Tetrahydropyran compound, liquid crystal composition and liquid crystal display device

Abstract

A compound represented by formula (1-1) or (1-2) is provided. ##STR00001##
For example, R.sup.1 and R.sup.2 are independently hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; the ring A.sup.1, the ring A.sup.2, the ring A.sup.3, the ring A.sup.4, the ring A.sup.5 and the ring A.sup.6 are independently 1,4-cyclohexylene or 1,4-phenylene; a, b, c, d, e and f are independently 0 or 1, and the sum of a, b, c, d, e and f is 2; and g, h, i, j, k and l are independently 0 or 1, and the sum of g, h, i, j, k and l is 2.

Claims

1. A compound represented by formula (1-1-1), (1-1-3), (1-1-4), or (1-1-6): ##STR00410## wherein R.sup.1 and R.sup.2 are independently hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; the ring A.sup.1, the ring A.sup.2, the ring A.sup.3, the ring A.sup.4, the ring A.sup.5 and the ring A.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyrimidine-3,6-diyl, pyridine-2,5-diyl or pyridine-3,6-diyl.

2. The compound according to claim 1, wherein in formula (1-1-1) according to claim 1, the ring A.sup.1 and the ring A.sup.2 are 1,4-cyclohexylene.

3. A compound represented by formula (1-1-2) or (1-2-2): ##STR00411## wherein R.sup.1 and R.sup.2 are independently hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; and the ring A.sup.1 and the ring A.sup.3 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyrimidine-3,6-diyl, pyridine-2,5-diyl or pyridine-3,6-diyl.

4. The compound according to claim 3, wherein in formulas (1-1-2) and (1-2-2) according to claim 3, the ring A.sup.1 and the ring A.sup.3 are 1,4-cyclohexylene.

5. The compound according to claim 1, wherein in formulas (1-1-3) according to claim 1, the ring A.sup.3 and the ring A.sup.4 are 1,4-cyclohexylene.

6. The compound according to claim 1, wherein in formula (1-1-4) according to claim 1, the ring A.sup.1 and the ring A.sup.5 are 1,4-cyclohexylene.

7. A compound represented by formula (1-1-5) or (1-2-5): ##STR00412## wherein R.sup.1 and R.sup.2 are independently hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; and the ring A.sup.3 and the ring A.sup.5 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyrimidine-3,6-diyl, pyridine-2,5-diyl or pyridine-3,6-diyl.

8. The compound according to claim 7, wherein in formula (1-1-5) or (1-2-5) according to claim 7, the ring A.sup.3 and the ring A.sup.5 are 1,4-cyclohexylene.

9. The compound according to claim 1, wherein in formula (1-1-6) according to claim 1, the ring A.sup.5 and the ring A.sup.6 are 1,4-cyclohexylene.

10. A compound represented by any one of formulas (1-A) to (1-F): ##STR00413## wherein R.sup.1 and R.sup.2 are independently hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; the ring A.sup.1 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydropyran-3,6-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyrimidine-3,6-diyl, pyridine-2,5-diyl or pyridine-3,6-diyl, the ring A.sup.11 and the ring A.sup.21 are independently tetrahydropyran-2,5-diyl or tetrahydropyran-3,6-diyl; and the ring A.sup.22, the ring A.sup.32 and the ring A.sup.52 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyrimidine-3,6-diyl, pyridine-2,5-diyl or pyridine-3,6-diyl.

11. The compound according to claim 10, wherein in formulas (1-A) to (1-F) according to claim 10, the ring A.sup.1, the ring A.sup.22, the ring A.sup.32 and the ring A.sup.52 are 1,4-cyclohexylene.

12. A liquid crystal composition including a first component and a second component, wherein the first component is at least one selected from compounds according to claim 1.

13. The liquid crystal composition according to claim 12, including at least one compound selected from the group of compounds represented by formulas (2) to (4) as the second component: ##STR00414## wherein R.sup.3 is independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one hydrogen may be replaced by fluorine and at least one CH.sub.2 may be replaced by O; X.sup.1 is independently 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; the ring B.sup.1, the ring B.sup.2 and the ring B.sup.3 are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, tetrahydropyran-2,5-diyl or 1,4-phenylene in which at least one hydrogen may be replaced by fluorine; Z.sup.5 and Z.sup.6 are independently (CH.sub.2).sub.2, (CH.sub.2).sub.4, COO, CF.sub.2O, OCF.sub.2, CHCH, CC, CH.sub.2O or a single bond; and L.sup.1 and L.sup.2 are independently hydrogen or fluorine.

14. The liquid crystal composition according to claim 12, including at least one compound selected from the group of compounds represented by formula (5) as the second component: ##STR00415## wherein R.sup.4 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one hydrogen may be replaced by fluorine and at least one CH2 may be replaced by O; X.sup.2 is CN or CCCN; the ring C.sup.1, the ring C.sup.2 and the ring C.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.7 is (CH.sub.2).sub.2, COO, CF.sub.2O, OCF.sub.2, CC, CH.sub.2O or a single bond; L.sup.3 and L.sup.4 are independently hydrogen or fluorine; and o is 0, 1 or 2, and p is 0 or 1.

15. The liquid crystal composition according to claim 12, including at least one compound selected from the group of compounds represented by formulas (6) to (11) as the second component: ##STR00416## wherein R.sup.5 and R.sup.6 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl at least one CH.sub.2may be replaced by O, and in the alkenyl at least one hydrogen may be replaced by fluorine; the ring D.sup.1, the ring D.sup.2, the ring D.sup.3 and the ring D.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine or tetrahydropyran-2,5-diyl; Z.sup.8, Z.sup.9, Z.sup.10, and Z.sup.11 are independently (CH.sub.2).sub.2, COO, CH.sub.2O, OCF.sub.2, OCF.sub.2(CH.sub.2).sub.2 or a single bond; L.sup.5 and L.sup.6 are independently fluorine or chlorine; and q, r, s, t, u and v are independently 0 or 1, and the sum of r, s, t and u is 1 or 2.

16. The liquid crystal composition according to claim 12, including at least one compound selected from the group of compounds represented by formulas (12) to (14) as the second component: ##STR00417## wherein R.sup.7 and R.sup.8 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl at least one CH.sub.2 may be replaced by O, and in the alkenyl at least one hydrogen may be replaced by fluorine; the ring E.sup.1, the ring E.sup.2 and the ring E.sup.3 are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; and Z.sup.12 and Z.sup.13 are independently CC, COO, (CH.sub.2).sub.2, CHCH or a single bond.

17. The liquid crystal composition according to claim 13, further including at least one compound selected from the group of compounds represented by formula (5): ##STR00418## wherein R.sup.4 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one hydrogen may be replaced by fluorine and at least one CH.sub.2 may be replaced by O; X.sup.2 is CN or CCCN; the ring C.sup.1, the ring C.sup.2 and the ring C.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.7 is (CH.sub.2).sub.2, COO, CF.sub.2O, OCF.sub.2, CC, CH.sub.2O or a single bond; L.sup.3 and L.sup.4 are independently hydrogen or fluorine; and o is 0, 1 or 2, and p is 0 or 1.

18. The liquid crystal composition according to claim 13, further including at least one compound selected from the group of compounds represented by formulas (12) to (14): ##STR00419## wherein R.sup.7 and R.sup.8 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl at least one CH.sub.2 may be replaced by O, and in the alkenyl at least one hydrogen may be replaced by fluorine; the ring E.sup.1, the ring E.sup.2 and the ring E.sup.3 are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; and Z.sup.12 and Z.sup.13 are independently CC, COO, (CH.sub.2).sub.2, CHCH or a single bond.

19. The liquid crystal composition according to claim 14, further including at least one compound selected from the group of compounds represented by formulas (12) to (14): ##STR00420## wherein R.sup.7 and R.sup.8 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl at least one CH.sub.2 may be replaced by O, and in the alkenyl at least one hydrogen may be replaced by fluorine; the ring E.sup.1, the ring E.sup.2 and the ring E.sup.3 are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; and Z.sup.12 and Z.sup.13 are independently CC, COO, (CH.sub.2).sub.2, CHCH or a single bond.

