JP2896648B2 - Fluorine-containing group-substituted liquid crystal compound, liquid crystal composition and liquid crystal display device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal compound and a liquid crystal composition, and more particularly, to a novel fluorine-substituted group-substituted liquid crystal compound, a liquid crystal composition containing the same and a liquid crystal composition comprising the same. The present invention relates to a liquid crystal display device.

[0002]

2. Description of the Related Art Liquid crystal display elements are widely used in watches, calculators, various measuring instruments, automobile panels, word processors, electronic organizers, printers, computers, televisions, and the like.
These liquid crystal display elements utilize optical anisotropy (△ n) and dielectric anisotropy (△ ε) of a liquid crystal compound, and a dynamic scattering type (DS type) is used as a display method. , Guest-host type (GH type), twisted nematic type (TN
Type), super twisted nematic type (STN type), thin film transistor type (TFT type) and ferroelectric liquid crystal (FLC)
Etc. are known. As the driving method, a static driving method, a time-division driving method, an active matrix driving method, a two-frequency driving method, and the like are known.
Among them, the TFT method has been particularly noted because of the advantage of the highest display performance.

Various properties are required for a liquid crystal material for a TFT system. 1) When added to a liquid crystal composition, the temperature range of the nematic phase is so wide that the temperature range of the nematic phase is not reduced. And 2) low viscosity including the low temperature range, and 3) large Δε are required as common characteristics. Among the above characteristics, 1) includes that the maximum temperature of the nematic phase is high, and that the melting point is low and that phase separation due to crystal precipitation and the like hardly occurs even in a low temperature region. Also,
2) is an extremely important factor upon improving the response speed to the electric field of the liquid crystal molecules oriented in the liquid crystal panel (Phys.Lett., 39 A, 69 (197
2)), Improving the response speed is the most demanded at present for improving the display quality of the liquid crystal composition. At that time, from the viewpoint that the display quality is not deteriorated even at a low temperature, it is important that the temperature dependency of the response speed, that is, the temperature dependency of the material viscosity is small, and that the low viscosity can be maintained even at a low temperature. Is done.

The reason why 3) is desired is as follows. That is, it is necessary to lower the drive voltage in order to reduce the power consumption and increase the screen size. The drive voltage, particularly the threshold voltage (V _th ), is a function of △ ε as shown by the following equation:

[0005]

(Equation 1)

(Where k represents a proportional constant and K represents an elastic constant.) As is apparent from this formula, a compound having a very large Δε is required to reduce power consumption. Regarding V _th , in order to maintain the display quality of the liquid crystal composition high and in a wide temperature range, it is desired that the temperature dependency is small even at a low temperature.

[0007] In order to meet such a demand, a search for a compound having a very large Δε has been conducted conventionally, and among the compounds having a particularly large Δε, a compound represented by the formula (a) Fluoromethylphenyl derivatives (JP-A-59-78129) and trifluoromethoxyphenyl derivatives represented by the formula (b) (Tokuhei 2-501131)
It has been known.

[0008]

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These compounds have a three-ring structure having CF ₃ or OCF ₃ at the terminal of the molecule, but all the linking groups connecting the three rings in a straight line are limited to covalent bonds.
For this reason, it cannot be said that the characteristics other than △ ε sufficiently satisfy these characteristics. Compounds having CF ₃ or ΔCF ₃ at the molecular terminal are, in addition to the above, Li
q. Cryst. , 18 (4), 665 (1995),
JP-T-63-503226, JP-T-Tokadaira each 3-5
033771, 4-500214, 4-500217
Nos. 4-500682, 4-501575, 4-5
01576, 4-507104, 5-502676
No. 6-504032, DE 4004 each
650A1, 4013083, 4106345,
Nos. 4108705A1 and 4113053A1, E
Some of them are shown in P0439089A1 and EP0449288, but there is no sufficient disclosure of physical properties.

The liquid crystal compound used in the liquid crystal composition for TFT must be stable to external environmental factors such as moisture, air, heat and light. In addition, in order to exhibit the characteristics required for each display element, generally, a mixture of several kinds or more than twenty kinds is used. Therefore, good compatibility with other liquid crystal compounds is required, and in particular, good low-temperature compatibility is required especially in recent years because of a wide use environment. That is,
In order to enable use in a wide temperature range, a liquid crystal composition for a TFT that has a nematic phase at a low temperature and does not precipitate crystals or exhibit a smectic phase is desired. Therefore, as the liquid crystal compound used therefor, a compound having excellent low-temperature compatibility with other liquid crystal compounds is particularly desired.

The TFT contains an integrated non-linear element for switching individual image points, and is an active matrix liquid crystal display which is suitable for advanced information displays such as those for televisions and computers, and for automobiles and aircraft. A liquid crystal composition designed for such an application must have an extremely high specific resistance (high voltage holding ratio) and good UV stability in addition to the large positive Δε described above. That is, when a liquid crystal composition having no such characteristics is used, the contrast decreases as the electric resistance in the liquid crystal panel decreases, and the problem of "afterimage erasure" occurs. This is because there is a strong tendency to impair the service life of the product.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and to provide a wide nematic phase temperature range, lower viscosity, large positive Δε, high chemical stability, low temperature, etc. Liquid crystal compounds for TFTs that simultaneously satisfy various properties such as high compatibility with liquid crystal compounds, small temperature dependence of viscosity and Δε, extremely high specific resistance (high voltage holding ratio) and good UV stability. The present invention provides a liquid crystal composition containing the same.

