)B(F,F)XB(F,F)-F (4-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (4-47) 6% 5-BB(F)B(F,F)XB(F,F)-F (4-47) 3% 3-HH-V (13-1) 38% 3-HH-V1 (13-1) 7% 3-HHEH-5 (14-13) 3% 3-HHB-1 (14-1) 4% V-HHB-1 (14-1) 4% V2-BB(F)B-1 (14-6) 5% 1V2-BB-F (2-1) 3% 3-BB(F,F)XB(F,F)-F (3-97) 6% 3-GB(F,F)XB(F,F)-F (3-113) 5% 3-HHBB(F,F)-F (4-6) 3%

Example 29

(156) TABLE-US-00016 2O-bt(7F)B(2F)B-3 (No. 56) 3% 2O-bt(7F)B(2F,3F)-O2 (No. 14) 1% 7-HB(F,F)-F (2-3) 3% 3-HB-O2 (13-5) 7% 2-HHB(F)-F (3-2) 8% 3-HHB(F)-F (3-2) 9% 5-HHB(F)-F (3-2) 9% 2-HBB(F)-F (3-23) 9% 3-HBB(F)-F (3-23) 9% 5-HBB(F)-F (3-23) 16% 2-HBB-F (3-22) 4% 3-HBB-F (3-22) 4% 5-HBB-F (3-22) 3% 3-HBB(F,F)-F (3-24) 5% 5-HBB(F,F)-F (3-24) 10%

(157) NI=89.2 C.; =26.5 mPa.Math.s; n=0.127; =5.7.

Example 30

(158) TABLE-US-00017 2O-bt(7F)B(2F)B-5 (No. 241) 3% 2O-bt(7F)B(2F,3F)O1H-3 (No. 243) 1% 5-HB-F (2-2) 12% 6-HB-F (2-2) 9% 7-HB-F (2-2) 7% 2-HHB-OCF3 (3-1) 7% 3-HHB-OCF3 (3-1) 5% 4-HHB-OCF3 (3-1) 7% 5-HHB-OCF3 (3-1) 5% 3-HH2B-OCF3 (5-36) 4% 5-HH2B-OCF3 (5-36) 4% 3-HHB(F,F)-OCF2H (5-30) 3% 3-HHB(F,F)-OCF3 (5-30) 4% 3-HH2B(F)-F (5-37) 3% 3-HBB(F)-F (5-32) 10% 5-HBB(F)-F (5-32) 10% 5-HBBH-3 (15-1) 3% 3-HB(F)BH-3 (15-2) 3%

(159) NI=89.0 C.; =16.2 mPa.Math.s; n=0.102; =4.4.

Example 31

(160) TABLE-US-00018 2O-bt(7F)B(2F)B-O4 (No. 242) 3% 2O-bt(7F)B(F,F)XB(F,F)-F (No. 247) 1% 5-HB-CL (2-2) 3% 7-HB(F)-F (2-3) 7% 3-HH-4 (13-1) 9% 3-HH-EMe (13-2) 22% 3-HHEB-F (3-10) 8% 5-HHEB-F (3-10) 8% 3-HHEB(F,F)-F (3-12) 10% 4-HHEB(F,F)-F (3-12) 5% 4-HGB(F,F)-F (3-103) 4% 5-HGB(F,F)-F (3-103) 5% 2-H2GB(F,F)-F (3-106) 4% 3-H2GB(F,F)-F (3-106) 5% 5-GHB(F,F)-F (3-109) 6%

(161) NI=84.4 C.; =21.5 mPa.Math.s; n=0.076; =6.0.

Example 32

(162) TABLE-US-00019 2O-bt(7F)B(2F)-3 (No. 244) 4% 2O-bt(7F)B(2F)B-4 (No. 249) 5% 3-HB-O2 (13-5) 10% 5-HB-CL (2-2) 11% 3-HBB(F,F)-F (3-24) 8% 3-PyB(F)-F (3-81) 10% 5-PyB(F)-F (3-81) 10% 3-PyBB-F (3-80) 7% 4-PyBB-F (3-80) 8% 5-PyBB-F (3-80) 9% 5-HBB(F)B-2 (15-5) 9% 5-HBB(F)B-3 (15-5) 9%

(163) NI=99.7 C.; =40.7 mPa.Math.s; n=0.119; =7.7.

INDUSTRIAL APPLICABILITY

(164) A liquid crystal compound of the invention has high stability to heat, light and so forth, a high clearing point, low minimum temperature of a liquid crystal phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, a suitable elastic constant and excellent compatibility with other liquid crystal compounds. A liquid crystal composition of the invention contains the compound, and has high maximum temperature of a nematic phase, low minimum temperature of the nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy and a suitable elastic constant. The composition has a suitable balance regarding at least two of physical properties. A liquid crystal display device of the invention includes the composition, and has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, low threshold voltage, a large contrast ratio and along service life. Accordingly, the device can be widely used in a display of a personal computer, a television and so forth.