20. The liquid crystal composition according to claim 15, further including at least one compound selected from the group of compounds represented by formulas (12) to (14): ##STR00421## wherein R.sup.7 and R.sup.8 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl at least one CH.sub.2 may be replaced by O, and in the alkenyl at least one hydrogen may be replaced by fluorine; the ring E.sup.1, the ring E.sup.2 and the ring E.sup.3 are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; and Z.sup.12 and .sup.13 are independently CC, COO, (CH.sub.2).sub.2, CHCH or a single bond.

21. The liquid crystal composition according to claim 12, further including at least one optically active compound and/or at least one polymerizable compound.

22. The liquid crystal composition according to claim 12, further including at least one antioxidant and/or at least one ultraviolet light absorber.

23. A liquid crystal display device containing the liquid crystal composition according to claim 12.

Description

EXAMPLES

(1) The invention will be explained below in more detail based on examples, and the invention is not limited to the examples at the same time. The term % means % by weight, unless otherwise noted.

(2) Analytical methods will be explained first, since the resulting compounds herein were identified on the basis of nuclear magnetic resonance spectra obtained by means of .sup.1H-NMR analysis, gas chromatograms obtained by means of gas chromatography (GC) analysis and so forth.

(3) .sup.1H-NMR Analysis:

(4) A model DRX-500 apparatus (made by Bruker BioSpin Corporation) was used for measurement. Samples prepared in the examples and so forth were dissolved in deuterated solvents such as CDCl.sub.3 in which the samples were soluble, and the measurement was carried out under the conditions of room temperature, twenty-four times of accumulation and 500 MHz. Tetramethylsilane (TMS) was used as the standard reference material for the zero point of the chemical shift ( values).

(5) GC Analysis

(6) A Gas Chromatograph Model GC-14B made by Shimadzu Corporation was used for measurement. A capillary column CBP1-M25-025 (length 25 m, bore 0.22 mm, film thickness 0.25 micrometer; dimethylpolysiloxane as a stationary liquid phase; non-polar) made by Shimadzu Corporation was used. Helium was used as a carrier gas, and its flow rate was adjusted to 1 ml per minute. The temperature of the sample injector was set at 280 C. and the temperature of the detector (FID) was set at 280 C.

(7) A sample was dissolved in toluene to give a 1% by weight solution, and then 1 microliter of the resulting solution was injected into the sample injector.

(8) Chromatopac Model C-R6A made by Shimadzu Corporation or its equivalent was used as a recorder. The resulting gas chromatogram showed the retention time of the peaks and the values of the peak areas corresponding to the component compounds.

(9) Incidentally, chloroform or hexane, for example, may also be used as a solvent for diluting the sample. The following capillary columns may also be used: DB-1 (length 30 m, bore 0.32 mm, film thickness 0.25 micrometer) made by Agilent Technologies Inc., HP-1 (length 30 m, bore 0.32 mm, film thickness 0.25 micrometer) made by Agilent Technologies Inc., Rtx-1 (length 30 m, bore 0.32 mm, film thickness 0.25 micrometer) made by Restek Corporation, BP-1 (length 30 m, bore 0.32 mm, film thickness 0.25 micrometer) made by SGE International Pty. Ltd, and so forth.

(10) The ratio of the peak areas in the gas chromatogram corresponds to the ratio of component compounds. In general, the percentage by weight of each component compound in an analytical sample is not completely the same as the percentage of each peak area in the analytical sample. In the invention, however, the percentage by weight of the component compound in the analytical sample corresponds substantially to the percentage of the peak area in the analytical sample, because the correction coefficient is essentially 1 (one) when the columns described above are used.

(11) Samples for the Measurement of the Physical Properties of Liquid Crystal Compounds and so Forth

(12) Two kinds of samples are used for measuring the physical properties of a liquid crystal compound: one is the compound itself, and the other is a mixture of the compound and mother liquid crystals.

(13) In the latter case using a sample in which the compound is mixed with mother liquid crystals, the measurement is carried out according to the following method. First, the sample is prepared by mixing 15% by weight of the liquid crystal compound obtained and 85% by weight of the mother liquid crystals. Then, extrapolated values are calculated from the measured values of the resulting sample by applying the following formula (extrapolation method). The extrapolated values are regarded as the physical properties of this compound.
[Extrapolated value]=(100[Measured value of sample][by weight of mother liquid crystals][Measured value of mother liquid crystals])/[% by weight of liquid crystal compound]

(14) When a smectic phase appears at 25 C. or crystals deposit at 25 C. in the sample described above, the ratio of the liquid crystal compound to the mother liquid crystals is changed in the order of (10% by weight: 90% by weight), (5% by weight: 95% by weight) and (1% by weight: 99% by weight). The physical properties of the sample are measured at the ratio in which the smectic phase does not appear at 25 C. or the crystals does not deposit at 25 C. Extrapolated values are determined according to the above equation, and are regarded as the physical properties of the liquid crystal compound.

(15) There are a variety of mother liquid crystals used for measurement and, for example, each component (% by weight) of the mother liquid crystals (A) is shown below.

(16) TABLE-US-00001 Mother liquid crystals (A): 17.2% 0 27.6% 20.7% 20.7% 13.8%

(17) Incidentally, in the case where the physical properties of a liquid crystal composition were measured, the liquid crystal composition itself was used as a sample.

(18) Methods for Measurements of the Physical Properties of Liquid Crystal Compounds and so Forth

(19) The physical properties of compounds were measured according to the following methods. Most are measurement methods described in the Standard of Electronic Industries Association of Japan, EIAJED-2521A, or the modified methods. No TFT was attached to a TN device or a VA device used for measurement.

(20) In measured values, when a liquid crystal compound itself or a liquid crystal composition itself was employed as a sample, a measured value itself was described here as experimental data. When a sample was prepared by mixing the compound with mother liquid crystals, values calculated from measured values according to the extrapolation method was described here as extrapolated values.

(21) Phase Structure and Transition Temperature ( C.)

(22) Measurements were carried out according to the following methods (1) and (2).

(23) (1) A compound was placed on a hot plate of a melting point apparatus (Hot Stage Model FP-52 made by Mettler Toledo International Inc.) equipped with a polarizing microscope, and the phase conditions and their changes were observed with the polarizing microscope, specifying the kind of phase while the compound was heated at the rate of 3 C. per minute.

(24) (2) A sample was heated and then cooled at the rate of 3 C. per minute using a Perkin-Elmer differential scanning calorimeter, a DSC-7 System or a Diamond DSC System. The starting point of an endothermic peak or an exothermic peak caused by the phase change of the sample was obtained by means of the extrapolation, and thus the phase transition temperature was determined.

(25) Hereinafter, the symbol C stood for crystals, which were expressed as C.sub.1 or C.sub.2 when the kind of crystals was distinguishable. The symbols S and N stood for a smectic phase and a nematic phase, respectively. The symbol Iso stood for a liquid (isotropic). When a smectic B phase or a smectic A were distinguishable in the smectic phases, they were expressed as S.sub.B and S.sub.A, respectively. Phase-transition temperatures were expressed as, for example, C 50.0 N 100.0 Iso, which means that the phase-transition temperature from crystals to a nematic phase (CN) is 50.0 C., and the phase-transition temperature from the nematic phase to a liquid (NI) is 100.0 C. The same applied to the other transition temperatures.

(26) Maximum Temperature of a Nematic Phase (T.sub.NI; C.):

(27) A sample (a liquid crystal composition, or a mixture of a liquid crystal compound and mother liquid crystals) was placed on a hot plate of a melting point apparatus (Hot Stage Model FP-52 made by Mettler Toledo International Inc.) equipped with a polarizing microscope, and was observed with the polarizing microscope while being heated at the rate of 1 C. per minute. A maximum temperature meant a temperature measured when part of the sample began to change from a nematic phase to an isotropic liquid. Hereinafter, the maximum temperature of a nematic phase may simply be abbreviated to the maximum temperature.