[0013]

Means for Solving the Problems The present inventors have a trifluoromethylphenyl group or a trifluoromethoxyphenyl group, which is a conventionally known example of a terminal substituent, in a molecule, but at the same time, have a specific main skeleton. The inventors have found that a liquid crystal compound having the above-mentioned various properties can be obtained by characteristically combining them, and have completed the present invention.

In order to achieve the above object, the present invention is characterized by the following constitutions. (1) General formula (1)

[0015]

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(Wherein, R ₁ is an alkyl group having 1 to 10 carbon atoms, ring A is 1,4-phenylene , X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom or a fluorine atom;
Y ₁ represents CF ₃ or OCF ₃ , m, n and p are each independently 1 or 0, but m + p = 1
And when n = 1 and p = 0, X ₁ and X ₂ are
If at least one is H and X ₃ and X ₄ are at least nothing
This is F, n = 1 and X ₃ and X ₄ are both F
In this case, X ₁ is H. )). (2) The liquid crystal compound according to (1), wherein n is 0, m is 1, X ₃ is a fluorine atom, and X ₄ is a hydrogen atom. (4) n is 1, m is 1, p is 0, X ₁ , X ₂ and X ₄
Is a hydrogen atom, and X ₃ is a fluorine atom. (5) n is 1, m is 0, p is 1, X ₁ is a fluorine atom, X
_2. The liquid crystal compound according to (1), wherein ₂ is a hydrogen atom. (6) A liquid crystal composition comprising at least one liquid crystal compound according to any one of (1) to (5). (7) As the first component, at least one kind of the liquid crystalline compound described in any of (1) to (5) is contained, and as the second component, the general formulas (2), (3) and (4)

[0017]

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(Wherein, R ₂ represents an alkyl group having 1 to 10 carbon atoms, and Y ₂ represents a fluorine atom, a chlorine atom, OCF ₃ , OCC
F ₂ H, CF ₃ , CF ₂ H or CFH ₂ , L ₁ ,
L ₂ , L ₃ and L ₄ independently represent a hydrogen atom or a fluorine atom, and Z ₁ and Z ₂ independently represent-(C
H ₂ ) ₂ —, —CH ＝ CH— or a covalent bond, and “a” is 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of: (8) As the first component, at least one kind of the liquid crystalline compound described in any of (1) to (5) is contained, and as the second component, the general formulas (5), (6), (7), (8) and (9)

[0019]

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(Wherein R ₃ is a fluorine atom, having 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl or alkenyl group may be substituted by an oxygen atom,
One or more methylene groups are not successively replaced by oxygen atoms. Ring B is 1,4-cyclohexylene, 1,4-
Phenylene or 1,3-dioxane-2,5-diyl, ring C represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, and ring D represents 1,4-cyclohexyl Represents silene or 1,4-phenylene; Z ₃ represents — (CH ₂ ) ₂ —, —COO— or a covalent bond; L ₅ and L ₆ independently represent a hydrogen atom or a fluorine atom; And c are each independently 0 or 1. )

[0021]

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

[0023]

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

[0025]

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(Wherein R ₆ and R ₇ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group is an oxygen atom May be replaced by
Two or more methylene groups are not successively replaced by oxygen atoms. Ring H is 1,4-cyclohexylene, 1,4
-Phenylene or pyrimidine-2,5-diyl, ring I represents 1,4-cyclohexylene or 1,4-phenylene, and Z ₆ represents -C≡C-, -COO-,-
(CH ₂ ) ₂ —, —CH ＝ CH—C≡C— or a covalent bond, and Z ₇ represents —COO— or a covalent bond. )

[0027]

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(Wherein R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In each case, any methylene group is an oxygen atom May be replaced by
Two or more methylene groups are not successively replaced by oxygen atoms. Ring J is 1,4-cyclohexylene, 1,4
-Phenylene or pyrimidine-2,5-diyl, ring K is 1,4-cyclohexylene, and one or more hydrogen atoms on the ring may be substituted with a fluorine atom,
-Phenylene or pyrimidine-2,5-diyl, ring L represents 1,4-cyclohexylene or 1,4-phenylene, Z ₈ and Z ₁₀ independently of one another
_{OO -, - (CH 2)} 2 - or indicates a covalent bond, Z ₉ is -CH = CH -, - C≡C - , - COO- or indicates a covalent bond, h is 0 or 1. A liquid crystal composition comprising at least one compound selected from the group consisting of: (9) As the first component, (1) to
At least one of the liquid crystal compounds described in (5);
Contains, as a part of the second component, general formula (2),
It contains at least one compound selected from the group consisting of (3) and (4), and as another portion of the second component,
A liquid crystal composition comprising at least one compound selected from the group consisting of general formulas (5), (6), (7), (8) and (9). (10) (6)-
A liquid crystal display device comprising the liquid crystal composition according to any one of (9).

The compound represented by the general formula (1) of the present invention has a known trifluoromethyl group or trifluoromethoxy group on a terminal phenylene group, and at the same time, one 1,2-amino group as a central bonding group. It is characterized by having a specific skeleton composed of two or three rings containing an ethylene group . These compounds have the formula (1-1) or (1-3)
3 shown in 2-ring compounds (group 1), the formula and the middle Hisashiwa 1,4-phenylene linking group linking this with end-phenylene is a covalent bond (1-8) to (1-9) shown in A ring compound (group 3) and a compound represented by formulas (1-10) to (1-15) in which the central ring is 1,4-phenylene and the bonding group connecting the terminal ring and the terminal phenylene is a 1,2-ethylene group; They are roughly classified into ring compounds (Group 4).

[0030]

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[0031]

Embedded image (In each formula, R ₁ has the same meaning as described above.)

Each of these compounds of the present invention has a wide nematic phase temperature range, a low viscosity, a large positive Δε, a high chemical stability, a high compatibility with other liquid crystal compounds at low temperatures, and an extremely high specific resistance (high It exhibits good stability to UV and heating at the same time, and has a very small temperature dependency of Δε and viscosity, so that it is useful as a component of a liquid crystal composition for TFT. The refractive index anisotropy value (△
For n), in the compound represented by the general formula (1) of the present invention, R ₁ , ring A, X ₁ , X ₂ , X ₃ , X ₄ , m,
It can be arbitrarily adjusted by appropriately selecting n and p. For example, when a large Δn is desired, a compound containing 1,4-phenylene as the ring A, and conversely, when a small Δn is desired, a compound containing more 1,4-cyclohexylene as the ring A may be selected. .

Among the compounds of the present invention, the compounds included in the first group exhibit particularly a large Δε, a low viscosity and a high clearing point, and are excellent as constituents of a liquid crystal composition.
Further, the compounds of the second group exhibit particularly excellent nematic properties, and a liquid crystal composition using the compound as one of the components does not show a smectic phase at a low temperature and exhibits preferable characteristics. The compounds of the third group exhibit particularly high clearing points and low viscosities, have a large Δε, and have a small temperature dependence of viscosity. It has excellent solubility and is excellent as a component of a liquid crystal composition. Further, the compounds of the fourth group exhibit particularly high clearing points and low viscosities, have large Δε and Δn, and have a small temperature dependence of viscosity. It has excellent compatibility and is suitable as a component of a liquid crystal composition. The compound of the present invention is most preferably used as a component of a liquid crystal composition for a TFT. However, since it has the above-mentioned excellent properties, it is not limited to this, and is not limited to this.
It can also be suitably used as a liquid crystal compound for N, guest host mode, polymer dispersion type liquid crystal display device and dynamic scattering mode.

The liquid crystal composition provided by the present invention may comprise only the first component containing at least one kind of the liquid crystal compound represented by the general formula (1). At least one compound selected from the group consisting of the general formulas (2), (3) and (4) (hereinafter referred to as the second component A) and / or the general formula (5);
A mixture of at least one compound selected from the group consisting of (6), (7), (8) and (9) (hereinafter, referred to as a second B component) is preferable. For the purpose of adjusting the phase temperature range, Δn, Δε, viscosity and the like, a known compound can be mixed as the third component.

Of the second component A, the general formula (2):
As preferred examples of the compounds contained in (3) and (4),
(2-1) to (2-15), (3-1) to (3)
-48) and (4-1) to (4-53).

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

Embedded image (In each formula, R ₂ has the same meaning as described above.)

The compounds represented by the general formulas (2) to (4) have a positive Δε, are very excellent in thermal stability and chemical stability, and particularly have a voltage holding ratio (VHR). This compound is indispensable when preparing a liquid crystal composition for TFT requiring high reliability such as a high or a large specific resistance value. However, a liquid crystal composition for an STN display method or a normal TN display method is prepared. It can also be used when doing so. When preparing a liquid crystal composition for a TFT, the amount of the compound is preferably in the range of 1 to 99% by weight, preferably 10 to 97% by weight, more preferably 10 to 97% by weight based on the total weight of the liquid crystal composition. Is 40 to 95% by weight.

Next, among the second component B, preferred examples of the compounds contained in the general formulas (5), (6) and (7) are (5-1) to (5-24) and (5-24), respectively. 6-
1) to (6-3) and (7-1) to (7-17).

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

Embedded image (In each formula, R ₃ , R ₄ and R ₅ each have the same meaning as described above.)

The compounds represented by the general formulas (5) to (7) have a large value of Δε and a large value, and are used as a component of the composition particularly for decreasing V _th . It is also used for the purpose of adjusting viscosity, adjusting Δn, increasing the clearing point to widen the nematic range, and improving the steepness of V _th .

Among the second component B, preferred examples of the compounds contained in the general formulas (8) and (9) are (8-1) to (8-8) to (9-1) to (9). -12).

[0054]

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[0055]

Embedded image (In each formula, R ₆ , R ₇ , R ₈ and R ₉ each have the same meaning as described above.)

The compounds represented by the general formulas (8) and (9) have a negative or slightly positive Δε. Among them, the compound represented by the general formula (8) is mainly used as a component of the composition for reducing the viscosity or reducing the viscosity. The compound represented by the general formula (9) is used for the purpose of adjusting Δn and for the purpose of increasing the clearing point and expanding the nematic range and / or for adjusting Δn.

The compounds represented by the above general formulas (5) to (9) are indispensable especially for preparing a liquid crystal composition for an STN display system or a normal TN display system.
It can also be used when preparing the above-mentioned liquid crystal composition for TFT. The amount of the compound used is preferably in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition when a liquid crystal composition for a normal TN display mode or STN display mode is prepared. It is in the range of 10-97% by weight, more preferably 40-95% by weight.