(28) Compatibility at Low Temperatures:

(29) Samples were prepared by mixing a liquid crystal compound with mother liquid crystals so that the amount of the liquid crystal compound became 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight and 1% by weight, and were placed in glass vials. After these glass vials had been kept in a freezer at 10 C. or 20 C. for a certain period of time, they were observed as to whether or not crystals or a smectic phase had been deposited.

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

(31) It is characterized that as viscosity is decreased, response time decreases.

(32) An E-type viscometer was used for measurement.

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

(34) It is characterized that as rotational viscosity is decreased, response time decreases.

(35) Rotational viscosity was measured according to the method described in M. Imai, et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample (a liquid crystal composition, or a mixture of a liquid crystal compound and mother liquid crystals) was poured into a VA device in which the distance between the two glass substrates (cell gap) was 20 micrometers. A voltage in the range of 30 V to 50 V was applied stepwise with an increment of 1 volt to the device. After a period of 0.2 second with no voltage, a voltage was applied repeatedly under the conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds). The peak current and the peak time of the transient current generated by the applied voltage were measured. The value of rotational viscosity was obtained from the measured values and the calculating equation (8) on page 40 of the paper presented by M. Imai, et al. Incidentally, the value of the dielectric anisotropy () necessary for the present calculation was obtained by the method described below under the heading Dielectric Anisotropy.

(36) Refractive Index Anisotropy (n; Measured at 25 C.)

(37) Measurement was carried out using an Abbe refractometer with a polarizing plate attached to the ocular, on irradiation with light at a wavelength of 589 nm at a temperature of 25 C. The surface of the main prism was rubbed in one direction, and then a sample (a liquid crystal composition, or a mixture of a liquid crystal compound and mother liquid crystals) was dropped onto the main prism. The refractive index (n) was measured when the direction of the polarized light was parallel to that of the rubbing. The refractive index (n) was measured when the direction of polarized light was perpendicular to that of the rubbing. The value of the refractive index anisotropy was calculated from the equation: n=nn.

(38) Dielectric Anisotropy (; Measured at 25 C.)

(39) An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-washed glass substrate. The glass substrate was rotated with a spinner, and then heated at 150 C. for 1 hour. A VA device in which the distance (cell gap) was 20 micrometers was assembled from the two glass substrates.

(40) A polyimide alignment film was prepared on glass substrates in a similar manner. After a rubbing-treatment to the alignment film formed on the glass substrates, a TN device in which the distance between the two glass substrates was 9 micrometers and the twist angle was 80 degrees was assembled.

(41) A sample (a liquid crystal composition, or a mixture of a liquid crystal compound and mother liquid crystals) was poured into the resulting VA device, a voltage of 0.5 V (1 kHz, sine waves) was applied to the sample, and then the dielectric constant () in the major axis direction of the liquid crystal molecules was measured.

(42) The sample (the liquid crystal composition, or the mixture of the liquid crystal compound and the mother liquid crystals) was poured into the resulting TN device, a voltage of 0.5 V (1 kHz, sine waves) was applied to the sample, and then the dielectric constant () in the minor axis direction of the liquid crystal molecules was measured.

(43) The value of the dielectric anisotropy was calculated from the equation of =.

Example 1

Preparation of trans-5-(4-ethoxy-2,3-difluorophenyl)-2-(trans-4-propylbi(cyclohexane)-trans-4-yl)tetrahydro-2H-pyran (No. 1)

(44) ##STR00074##

(45) First Step:

(46) trans-4-Propylbi(cyclohexane)-trans-4-carboxylic acid (1) (30.0 g; 0.119 mmol) in a toluene (200 ml) solution was heated at 50 C. in a reaction vessel under an atmosphere of nitrogen. Pyridine (0.05 ml) and thionyl chloride (14.9 g; 0.125 mmol) were added, and the mixture was stirred for 3 hours. The unreacted thionyl chloride was distilled off at ordinary pressure, and then the solvent was distilled off under reduced pressure to give trans-4-propylbi(cyclohexane)-trans-4-carboxylic acid chloride (2). The compound was used in the following reaction without further purification.

(47) Second Step:

(48) Lithium diisopropylamide (1.08M in tetrahydrofuran solution; 198 ml; 0.202 mmol) was added to tetrahydrofuran (300 ml) in a reaction vessel under an atmosphere of nitrogen, and the solution was cooled to 65 C. or less. Ethyl acetate (18.2 g; 0.207 mmol), and then a tetrahydrofuran (100 ml) solution of trans-4-propylbi(cyclohexane)-trans-4-carboxylic acid chloride (2) (32.0 g; 0.119 mmol) obtained in the first step were added dropwise. The reaction mixture was slowly warmed up to room temperature with stirring, and then it was quenched with a saturated aqueous solution of ammonium chloride. Water (500 ml) was added to give two layers. The aqueous layer was extracted with toluene (300 ml) three times. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent toluene) to give (3-oxo-3-(trans-4-propylbi(cyclohexane)-trans-4-yl)propion ic acid ethyl ester (3) (34.5 g; 90% yield).

(49) Third Step:

(50) A tetrahydrofuran (100 ml) solution of (3-oxo-3-(trans-4-propylbi(cyclohexane)-trans-4-yl)propionic acid ethyl ester (3) (34.5 g; 0.107 mmol) obtained in the second step was added dropwise to sodium borohydride (12.1 g; 0.321 mmol) in a ethanol (100 ml) suspension in a reaction vessel at 50 C. or less under an atmosphere of nitrogen, and the mixture was reacted at room temperature for 5 hours. The reaction mixture was quenched with water (500 ml), and ethyl acetate (200 ml) was added to give two layers. The aqueous layer was extracted with ethyl acetate (100 ml) twice. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent heptane/ethyl acetate=50/50 by volume) to give 1-(trans-4-propylbi(cyclohexane)-trans-4-yl) propane-1,3-diol (4) (22.7 g; 74% yield).

(51) Fourth Step:

(52) Tetrahydrofuran (100 ml) was added to 1-(trans-4-propylbi(cyclohexane)-trans-4-yl)propane-1,3-diol (4) (9.4 g; 33.3 mmol) obtained in the third step in a reaction vessel under an atmosphere of nitrogen. n-Butyllithium (1.66 M in n-hexane solution; 20.0 ml; 33.2 mmol) was added dropwise to the solution at temperatures of around 5 C. After 30 minutes of stirring, p-toluenesulfonyl chloride (6.34 g; 33.3 mmol) in a tetrahydrofuran (50 ml) solution was added dropwise. After the reaction mixture had been stirred for 30 minutes, n-butyllithium (1.66M in n-hexane solution; 20.0 ml; 33.2 mmol) was added dropwise at temperatures of around 5 C. The reaction mixture was slowly heated to the refluxing temperature. After the evolution of gas had ceased, the reaction mixture was cooled to room temperature, and quenched with a saturated aqueous solution of ammonium chloride. Water (200 ml) was added to give two layers. The aqueous layer was extracted with toluene (100 ml) twice. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent toluene) to give 2-(trans-4-propylbi(cyclohexane)-trans-4-yl)oxetane (5) (6.2 g; 70% yield).

(53) Fifth Step:

(54) n-Butyllithium (1.66 M in n-hexane solution; 33.9 ml; 56.25 mmol) was added dropwise to a THF (100 ml) solution of 2-(4-ethoxy-2,3-difluorophenyl)acetic acid (6) (6.08 g; 28.13 mmol), which was prepared by a general method, in a reaction vessel at 5 C. under an atmosphere of nitrogen. The reaction mixture was then returned to room temperature, and the stirring was continued for another 30 minutes. The solution was cooled to 65 C., and a tetrahydrofuran (30 ml) solution of 2-(trans-4-propylbi(cyclohexane)-trans-4-yl)oxetane (5) (6.2 g; 23.44 mmol) obtained in the fourth step and a boron trifluoride-diethyl ether complex (3.66 g; 25.79 mmol) were added dropwise. The reaction mixture was returned to room temperature, and it was reacted for 3 hours. A 10% aqueous solution of formic acid (100 ml) was added to the reaction mixture to give two layers. The aqueous layer was extracted with toluene (20 ml) three times. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 50 g; eluent heptane/ethyl acetate=80/20 by volume) to give 3-(4-ethoxy-2,3,-difluorophenyl)-6-(trans-4-propylbi(cyclohexane)-trans-4-yl)tetrahydro-2H-pyran-2-one (7) (9.35 g; 86.2% yield).