The thus prepared liquid crystal composition of the present invention can improve the steepness of _Vth and the viewing angle by using it for a TFT liquid crystal display device. Further, since the compound of the present invention represented by the general formula (1) has low viscosity, the use of the compound can improve the response speed of the liquid crystal display device. The composition of the present invention contains at least one of the liquid crystal compounds of the present invention represented by the general formula (1) in a proportion of 0.1 to 99% by weight.
It is preferable to exhibit excellent characteristics.

The liquid crystal composition of the present invention can be prepared by a conventional method, such as dissolving each component at a high temperature or dissolving each component in an organic solvent and then distilling off the solvent under reduced pressure. Is generally prepared by Further, by adding appropriate additives as needed, improvements and optimization depending on the intended use can be made. Such additives are well known to those skilled in the art and are described in detail in the literature and the like. Usually, a chiral dopant having an effect of inducing a helical structure of a liquid crystal to adjust a required twist angle and prevent reverse twist.
Are added.

When dichroic dyes such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone and tetrazine are added, a liquid crystal for guest-host (GH) mode can be obtained. It can also be used as a composition. The composition according to the present invention comprises an NCA prepared by microencapsulating a nematic liquid crystal.
P and liquid crystal display devices (PDLCD) represented by a polymer network liquid crystal display device (PNLCD) produced by forming a three-dimensional network polymer in liquid crystal, and birefringence control ( ECB) mode and dynamic scattering (DS)
It can also be used as a liquid crystal composition for a mode.

The liquid crystal composition of the present invention is prepared as described above, and the following composition examples 1 to 21 can be given as examples. In each of the composition examples, the compounds are indicated according to the rules shown in Table 1 below, and the left terminal group is represented by r-, rO-, rOs-, Vr-, rVs- and rV-.
by sVk- (r, s and k are integers of 1 or more), by 2, E, T, V and CF2O for the linking group
For the ring structure, B, B (F), B (F, F), H, P
According to y, D and Ch, -F,-
CL, -C, -CF3, -OCF3, -OCF2H,-
The values are represented by w, -Ow and -EMe (w is an integer of 1 or more). Compound N attached to the compound of the present invention
o. Is the same as that shown in the embodiment described later.

[0062]

[Table 1]

Composition Example 1 3-H2B (F) -CF3 (No. 1) 5.0% 5-H2B (F) -CF3 (No. 3) 5.0% 7-HB (F) -F 0% 2-HHB (F) -F 13.4% 3-HHB (F) -F 13.3% 5-HHB (F) -F 13.3% 2-H2HB (F) -F 6.4% 3-H2HB (F) -F 3.2% 5-H2HB (F) -F 6.4% 2-HBB (F) -F 7.5% 3-HBB (F) -F 7.5% 5- HBB (F) -F 15.0%

Composition Example 2 3-H2H2B (F) -OCF3 (No. 24) 10.0% 3-H2H2B (F, F) -CF3 (No. 29) 10.0% 3-H2H2B (F, F) -OCF3 (No. 34) 10.0% 5-H2HB (F, F) -F 3.0% 3-HHB (F, F) -F 10.0% 4-HHB (F, F) -F6 3.0% 3-HH2B (F, F) -F 3.0% 5-HH2B (F, F) -F 3.0% 3-HBB (F, F) -F 12.0% 5-HBB (F , F) -F 12.0% 3-H2BB (F, F) -F 4.0% 3-HBEB (F, F) -F 3.0% 3-HHEB (F, F) -F 6.0 % 4-HHEB (F, F) -F 2.0% 5-HHEB (F, F) -F 2.0% 3-HHHB (F, F) -F 2.0% 3-HH2BB F, F) -F 2.0%

Composition Example 3 3-HB (F) 2B (F) -OCF3 (No. 60) 5.0% 3-HB (F) 2B (F, F) -OCF3 (No. 70) 5.0% 7-HB (F, F) -F 4.0% 7-HB (F) -F 7.0% 2-HHB (F) -F 13.4% 3-HHB (F) -F 13.3% 5-HHB (F) -F 13.3% 2-H2HB (F) -F 4.0% 3-H2HB (F) -F 2.0% 5-H2HB (F) -F 4.0% 3- H2HB (F, F) -F 3.0% 5-H2HB (F, F) -F 3.0% 3-HHB (F, F) -F 8.0% 3-HH2B (F, F) -F 8.0% 5-HH2B (F, F) -F 7.0%

Composition Example 4 3-H2BB (F) -CF3 (No. 39) 6.0% 3-H2BB (F) -OCF3 (No. 44) 5.0% 3-HB (F) 2B (F, F) -OCF3 (No. 70) 11.0% 3-HB-CL 7.0% 7-HB (F, F) -F 10.0% 2-HBB (F) -F 5.0% 3- HBB (F) -F 5.0% 5-HBB (F) -F 10.0% 2-HHB-CL 5.0% 4-HHB-CL 10.0% 5-HHB-CL 5.0% 5 -HBB (F, F) -F 11.0% 3-HB (F) VB-2 5.0% 3-HB (F) VB-3 5.0%

Composition Example 5 5-H2B (F) -CF3 (No. 3) 5.0% 3-H4B (F) -CF3 (No. 13) 5.0% 3-HB (F) 2B (F) -OCF3 (No. 60) 11.0% 3-H2H2B (F) -OCF3 (No. 24) 5.0% 7-HB (F) -F 5.0% 7-HB (F, F) -F 3.0% 5-H2B (F) -F 3.0% 2-HHB (F) -F 3.0% 3-HHB (F) -F 3.0% 5-HHB (F) -F 3.0% 0% 2-HBB (F) -F 7.0% 3-HBB (F) -F 7.0% 5-HBB (F) -F 14.0% 3-HHB-F 2.0% 2-HBB -F 3.0% 3-HBB-F 3.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% 3-HB (F) TB-4 6.0%

Composition Example 6 3-H2BB (F) -CF3 (No. 39) 8.0% 3-H2H2B (F, F) -CF3 (No. 29) 7.0% 5-HEB-F2.5 % 7-HEB-F 2.5% 2-HHB (F) -F 8.0% 3-HHB (F) -F 8.0% 5-HHB (F) -F 8.0% 2-HBB ( F) -F 2.5% 3-HBB (F) -F 5.0% 5-HBB (F) -F 2.5% 4-H2BB (F) -F 5.0% 5-H2BB (F) -F 6.0% 3-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 10.0% 3-HH2B (F, F) -F 5.0% 5- HH2B (F, F) -F 8.0% 5-HHEBB-F 2.0%

Composition Example 7 3-H2B (F) -CF3 (No. 1) 10.0% 3-H2BB (F) -CF3 (No. 39) 4.0% V2-HB-C 9.0% 1V2 -HB-C 9.0% 3-HB-C 4.0% 1O1-HB-C 8.0% 2O1-HB-C 4.0% 2-HHB-C 3.0% 3-HHB-C 3 0.0% 3-HH-4 10.0% 1O1-HH-5 8.0% 2-BTB-O1 11.0% 3-HHB-1 8.0% 3-HHB-3 9.0% Physical properties of the product were as follows: NI point: 62.8 ° C, viscosity (20 ° C): 18.3 mPa · s, Δn (25 ° C):
0.112, Δε (25 ° C.): 7.4, V _th (20
° C): 1.68V.

Composition Example 8 3-HB (F) 2B (F) -OCF3 (No. 60) 3.0% 3-H2H2B (F, F) -OCF3 (No. 34) 3.0% V2-HB- C 12.0% 1V2-HB-C 11.0% 1V2-BEB (F, F) -C 5.0% 2-BTB-1 8.0% 4-BTB-O2 8.0% 5-BTB- O1 6.0% 3-HH-4 3.0% 3-HH-EMe 3.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 2-H2BTB-3 4.0% 2-H2BTB-2 4.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% 3-HB (F) TB-4 6.0%

Composition Example 9 3-H2B (F) -CF3 (No. 1) 3.0% 5-H2B (F) -CF3 (No. 3) 3.0% 3-H4B (F) -CF3 (No. 3) .13) 3.0% 2O1-BEB (F) -C 4.0% 3O1-BEB (F) -C 3.0% 5O1-BEB (F) -C 4.0% 1V2-BEB (F, F 10.)-C 15.0% 3-HHEB-F 5.0% 5-HHEB-F 5.0% 3-HBEB-F 6.0% 3-HHB-F 3.0% 3-HB-O2 0% 3-HH-4 5.0% 3-HHB-1 8.0% 3-HHB-3 6.0% 3-HHB-O1 4.0% 3-H2BTB-2 4.0% 3-H2BTB -3 4.0% 3-HB (F) TB-2 5.0%

Composition Example 10 3-H2H2B (F) -OCF3 (No. 24) 6.0% 3-H2BB (F) -OCF3 (No. 44) 3.0% 2-HB (F) -C 0% 3-HB (F) -C 13.0% 5-HB (F) -C 9.0% 2-BB-C 13.0% 2-BEB-C 12.0% 3-BEB-C 4 0.0% 2-HHB (F) -C 6.0% 3-HHB (F) -C 6.0% 2-HHB-C 3.0% 3-HHB-C 3.0% 3-PyBB-F 8.0%

Composition Example 11 5-H2B (F) -CF3 (No. 3) 3.0% 3-HB (F) 2B (F, F) -OCF3 (No. 60) 3.0% 2-BB- C 8.0% 4-BB-C 6.0% 2-HB-C 10.0% 3-HB-C 10.0% 3-HHB-F 4.0% 2-HHB-C 3.0% 3-HHB-C 3.0% 3-HBEBB-C 2.0% 5-PyB-F 6.0% 3-PyBB-F 6.0% 2-BTB-O1 2.0% 2-HHB-1 6.0% 3-HHB-1 8.0% 3-HHB-3 15.0% 3-HHB-O1 5.0%

Composition Example 12 3-H2B (F) -CF3 (No. 1) 5.0% 3-DB-C 5.0% 4-DB-C 12.0% 5-DB-C 8.0% 2-BEB-C 10.0% 5-PyB (F) -F 7.0% 2-PyB-2 1.4% 3-PyB-2 1.3% 4-PyB-2 1.3% 6- PyB-O5 1.5% 6-PyB-O6 1.5% 3-HEB-O4 5.0% 4-HEB-O2 3.7% 3-HEB-O2 3.1% 10-BEB-2 2. 5% 5-HEB-1 3.7% 4-HEB-4 5.0% 3-HHB-3 13.0% 3-HHB-O1 4.0% 2-PyBH-3 4.0% 3-PyBB -2 2.0%