(55) Sixth Step:

(56) Diisobutylaluminum hydride (0.99M in toluene solution; 40.8 ml; 40.4 mmol) was added dropwise to a tetrahydrofuran (100 ml) solution of 3-(4-ethoxy-2,3,-difluorophenyl)-6-(trans-4-propylbi(cyclohexane)-trans-4-yl)tetrahydro-2H-pyran-2-one (7) (9.35 g; 20.2 mmol) obtained in the fifth step in a reaction vessel at 50 C. or less under an atmosphere of nitrogen, and the mixture was reacted for 3 hours. The reaction mixture was poured into a 10% aqueous solution of formic acid (50 ml) to give two layers. The aqueous layer was extracted with toluene (100 ml) twice. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 3-(4-ethoxy-2,3-difluorophenyl)-6-(4-propylbi(cyclohexane)-4-yl)tetrahydro-2H-pyran-2-ol (8) (9.36 g; 99% yield).

(57) Seventh Step:

(58) Triethylsilane (1.93 g) and a boron trifluoride-ethyl ether complex (2.37 g) were added dropwise at 30 C. to a dichloromethane (30 ml) solution of 3-(4-ethoxy-2,2,3,3-tetrafluorobiphenyl-4-yl)-6-(4-propylcyclohexyl)tetrahydro-2H-pyran-2-ol (8) (11.0 g; 23.7 mmol) obtained in the sixth step. The reaction mixture was returned to room temperature, and the stirring was continued for another 3 hours. Water (30 ml) was added to give two layers. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent: heptane/ethyl acetate=80/20 by volume) and then by recrystallization (heptane/ethyl acetate=80/20 by volume) to give trans-5-(4-ethoxy-2,3-difluorophenyl)-2-(trans-4-propylbi(cyclohexane)-trans-4-yl)tetrahydro-2H-pyran (9) (the compound No. 1; 3.1 g; 29% yield).

(59) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(4-ethoxy-2,3-difluorophenyl)-2-(trans-4-propyl bi(cyclohexane)-trans-4-yl)tetrahydro-2H-pyran(9). The solvent for measurement was CDCl.sub.3.

(60) Chemical shift ( ppm): 6.80 (dt, 1H), 6.67 (dt, 1H), 4.19 (q, 2H), 4.02-3.97 (m, 1H), 3.37 (t, 1H), 3.07-3.00 (m, 2H), 2.03-1.95 (m, 2H), 1.83-1.67 (m, 10H), 1.46-0.90 (m, 17H) and 0.90-0.75 (m, 5H)

(61) The phase transition temperature of the resulting compound (9), that is to say, the compound No. 1 was as follows.

(62) Transition temperature: C 83.6 SB 250.3 N 310.1 Iso.

Example 2

Preparation of trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran (No. 41)

(63) ##STR00075##

(64) First Step:

(65) N,N-Dicyclohexylcarbodiimide (DCC; 24.8 g; 0.12 mol) was added to a dichloromethane (300 ml) solution of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid (10) (29.8 g; 0.10 mol), 4-di(methylamino)pyridine (DMAP; 1.22 g; 0.01 mol) and t-butanol (8.88 g; 0.12 mol) in a reaction vessel with ice-cooling under an atmosphere of nitrogen. After 8 hours of stirring at room temperature, insoluble matters deposited were filtered off, and water (300 ml) was added to the filtrate to give two layers. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent toluene) to give 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid t-butyl ester (11) (18.3 g; 52% yield).

(66) Second Step:

(67) Lithium diisopropylamide(LDA; 1.98M in tetrahydrofuran solution; 52 ml; 0.103 mol) was added dropwise at 60 C. to a tetrahydrofuran (200 ml) solution of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid t-butyl ester (11) (18.3 g; 51.7 mmol) obtained in the first step, and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was cooled to 90 C. or less. A tetrahydrofuran (10 ml) solution of 2-(trans-4-pentylcyclohexyl)oxetane (12) (9.05 g; 43.1 mmol) which was prepared by a general method and a boron trifluoride-ethyl ether complex (6.12 g; 43.1 mmol) were added dropwise. After 3 hours of stirring at 70 C. or less, a saturated aqueous solution of ammonium chloride was added to give two layers. The aqueous layer was extracted with toluene (50 ml) three times. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent heptane/ethyl acetate=80/20 by volume) to give 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-5-hydroxy-5-(trans-4-pentylcyclohexyl)pentanoic acid t-butyl ester (13) (15.4 g; 63% yield).

(68) Third Step:

(69) Trifluoroacetic acid (TFA; 13.2 ml; 135.5 mmol) was added dropwise to a dichloromethane (100 ml) solution of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-5-hydroxy-5-(trans-4-pentylcyclohexyl)pentanoic acid t-butyl ester (13) (15.4 g; 27.1 mmol) obtained in the second step with ice-cooling, and the mixture was reacted at room temperature for 5 hours. The reaction mixture was poured into 100 ml to give two layers. The resulting organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent heptane/ethyl acetate=90/10 by volume) to give 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-one (14) (12.1 g; 91% yield).

(70) Fourth Step:

(71) Diisobutylaluminum hydride (0.99M in toluene solution; 69 ml; 68.2 mmol) was added dropwise to a tetrahydrofuran (200 ml) solution of 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-one (14) (15.2 g; 31.0 mmol) obtained in the third step in a reaction vessel at 50 C. or less under an atmosphere of nitrogen, and the mixture was reacted for 3 hours. The reaction mixture was poured into a 10% aqueous solution of formic acid (200 ml) to give two layers. The aqueous layer was extracted with toluene (100 ml) twice. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-ol (15) (15.2 g; 99% yield).

(72) Fifth Step:

(73) Triethylsilane (7.17 g; 61.8 mmol) and a boron trifluoride-ethyl ether complex (8.78 g; 61.8 mmol) were added dropwise at 30 C. to a dichloromethane (100 ml) solution of 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-ol (15) (15.2 g; 30.9 mmol) obtained in the fourth step. The reaction mixture was returned to room temperature, and it was reacted for 3 hours. Water (100 ml) was added to the reaction mixture to give two layers. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 200 g; eluent: heptane/ethyl acetate=80/20 by volume) and then by recrystallization (heptane/ethyl acetate=90/10 by volume) to give trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran (16) (the compound No. 41; 4.6 g; 31% yield).

(74) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran (16). The solvent for measurement was CDCl.sub.3.

(75) Chemical shift ( ppm): 6.81 (dt, 1H), 6.56 (dt, 1H), 4.16-4.02 (m, 3H), 3.13 (t, 1H), 2.91 (qd, 1H), 2.72 (tt, 1H), 1.97-1.64 (m, 10H) and 1.50-0.79 (m, 28H)

(76) The phase transition temperature of the resulting compound (16), that is to say, the compound No. 41 was as follows.

(77) Transition temperature: C 82.2 SB 257.2 N 298.1 Iso.

Example 3

Preparation of trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-pentyltetrahydro-2H-pyran (No. 109)

(78) ##STR00076##

(79) First Step:

(80) Lithium diisopropylamide (1.98M in tetrahydrofuran solution; LDA; 35 ml; 69.7 mmol) was added dropwise at 60 C. to a tetrahydrofuran (200 ml) solution of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)acetic acid t-butyl ester (17) (15.2 g; 34.9 mmol) prepared in a method similar to that in the compound (11), and the mixture was reacted at the same temperature for 1 hour. The reaction mixture was cooled to 90 C. or less, and a tetrahydrofuran (5 ml) solution of 2-pentyloxetane (18) (3.72 g; 29.1 mmol) prepared by the generally known method and a boron trifluoride-ethyl ether complex (2.37 g) were added dropwise. After 3 hours of stirring at temperatures of 70 C. or less, a saturated aqueous solution of ammonium chloride was added to give two layers. The aqueous layer was extracted with toluene (100 ml) three times. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 200 g; eluent: heptane/ethyl acetate=80/20 by volume) to give 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-5-hydroxydecanoic acid t-butyl ester (19) (10.8 g; 66% yield).