Composition Example 13 3-H2BB (F) -CF3 (No. 39) 6.0% 3-H2H2B (F) -OCF3 (No. 24) 7.0% 5-HB-F 9.0% 6 -HB-F 7.0% 7-HB-F 7.0% 5-HB-3 5.0% 3-HB-O1 5.0% 2-HHB-OCF3 5.0% 3-HHB-OCF3 5 0.0% 4-HHB-OCF3 5.0% 5-HHB-OCF3 7.0% 3-HH2B-OCF3 2.0% 5-HH2B-OCF3 3.0% 3-HH2B-F 3.0% 5- HH2B-F 3.0% 5-HBB (F) -F 5.0% 5-HH2B (F) -F 9.0% 3-HB (F) BH-3 3.0% 5-HB (F) BH-3 2.0% 5-HB (F) BH-5 2.0%

Composition Example 14 3-H2H2B (F, F) -CF3 (No. 29) 6.0% 3-HB (F) 2B (F, F) -OCF3 (No. 70) 8.0% 5- HB-F 4.0% 7-HB-F 7.0% 3-HHB-OCF3 12.0% 5-HHB-OCF3 8.0% 3-H2HB-OCF3 5.0% 5-H2HB-OCF3 5. 0% 2-HHB (F) -F 6.6% 3-HHB (F) -F 6.7% 5-HHB (F) -F 6.7% 4-H2HB (F, F) -F 5. 0% 5-H2HB (F, F) -F 5.0% 3-HH2B (F, F) -F 8.0% 4-HH2B (F, F) -F 7.0%

Composition Example 15 3-H2B (F) -CF3 (No. 1) 6.0% 5-H2B (F) -CF3 (No. 3) 4.0% 2O1-BEB (F) -C 0% 3O1-BEB (F) -C 5.0% 5O1-BEB (F) -C 3.0% V-HB-C 10.0% 1V-HB-C 10.0% 3-HB-C 11 2.0% 2-HHB-C 4.0% 3-HHB-C 5.0% 4-HHB-C 4.0% 5-HHB-C 4.0% 3-HB-O2 7.0% V- HHB-1 7.0% V-HBB-2 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 3.0% 3-H2BTB-4 3.0%

Composition Example 16 3-HB (F) 2B (F) -OCF3 (No. 60) 10.0% 3-H2H2B (F) -OCF3 (No. 24) 5.0% 2-HB (F) -C 10.0% 3-HB (F) -C 10.0% 3-HB-O2 10.0% V-HH-5 5.0% V2-HH-3 5.0% 2-BTB-O1 10.0% V-HHB-1 10.0% V-HBB-2 5.0% 1V2-HBB-2 5.0% 3-HHB-O1 5.0% 3-H2BTB-2 5.0% 3 -H2BTB-3 5.0%

Composition Example 17 3-HB (F) 2B (F) -OCF3 (No. 60) 3.0% 3-H2H2B (F, F) -CF3 (No. 29) 3.0% V2-HB- C 12.0% 1V2-HB-C 11.0% 1V2-BEB (F, F) -C 5.0% 2-BTB-1 8.0% 4-BTB-O2 8.0% 5-BTB- O1 6.0% 3-HH-4 3.0% 3-HH-EMe 3.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% 3-HB (F) VB-4 6.0% The physical properties of this composition were as follows: NI point: 91.4 ° C., viscosity (20 ° C.): 25.0 mPa · s, Δn (2 ℃):
0.198, Δε (25 ° C.): 7.4, V _th (20
° C): 1.68V.

Composition Example 18 3-H2B (F) -CF3 (No. 1) 4.0% 5-H2B (F) -CF3 (No. 3) 4.0% 2O1-BEB (F) -C 0% 3O1-BEB (F) -C 4.0% 5O1-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 14.0% 3-HBEB-F 6.0% 3 -HHEB-F 5.0% 5-HHEB-F 5.0% 3-HHB-F 3.0% 3-HB-O2 10.0% 3-HH-4 6.0% 3-HHB-18 3.0% 3-HHB-3 6.0% 3-HHB-O1 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-HB (F) TB-2 5. 0% The physical properties of this composition are as follows: NI point: 88.0 ° C., viscosity (20 ° C.): 27.0 mPa · s, Δn (25 ° C.):
0.122, Δε (25 ° C.): 18.1, V _th (20
° C): 1.24V.

Composition Example 19 3-H2B (F) -CF3 (No. 1) 4.0% 3-HB (F) 2B (F, F) -OCF3 (No. 70) 2.0% 2-BB- C 8.0% 4-BB-C 6.0% 2-HB-C 10.0% 3-HB-C 10.0% 3-HHB-F 4.0% 2-HHB-C 3.0% 3-HHB-C 3.0% 3-HBEBB-C 2.0% 5-PyB-F 6.0% 3-PyBB-F 6.0% 2-BTB-O1 2.0% 2-HHB-1 6.0% 3-HHB-1 8.0% 3-HHB-3 15.0% 3-HHB-O1 5.0% The physical property values of this composition are as follows: NI point: 90.9 ° C., viscosity (20 ° C): 21.9 mPa · s, Δn (25 ° C):
0.140, Δε (25 ° C.): 9.2, V _th (20
° C): 1.79V.

Composition Example 20 3-H2H2B (F) -OCF3 (No. 24) 2.0% 3-H2BB (F) -OCF3 (No. 44) 4.0% 2-HB (F) -C 0% 3-HB (F) -C 12.0% 5-HB (F) -C 10.0% 2-BB-C 12.0% 4-BEB-C 12.0% 3-BEB-C 4 0.0% 2-HHB (F) -C 6.0% 3-HHB (F) -C 6.0% 2-HHB-C 2.0% 3-HHB-C 4.0% 3-PyBB-F 8.0% 3-HB (F) EB (F) -C 4.0% The physical properties of this composition are as follows: NI point: 56.8 ° C., viscosity (20 ° C.): 51.6 mPa · s, Δn (25 ° C.):
0.143, Δε (25 ° C.): 18.0, V _th (20
° C): 0.91V.

Composition Example 21 3-H2B (F) -CF3 (No. 1) 5.0% 3-DB-C 5.0% 4-DB-C 12.0% 5-DB-C 8.0% 2-BEB-C 10.0% 5-PyB (F) -F 7.0% 2-PyB-2 1.4% 3-PyB-2 1.3% 4-PyB-2 1.3% 6- PyB-O4 2.0% 6-PyB-O5 1.0% 3-HEB-O4 5.0% 4-HEB-O2 3.8% 3-HEB-O2 3.0% 10-BEB-2 2. 4% 5-HEB-1 3.8% 4-HEB-4 5.0% 3-HHB-3 13.0% 3-HHB-O1 4.0% 2-PyBH-3 4.0% 3-PyBB -2 2.0% The physical properties of this composition were as follows: NI point: 53.6 ° C, viscosity (20 ° C): 29.6 mPa · s, Δn (25 ° C):
0.109, Δε (25 ° C.): 9.3, V _th (20
° C): 1.23V.

The compound represented by the general formula (1) of the present invention can be prepared by a conventional organic synthetic chemistry method, for example, an organic compound.
It can be easily produced by appropriately combining techniques described in Synthesis, Organic Reactions, Laboratory Chemistry, etc. In the following, examples of their synthesis are shown, in which R ₁ , Y ₁ , X ₃ and X ₄ have the same meaning as described above, q is 1 or 0, and The abbreviations represent the compound names described in the right column. DIBAL: diisobutylaluminum hydride PTS: p-toluenesulfonic acid monohydrate Pd-C: palladium carbon R-Ni: Raney nickel LAH: lithium aluminum hydride FSDF: fluorosulfonyl difluoroacetic acid methyl ester DPAE: diethyl phosphinoacetate ethyl chloranil : Tetrachloro-p-benzoquinone

Production of the first group of the compounds of the present invention (compounds represented by the formula (1), wherein n is 0): It can be produced more preferably as follows.

[0086]

Embedded image

That is, an ester (12) was obtained by esterifying a carboxylic acid produced according to the method described in EP 315050 by a conventional method.
Reduction with L gives the aldehyde (13). 3 for this one
-Fluoro-4-substituted phenylmagnesium bromide (14) was allowed to act, followed by a dehydration reaction in the presence of an acidic catalyst such as PTS or sulfuric acid and a hydrogenation reaction using a catalyst such as Pd-C or R-Ni. Thus, the first group of the compound example (1) of the present invention can be produced. In addition, the compound example (1) can also be produced by the following route when the substituent Y ₁ is particularly a trifluoromethyl group.

[0088]

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That is, a carboxylic acid produced according to a method described in the above-mentioned EP 315050 is added to Can.
J. Chem. , 46 , 466 (1968) was applied to give acid chloride (15), to which Tetra
hedron Lett. , 25 , 4805 (198
4) According to the method described, 3-fluorophenylmagnesium bromide (16) is reacted to produce ketone (17). This was sequentially subjected to a reduction reaction using LAH, a dehydration reaction under acidic conditions, and hydrogenation to obtain a compound (18). Synth. , I, 323 (194
1) Iodination according to the described method (19)
Get. Tetrahedron, 48 , 6
FSDF (20) according to the method described in 555 (1992)
To give trifluoromethyl to produce the first group of compounds of the present invention wherein Y ₁ is a trifluoromethyl group.

A second group of the compounds of the present invention (compounds of the formula (1) wherein n is 1, ring A is 1,4-cyclohexylene, m and p are both 1, and X ₃ is a fluorine atom) Production: It can be produced more preferably as follows.

[0091]

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That is, Chem. Ber. , 121 ,
219 (1988) to the cyclohexanone derivative (21) produced according to the method described in Org. Synth. ,
V, 547 (1973), followed by DPAE, followed by a hydrogenation reaction and a reduction reaction with DIBAL to produce aldehyde (22). This is 3
-Fluoro-4-substituted phenylmagnesium bromide or 3,4-difluoro-4-substituted phenylmagnesium bromide (23) was allowed to act thereon, followed by dehydration and hydrogenation under acidic conditions in the same manner as described above.
A group of compounds of the invention (1) can be prepared.

A third group of the compounds of the present invention (wherein n is 1, ring A is 1,4-phenylene, m
Production of a compound in which X is 1, p is 0, X ₁ , X ₂ , and X ₄ are a hydrogen atom and X ₃ is a fluorine atom).