(81) Second Step:

(82) Trifluoroacetic acid (TFA; 7.4 ml; 96.6 mmol) was added dropwise to a dichloromethane (100 ml) solution of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-5-hydroxydecanoic acid t-butyl ester (19) (10.8 g; 19.1 mmol) obtained in the first step with ice-cooling, and the mixture was reacted at room temperature for 5 hours. The reaction mixture was poured into water (100 ml) to give two layers. The resulting organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent heptane/ethyl acetate=80/20 by volume) to give 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-one (20) (8.0 g; 85% yield).

(83) Third Step:

(84) A toluene solution of diisobutylaluminum hydride (0.99M; 36 ml; 35.6 mmol) was added dropwise to a tetrahydrofuran (100 ml) solution of 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-one (20) (8.0 g; 16.3 mmol) obtained in the second step in a reaction vessel at temperatures of 50 C. or less under an atmosphere of nitrogen, and the mixture was reacted for 3 hours. The reaction mixture was poured into a 10% aqueous solution of formic acid (50 ml) to give two layers. The aqueous layer was extracted with toluene (20 ml) twice. The combined organic layers were washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-6-pentyltetrahydro-2H-pyran-2-ol (21) (6.9 g; 86% yield).

(85) Fourth Step:

(86) Triethylsilane (3.25 g; 28.0 mmol) and a boron trifluoride-ethyl ether complex (3.98 g; 28.0 mmol) were added dropwise at 30 C. to a dichloromethane (50 ml) solution of 3-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-6-(trans-4-pentylcyclohexyl)tetrahydro-2H-pyran-2-ol (21) (6.9 g; 14.0 mmol) obtained in the third step. The reaction mixture was returned to room temperature, and the stirring was continued for another 3 hours. Water (50 ml) was added to the reaction mixture to give two layers. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (silica gel: 100 g; eluent heptane/ethyl acetate=80/20 by volume) and then by recrystallization (heptane/ethyl acetate=90/10 by volume) to give trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-pentyltetrahydro-2H-pyran (22) (the compound No. 109; 1.2 g; 18% yield).

(87) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-pentyltetrahydro-2H-pyran (22). The solvent for measurement was CDCl.sub.3.

(88) Chemical shift ( ppm): 6.83 (dt, 1H), 6.66 (dt, 1H), 4.12-4.05 (q, 2H), 4.01 (dq, 1H), 3.20-3.08 (m, 2H), 2.71 (tt, 1H) and 1.91-0.84 (m, 38H)

(89) The phase transition temperature of the resulting compound (22), that is to say, the compound No. 109 was as follows.

(90) Transition temperature: C 70.7 SB 265.5 N 309 Iso.

Example 4

Preparation of trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran (No. 44)

(91) trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran was prepared by a method similar to that described in Example 2, using 2-(trans-4-propylcyclohexyl)oxetane instead of 2-(trans-4-pentylcyclohexyl)oxetane in the second step of Example 2.

(92) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(93) Chemical shift ( ppm): 6.81 (dt, 1H), 6.66 (dt, 1H), 4.08 (q, 2H), 4.07-4.03 (m, 1H), 3.13 (t, 1H), 2.93-2.89 (m, 1H), 2.75-2.70 (m, 1H), 1.94-1.67 (m, 10H), 1.43 (t, 3H), 1.42-1.09 (m, 13H), 1.05-0.80 (m, 5H) and 0.87 (t, 3H).

(94) The phase transition temperature of the resulting compound (the compound No. 44) was as follows.

(95) Transition temperature: C 82.3 SB 233.2 N 299.8 Iso.

Example 5

Preparation of trans-5-(4-ethoxy-2,3-difluorobiphenyl-4-yl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran (No. 40)

(96) trans-5-(4-Ethoxy-2,3-difluorobiphenyl-4-yl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran was prepared by a method similar to that described in Example 2, using 2-(4-ethoxy-2,3-difluorobiphenyl-4-yl)acetic acid t-butyl ester instead of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid t-butyl ester in the second step of Example 2.

(97) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(4-ethoxy-2,3-difluorobiphenyl-4-yl)-2-(trans-4-propylcyclohexyl)tetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(98) Chemical shift ( ppm): 7.43 (d, 2H), 7.29 (d, 2H), 7.07 (td, 1H), 6.79 (td, 1H), 4.15 (q, 2H), 4.06 (dq, 2H), 3.42 (t, 1H), 3.10 (dq, 1H), 2.84 (t, 1H), 2.09 (d, 1H), 1.97 (d, 1H), 1.81-1.72 (m, 5H), 1.57-1.45 (m, 1H), 1.47 (t, 3H), 1.35-1.29 (m, 3H), 1.22-1.11 (m, 3H), 1.05 (sex, 1H) 0.95-0.81 (m, 2H) and 0.87 (t, 3H).

(99) The phase transition temperature of the resulting compound (the compound No. 40) was as follows.

(100) Transition temperature: C 70.3 SB 158.8 SA 184.0 N 293.1 Iso.

Example 6

Preparation of trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-propyltetrahydro-2H-pyran (No. 108)

(101) trans-5-(trans-4-(4-Ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-propyltetrahydro-2H-pyran was prepared by a method similar to that described in Example 3, using 2-propyloxetane instead of 2-pentyloxetane in the first step of Example 3.

(102) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-5-(trans-4-(4-ethoxy-2,3-difluorophenyl)bi(cyclohexane)-trans-4-yl)-2-propyltetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(103) Chemical shift ( ppm): 6.82 (dt, 1H), 6.66 (dt, 1H), 4.08 (q, 2H), 4.03-3.99 (m, 1H), 3.17-3.10 (m, 1H), 3.12 (t, 1H), 2.74-2.69 (m, 1H), 1.89-1.63 (m, 10H), 1.51-1.30 (m, 7H), 1.43 (t, 3H), 1.27-0.92 (m, 11H) and 0.91 (t, 3H).

(104) The phase transition temperature of the resulting compound (the compound No. 108) was as follows.

(105) Transition temperature: C 99.0 SB 234.0 N 313.5 Iso.

Example 7

Preparation of trans-2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-5-(4-pentylcyclohexyl)tetrahydro-2H-pyran (No. 75)

(106) trans-2-(trans-4-(4-Ethoxy-2,3-difluorophenyl)cyclohexyl)-5-(4-pentylcyclohexyl)tetrahydro-2H-pyran was prepared was prepared by a method similar to that described in Example 2, using 2-(4-pentylcyclohexyl)acetic acid instead of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid in the first step of Example 2, and using 2-(4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)oxetane instead of 2-(trans-4-pentylcyclohexyl)oxetane in the second step.

(107) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)-5-(4-pentylcyclohexyl)tetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(108) Chemical shift ( ppm): 6.83 (t, 1H), 6.66 (t, 1H), 4.08 (q, 2H), 4.01-4.06 (m, 1H), 3.12 (t, 1H), 2.92-2.98 (m, 1H), 2.12-2.09 (m, 1H), 1.65-1.94 (m, 10H), 1.43 (t, 3H), 1.08-1.48 (m, 17H), 0.78-1.02 (m, 5H) and 0.88 (t, 3H).

(109) The phase transition temperature of the resulting compound (the compound No. 75) was as follows.

(110) Transition temperature: C 70.7 SB 261.5 N 301.4 Iso.

Example 8

Preparation of trans-2-(trans-4-(4-ethoxy-2,3-difluorophenyl)-[1,1-bi(cyclohexane)]-4-yl)-5-pentyltetrahydro-2H-pyran (No. 143)

(111) trans-2-(trans-4-(4-Ethoxy-2,3-difluorophenyl)-[1,1-bi(cyclohexane)]-4-yl)-5-pentyltetrahydro-2H-pyran was prepared by a method similar to that described in Example 2, using enanthic acid instead of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid in the first step of Example 2, and using 2-(4-(4-ethoxy-2,3-difluorophenyl)-[1,1-bi(cyclohexane)]-4-yl)oxetane instead of 2-(trans-4-pentylcyclohexyl)oxetane in the second step.

(112) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-2-(trans-4-(4-ethoxy-2,3-difluorophenyl)-[1,1-bi(cyclohexane)]-4-yl)-5-pentyltetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(113) Chemical shift ( ppm): 6.83 (t, 1H), 6.66 (t, 1H), 4.08 (q, 2H), 3.90-3.96 (m, 1H), 2.98 (t, 1H), 2.88-2.95 (m, 1H), 2.68-2.76 (m, 1H), 1.61-2.02 (m, 9H), 0.90-1.55 (m, 23H), 1.43 (t, 3H) and 0.88 (t, 3H).

(114) The phase transition temperature of the resulting compound (the compound No. 75) was as follows.

(115) Transition temperature: C 72.0 SB 290.5 N 313.6 Iso.

Example 9

Preparation of trans-2-(4-ethoxy-2,3-difluoro-[1,1-biphenyl]-4-yl)-5-(4-propylcyclohexyl)tetrahydro-2H-pyran (No. 313)

(116) trans-2-(4-Ethoxy-2,3-difluoro-[1,1-biphenyl]-4-yl)-5-(4-propylcyclohexyl)tetrahydro-2H-pyran was prepared by a method similar to that described in Example 2, using 2-(4-pentylcyclohexyl)acetic acid instead of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid in the first step of Example 2, and using 2-(4-ethoxy-2,3-difluoro-[1,1-biphenyl]-4-yl)oxetane instead of 2-(trans-4-pentylcyclohexyl)oxetane in the second step.

(117) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-2-(4-ethoxy-2,3-difluoro-[1,1-biphenyl]-4-yl)-5-(4-propylcyclohexyl)tetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(118) Chemical shift ( ppm): 7.467 (m, 2H), 7.408 (m, 2H), 7.077 (m, 1H), 6.781 (m, 1H), 4.295 (m, 1H), 4.192 (m, 1H), 4.170 (q, 2H), 3.346 (t, 1H), 2.050-1.980 (m, 1H), 1.960-1.900 (m, 1H), 1.825-1.710 (m, 4H), 1.665-1.570 (m, 1H), 1.530-1.430 (m, 4H), 1.420-1.265 (m, 3H), 1.230-0.950 (m, 6H) and 0.910-0.800 (m, 5H).

(119) The phase transition temperature of the resulting compound (the compound No. 313) was as follows.

(120) Transition temperature: C 97.8 N 312.1 Iso.

Example as a reference Preparation of trans-2-(4-ethoxy-2,3-difluorophenyl)-5-(4-pentyl-[1,1-bi(cyclohexane)]-4-yl)tetrahydro-2H-pyran (the compound (c))

(121) ##STR00077##

(122) trans-2-(4-Ethoxy-2,3-difluorophenyl)-5-(4-pentyl-[1,1-bi(cyclohexane)]-4-yl)tetrahydro-2H-pyran was prepared by a method similar to that described in Example 2, using 2-(trans-4-pentyl-[1,1-bi(cyclohexane)]-4-yl)acetic acid instead of 2-(trans-4-(4-ethoxy-2,3-difluorophenyl)cyclohexyl)acetic acid in the first step of Example 2, and using 2-(4-ethoxy-2,3-difluorophenyl)oxetane instead of 2-(trans-4-pentylcyclohexyl)oxetane in the second step.

(123) The chemical shift (, ppm) in .sup.1H-NMR analysis was described below, and the resulting compound was identified as trans-2-(4-ethoxy-2,3-difluorophenyl)-5-(4-pentyl-[1,1-bi(cyclohexane)]-4-yl)tetrahydro-2H-pyran. The solvent for measurement was CDCl.sub.3.

(124) Chemical shift ( ppm): 7.095 (m, 1H), 6.714 (m, 1H), 4.485 (m, 1H), 4.148 (m, 1H), 4.112 (q, 2H), 3.333 (t, 1H), 2.005-1.840 (m, 2H), 1.830-1.645 (m, 8H) and 1.600-0.770 (m, 29H).

(125) The phase transition temperature of the resulting compound (the compound (c)) was as follows.

(126) Transition temperature: C 99.3 SB 267.1 N 312.9 Iso.

(127) The following compounds can be prepared according to the methods described in Examples 1 to 9.

(128) TABLE-US-00002 No. 1 2 3 0 4 5 6 7 8 9 10 11 12 13 0 14 15 16 17 18 19 20 21 22 23 00 24 01 25 02 26 03 27 04 28 05 29 06 30 07 31 08 32 09 33 0 34 35 36 37 38 39 40 41 42 43 0 44 45 46 47 48 49 50 51 52 53 0 54 55 56 57 58 59 60 61 62 63 0 64 65 66 67 68 69 70 71 72 73 0 74 75 76 77 78 79 80 81 82 83 0 84 85 86 87 88 89 90 91 92 93 0 94 95 96 97 98 99 100 101 102 103 0 104 105 106 107 108 109 110 111 112 113 0 114 115 116 117 118 119 120 121 122 123 00 124 01 125 02 126 03 127 04 128 05 129 06 130 07 131 08 132 09 133 0 134 135 136 137 138 139 140 141 142 143 0 144 145 146 147 148 149 150 151 152 153 0 154 155 156 157 158 159 160 161 162 163 0 164 165 166 167 168 169 170 171 172 173 0 174 175 176 177 178 179 180 181 182 183 0 184 185 186 187 188 189 190 191 192 193 0 194 195 196 197 198 199 200 201 202 203 0 204 205 206 207 208 209 210 211 212 213 0 214 215 216 217 218 219 220 221 222 223 00 224 01 225 02 226 03 227 04 228 05 229 06 230 07 231 08 232 09 233 0 234 235 236 237 238 239 240 241 242 243 0 244 245 246 247 248 249 250 251 252 253 0 254 255 256 257 258 259 260 261 262 263 0 264 265 266 267 268 269 270 271 272 273 0 274 275 276 277 278 279 280 281 282 283 0 284 285 286 287 288 289 290 291 292 293 0 294 295 296 297 298 299 300 301 302 303 0 304 305 306 307 308 309 310 311 312 313 0

Comparative Example 1

(129) The liquid crystal composition B was prepared from 15% by weight of the compound (b) that had been synthesized by the synthetic method described in JP 2000-008040 A (Patent document No. 3) and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the liquid crystal compound (b) were calculated by measuring the physical property values of the resulting liquid crystal composition B and then by extrapolating the measured value. The extrapolated values were as follows.

(130) Maximum temperature (NI)=121.3 C.; dielectric anisotropy ()=7.3; refractive index anisotropy (n)=0.107; viscosity ()=61.4 mPa.Math.s.

Example 10

(131) The liquid crystal composition D was prepared from 10% by weight of the compound No. 1 and 90% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 1 were calculated by measuring the physical property values of the resulting liquid crystal composition D and then by extrapolating the measured value. The extrapolated values were as follows.

(132) Maximum temperature (NI)=234.6 C.; dielectric anisotropy ()=6.70; refractive index anisotropy (n)=0.126; viscosity ()=63.5 mPa.Math.s.

Example 11

(133) The liquid crystal composition E was prepared from 15% by weight of the compound No. 41 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 41 were calculated by measuring the physical property values of the resulting liquid crystal composition E and then by extrapolating the measured value. The extrapolated values were as follows.

(134) Maximum temperature (NI)=238.6 C.; dielectric anisotropy ()=5.48; refractive index anisotropy (n)=0.122; viscosity ()=66.1 mPa.Math.s.

Example 12

(135) The liquid crystal composition F was prepared from 15% by weight of the compound No. 109 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 109 were calculated by measuring the physical property values of the resulting liquid crystal composition F and then by extrapolating the measured value. The extrapolated values were as follows.

(136) Maximum temperature (NI)=243.3 C.; dielectric anisotropy ()=5.59; refractive index anisotropy (n)=0.126; viscosity ()=65.4 mPa.Math.s.

Example 13

(137) The liquid crystal composition G was prepared from 15% by weight of the compound No. 44 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 44 were calculated by measuring the physical property values of the resulting liquid crystal composition G and then by extrapolating the measured value. The extrapolated values were as follows.

(138) Maximum temperature (NI)=238.6 C.; dielectric anisotropy ()=5.42; refractive index anisotropy (n)=0.182; viscosity ()=82.4 mPa.Math.s.

Example 14

(139) The liquid crystal composition H was prepared from 15% by weight of the compound No. 40 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 40 were calculated by measuring the physical property values of the resulting liquid crystal composition H and then by extrapolating the measured value. The extrapolated values were as follows.

(140) Maximum temperature (NI)=245.3 C.; dielectric anisotropy ()=5.71; refractive index anisotropy (n)=0.122; viscosity ()=72.3 mPa.Math.s.

Example 15

(141) The liquid crystal composition I was prepared from 15% by weight of the compound No. 108 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 108 were calculated by measuring the physical property values of the resulting liquid crystal composition I and then by extrapolating the measured value. The extrapolated values were as follows.

(142) Maximum temperature (NI)=245.3 C.; dielectric anisotropy ()=5.41; refractive index anisotropy (n)=0.128; viscosity ()=69.5 mPa.Math.s.

Example 16

(143) The liquid crystal composition J was prepared from 15% by weight of the compound No. 75 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 75 were calculated by measuring the physical property values of the resulting liquid crystal composition J and then by extrapolating the measured value. The extrapolated values were as follows.

(144) Maximum temperature (NI)=245.9 C.; dielectric anisotropy ()=4.05; refractive index anisotropy (n)=0.122; viscosity ()=60.6 mPa.Math.s.

Example 17

(145) The liquid crystal composition K was prepared from 15% by weight of the compound No. 143 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 143 were calculated by measuring the physical property values of the resulting liquid crystal composition K and then by extrapolating the measured value. The extrapolated values were as follows.

(146) Maximum temperature (NI)=243.9 C.; dielectric anisotropy ()=4.74; refractive index anisotropy (n)=0.124; viscosity ()=63.3 mPa.Math.s.

Example 18

(147) The liquid crystal composition L was prepared from 15% by weight of the compound No. 313 and 85% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the compound No. 313 were calculated by measuring the physical property values of the resulting liquid crystal composition L and then by extrapolating the measured value. The extrapolated values were as follows.

(148) Maximum temperature (NI)=252.6 C.; dielectric anisotropy ()=4.88; refractive index anisotropy (n)=0.191; viscosity ()=88.9 mPa.Math.s.

Comparative Example 2

(149) The liquid crystal composition M was prepared from 3% by weight of the compound (c) prepared by the method described in the example as a reference and 97% by weight of the mother liquid crystals (A). The extrapolated values of physical properties of the liquid crystal compound (c) were calculated by measuring the physical property values of the resulting liquid crystal composition M and then by extrapolating the measured value. The extrapolated values were as follows.

(150) Maximum temperature (NI)=261.3 C.; dielectric anisotropy ()=2.7; refractive index anisotropy (n)=0.150; viscosity ()=70.5 mPa.Math.s.

(151) It was found that the absolute value of the dielectric anisotropy of the liquid crystal compound (c) was small in comparison with the compound No. 1 that was similar to the compound (c).

(152) As a molecular weight increases, viscosity increases generally. The compound No. 1 in Example 4, the compound No. 41 in Example 5 and the compound No. 109 in Example 6 have an additional molecular weight corresponding to one cyclohexane ring in comparison with the compound (b) in Comparative example. However, their viscosities were surprisingly equivalent. Furthermore, it was found that the compound No. 1, the compound No. 41 and the compound No. 109 had a much high maximum temperature (NI) when they were compared with the compound (b).

(153) Accordingly, it was found that the compound No. 1, the compound No. 41 and the compound No. 109 were superior in view of a much high maximum temperature (NI) in comparison with the compound (b), although they had an equivalent viscosity.

(154) Examples of the Liquid Crystal Composition

(155) Typical compositions of the invention were summarized in Examples 19 to 32. First, compounds that are a component of the composition and their amounts (% by weight) were shown. The compounds were expressed in the symbols of a left-terminal group, a bonding group, a ring structure and a right-terminal group according to the definition in Table 1.

(156) TABLE-US-00003 TABLE 1 Method of 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 CHCH.sub.2 V CHCHC.sub.nH.sub.2n+1 Vn C.sub.nH.sub.2nCHCH.sub.2 nV CHCF.sub.2 VFF COOCH.sub.3 EMe CN C F F Cl CL OCF.sub.3 OCF3 CF.sub.3 CF3 3) Bonding Group Z.sub.n Symbol C.sub.nH.sub.2n n COO E CHCH V CH.sub.2O 1O CF.sub.2O X CC T 4) Ring Structure A.sub.n Symbol H Ch Dh dh G B Py B(2F) B(F) 00 B(F,F) 01 B(2F,3F) 02 B(2F,3CL) 03 B(2CL,3F) 04 Cro(7F,8F) 05 Np(1F,7F,8F) 5) Examples of Description Example 1. 3-HHDhB(2F,3F)O2 06 Example 2. 3-DhHHB(2F,3F)O2 07 Example 3. 3-HHB-3 08 Example 4. 5-HBB(2F,3CL)O2 09

Example 19

(157) TABLE-US-00004 3-HHDhB(2F,3F)-O2 (No. 1) 4% 5-DhHHB(2F,3F)-O2 (No. 109) 4% 3-HH-O1 (12-1) 8% 5-HH-O1 (12-1) 4% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 21% 2-HHB(2F,3F)-1 (7-1) 5% 3-HHB(2F,3F)-1 (7-1) 7% 3-HHB(2F,3F)-O2 (7-1) 10% 5-HHB(2F,3F)-O2 (7-1) 20% NI = 74.6 C.; n = 0.080; = 25.3 mPa .Math. s; = 4.3.

Example 20

(158) TABLE-US-00005 5-HDhHB(2F,3F)-O2 (No. 41) 3% 3-HDhBB(2F,3F)-O2 (No. 44) 7% 3-HB-O1 (12-5) 15% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 12% 2-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-O2 (7-1) 13% 5-HHB(2F,3F)-O2 (7-1) 3% 3-HHB-1 (13-1) 6% NI = 94.2 C.; n = 0.095; = 38.8 mPa .Math. s; = 3.4.

Example 21

(159) TABLE-US-00006 3-HHDhB(2F,3F)-O2 (No. 1) 3% 3-HDhBB(2F,3F)-O2 (No. 44) 3% 3-HB-O1 (12-5) 15% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 12% 2-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-O2 (7-1) 13% 5-HHB(2F,3F)-O2 (7-1) 7% 6-HEB(2F,3F)-O2 (6-6) 6% NI = 86.2 C.; n = 0.089; = 36.0 mPa .Math. s; = 3.7.

Example 22

(160) TABLE-US-00007 5-DhHHB(2F,3F)-O2 (No. 109) 3% 3-HDhBB(2F,3F)-O2 (No. 44) 5% 3-HH-4 (12-1) 14% 3-H2B(2F,3F)-O2 (6-4) 22% 5-H2B(2F,3F)-O2 (6-4) 22% 2-HHB(2F,3CL)-O2 (7-12) 2% 3-HHB(2F,3CL)-O2 (7-12) 3% 4-HHB(2F,3CL)-O2 (7-12) 2% 3-HBB(2F,3F)-O2 (7-7) 9% V-HHB-1 (13-1) 6% 3-HHB-3 (13-1) 6% 3-HHEBH-3 (14-6) 3% 3-HHEBH-4 (14-6) 3% NI = 85.9 C.; n = 0.096; = 27.9 mPa .Math. s; = 3.8.

Example 23

(161) TABLE-US-00008 3-HDhHB(2F,3F)-O2 (No. 40) 3% 3-DhHHB(2F,3F)-O2 (No. 108) 3% 2-HH-5 (12-1) 3% 3-HH-4 (12-1) 15% 3-HH-5 (12-1) 4% 3-H2B(2F,3F)-O2 (6-4) 12% 5-H2B(2F,3F)-O2 (6-4) 15% 3-HHB(2F,3CL)-O2 (7-12) 5% 2-HBB(2F,3F)-O2 (7-7) 3% 3-HBB(2F,3F)-O2 (7-7) 9% 5-HBB(2F,3F)-O2 (7-7) 6% 3-HHB-1 (13-1) 3% 3-HHB-3 (13-1) 4% 3-HHB-O1 (13-1) 3% 3-HB-O2 (12-5) 12% NI = 84.9 C.; n = 0.093; = 20.6 mPa .Math. s; = 4.0.

(162) The helical pitch was 60.3 m when 0.25 part of the compound (Op-05) was added to the preceding composition.

Example 24

(163) TABLE-US-00009 3-HdhHB(2F,3F)-O2 (No. 74) 3% 3-dhHHB(2F,3F)-O2 (No. 142) 3% 3-HB-O1 (12-5) 15% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 12% 2-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-1 (7-1) 6% 3-HHB(2F,3F)-O2 (7-1) 13% 5-HHB(2F,3F)-O2 (7-1) 13% 3-HHB-1 (13-1) 6%

Example 25

(164) TABLE-US-00010 3-HHDhB(2F,3F)-O2 (No. 1) 4% 5-DhHHB(2F,3F)-O2 (No. 109) 3% 2-BEB(F)-C (5-14) 5% 3-BEB(F)-C (5-14) 4% 4-BEB(F)-C (5-14) 12% 1V2-BEB(F,F)-C (5-15) 16% 3-HB-O2 (12-5) 10% 3-HH-4 (12-1) 3% 3-HHB-F (3-1) 3% 3-HHB-1 (13-1) 8% 3-HHB-O1 (13-1) 4% 3-HBEB-F (3-37) 4% 5-HHEB-F (3-10) 7% 3-H2BTB-2 (13-17) 4% 3-H2BTB-3 (13-17) 4% 3-H2BTB-4 (13-17) 4% 3-HB(F)TB-2 (13-18) 5% NI = 89.1 C.; n = 0.141; = 27.2; Vth; = 39.3 mPa .Math. sec.

Example 26

(165) TABLE-US-00011 5-HDhHB(2F,3F)-O2 (No. 41) 5% 3-HDhBB(2F,3F)-O2 (No. 44) 7% 1V2-BEB(F,F)-C (5-15) 6% 3-HB-C (5-1) 18% 2-BTB-1 (12-10) 10% 5-HH-VFF (12-1) 30% 3-HHB-1 (13-1) 4% VFF-HHB-1 (13-1) 5% VFF2-HHB-1 (13-1) 11% 3-H2BTB-4 (13-17) 4% NI = 90.6 C.; n = 0.124; = 5.3; = 18.7 mPa .Math. sec.

Example 27

(166) TABLE-US-00012 3-HHDhB(2F,3F)-O2 (No. 1) 4% 5-DhHHB(2F,3F)-O2 (No. 109) 4% 2-HB-C (5-1) 5% 3-HB-C (5-1) 12% 3-HB-O2 (12-5) 11% 2-BTB-1 (12-10) 3% 3-HHB-F (3-1) 4% 3-HHB-1 (13-1) 8% 3-HHB-O1 (13-1) 5% 3-HHB-3 (13-1) 14% 5-HHEB-F (3-10) 4% 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) 5% NI = 109.2 C.; n = 0.101; = 3.7; = 20.8 mPa .Math. sec.

Example 28

(167) TABLE-US-00013 3-HDhHB(2F,3F)-O2 (No. 40) 3% 3-DhHHB(2F,3F)-O2 (No. 108) 3% 5-HB-CL (2-2) 18% 3-HH-4 (12-1) 12% 3-HH-5 (12-1) 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) 7% 4-HHB(F)-F (3-2) 9% 5-HHB(F)-F (3-2) 9% 7-HHB(F)-F (3-2) 8% 5-HBB(F)-F (3-23) 4% 1O1-HBBH-5 (14-1) 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% NI = 116.7 C.; n = 0.090; = 2.8; = 18.3 mPa .Math. sec.

Example 29

(168) TABLE-US-00014 3-HdhHB(2F,3F)-O2 (No. 74) 5% 3-dhHHB(2F,3F)-O2 (No. 142) 3% 2-BEB(F)-C (5-14) 5% 3-BEB(F)-C (5-14) 4% 4-BEB(F)-C (5-14) 12% 1V2-BEB(F,F)-C (5-15) 16% 3-HB-O2 (12-5) 10% 3-HH-4 (12-1) 5% 3-HHB-F (3-1) 3% 3-HHB-1 (13-1) 8% 3-HHB-O1 (13-1) 4% 3-HBEB-F (3-37) 4% 3-HHEB-F (3-10) 4% 3-H2BTB-2 (13-17) 4% 3-H2BTB-3 (13-17) 4% 3-H2BTB-4 (13-17) 4% 3-HB(F)TB-2 (13-18) 5%

Example 30

(169) TABLE-US-00015 3-HHDhB(2F,3F)-O2 (No. 1) 4% 5-DhHHB(2F,3F)-O2 (No. 109) 4% 3-HH-O1 (12-1) 8% 5-HH-O1 (12-1) 4% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 7% 5-HB(2F,3F)-O2 (6-1) 21% 3-HHB(2F,3F)-1 (7-1) 7% 3-HHB(2F,3F)-O2 (7-1) 10% 5-HHB(2F,3F)-O2 (7-1) 20% 2-BB(2F,3F)B-3 (8-1) 5% 2-BB(2F,3F)B-4 (8-1) 5% NI = 79.3 C.; n = 0.095; = 26.2 mPa .Math. s; = 4.0.

Example 31

(170) TABLE-US-00016 3-HdhHB(2F,3F)-O2 (No. 74) 3% 3-dhHHB(2F,3F)-O2 (No. 142) 7% 3-HB-O1 (12-5) 20% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 12% 2-HHB(2F,3F)-1 (7-1) 10% 3-HHB(2F,3F)-l (7-1) 12% 3-HHB(2F,3F)-O2 (7-1) 8% 3-HHB-1 (13-1) 6% 5-HH1ONp(1F,7F,8F)-O4 (9-3) 5%

Example 32

(171) TABLE-US-00017 3-HHDhB(2F,3F)-O2 (No. 1) 3% 3-HDhBB(2F,3F)-O2 (No. 44) 3% 3-HB-O1 (12-5) 15% 3-HH-4 (12-1) 5% 3-HB(2F,3F)-O2 (6-1) 12% 5-HB(2F,3F)-O2 (6-1) 12% 2-HHB(2F,3F)-1 (7-1) 12% 3-HHB(2F,3F)-1 (7-1) 2% 3-HHB(2F,3F)-O2 (7-1) 13% 5-HHB(2F,3F)-O2 (7-1) 7% 6-HEB(2F,3F)-O2 (6-6) 6% 3-HH1OCro(7F,8F)-5 (10-6) 5% 3-HH1OB(2F,3F,6Me)-O2 (11-7) 5% NI = 85.9 C.; n = 0.089; = 40.7 mPa .Math. s; = 4.1.

INDUSTRIAL APPLICABILITY

(172) The invention provides a liquid crystal compound having an excellent compatibility with other liquid crystal materials and a large negative dielectric anisotropy ().

(173) The invention also provides a new liquid crystal composition including the liquid crystal compound as a component, and having features that are desired physical properties, by suitably selecting the rings, the substituents and so forth of the compound. It also provides a liquid crystal display device containing the liquid crystal composition.