[0094]

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That is, the iodide (24) produced according to the method described in WO 9014405 includes, for example, Org. Chem. , 42 , 1821 (1977)
According to the above method, the Grignard reagent (14) is added to carry out a cross-coupling reaction to produce the third group of the compound (1) of the present invention. Among these compounds, those in which Y ₁ is particularly a trifluoromethyl group can be suitably produced by the following method.

[0096]

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That is, after adding 3-fluorophenylmagnesium bromide to the above-mentioned cyclohexanone derivative (21), a dehydration reaction under acidic conditions, a dehydrogenation reaction using chloranil, and an iodination reaction are sequentially performed to give iodine. The compound (1) of the third group can be obtained by producing the compound (25) and then reacting the compound with the FSDF (20) in the same manner as in the production of the compound of the first group.

A fourth group of the compounds of the present invention (wherein n is 1, ring A is 1,4-phenylene, m
Is 0, p is 1, X ₁ is a fluorine atom, and X ₂ is a hydrogen atom).

[0099]

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That is, Mol. Cryst. Liq.
Cryst. ,82331 (1982)
Thus, the cyanide produced is hydrolyzed and then treated with esthetics.
To give compound (26). This is already described
After subjecting to the reference LAH reduction reaction, treatment with hydrobromic acid
(Org. Synth., I, 25 (1941)) bromine
And J.I. Am. Chem. Soc. ,9
3, 195 (1971).
After reacting with Grignard reagent (27)
(28) is obtained. This is subjected to a reduction reaction with LAH,
Dehydration reaction and hydrogenation reaction under
A group of compounds of the invention (1) can be prepared.

[0101]

The present invention will be described in more detail with reference to the following examples. In each of the examples, C represents a crystal, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid, and the unit of the phase transition temperature is ° C.

Example 1 1-trifluoromethyl-2-fluoro-4- (2-
(4-propylcyclohexyl) ethyl) benzene (in the formula (1), R ₁ = propyl group, m = 1, n = p =
0, X ₁ = X ₂ = X ₄ = hydrogen atom, X ₃ = fluorine atom, Y ₁
= Compound (No. 1) having trifluoromethyl group)

4-propylcyclohexylacetic acid (100
mmol) and thionyl chloride (150 mmol) were heated under reflux for 3 hours, and then excess thionyl chloride was removed under reduced pressure of an aspirator to obtain a crude acidification product (100 m
mol). This acidification product (100 mmol)
Iron acetylacetone (5 mmol) and dry toluene 3
3-fluorobromobenzene (110 mmol), magnesium (110 mmol)
l) and tetrahydrofuran (hereinafter abbreviated as THF) 1
A Grignard reagent prepared from 00 ml was added dropwise at -50 ° C or lower, and the mixture was stirred at the same temperature for 1 hour. The obtained reaction product was added to 200 ml of 6M hydrochloric acid, and then toluene (100 ml ×
Extracted in 2). The extract was dried over anhydrous magnesium sulfate, and then the solvent was distilled off.
By recrystallization from l, 2-fluoro-4- (1-
Oxo-2- (4-propylcyclohexyl) ethyl)
Benzene (75 mmol) was obtained. This one (75mm
ol) and 200 ml of ethanol were added with sodium borohydride (75 mmol) while maintaining the temperature at 10 ° C. or lower, and the mixture was stirred at room temperature for 3 hours. After adding 50 ml of 6M hydrochloric acid and 200 ml of water to the obtained reaction product, ethyl acetate (1%) was added.
00 ml × 4). The solvent was distilled off from the extract under reduced pressure to obtain 2-fluoro-4- (1-hydroxy-2- (4-propylcyclohexyl) ethyl) benzene (70 mmol) as a residue.

To this (70 mmol) was added toluene 10
0 ml and 1.5 g of p-toluenesulfonic acid monohydrate were added, and the mixture was refluxed for 4 hours while removing generated water. After cooling, the reaction product was transferred to a separating funnel and water (100 ml × 3)
And dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain crude 2-fluoro-4- (2-
(4-Propylcyclohexyl) ethenyl) benzene (66 mmol) was obtained. 70 ml of ethanol, 60 ml of ethyl acetate and 3 g of 5% palladium on carbon as a catalyst were added to this (66 mmol) to obtain a mixture, which was stirred for 4 hours under a hydrogen atmosphere, followed by filtration of the catalyst, and then evaporation of the solvent. Was. The obtained residue was subjected to silica gel column chromatography (eluent: heptane), and then purified by recrystallization (ethanol 25 ml × 2) to give 2
-Fluoro-4- (2- (4-propylcyclohexyl) ethyl) benzene (34 mmol) was obtained. To this (34 mmol), iodine (34 mmol), iodic acid (18 mmol), 100 ml of acetic acid, 20 ml of water and 20 ml of carbon tetrachloride were added to obtain a mixture.
Heated to reflux for an hour. After cooling, 500 ml of water was added to the reaction product, and the mixture was extracted with toluene (200 ml). After the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a yellow oil.

The thiourea (264 mmo) was added to this yellow oil.
The mixture obtained by adding 1) and ethanol (600 ml) was heated, and the obtained homogeneous solution was allowed to stand at room temperature overnight. The precipitated needle-shaped crystals were collected by filtration, decomposed with water at 90 ° C., and heptane 10
After extraction with 0 ml, the extract was dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure.
Recrystallized with 1 ml of 1-iodo-2-fluoro-4- (2
-(4-Propylcyclohexyl) ethyl) benzene (10 mmol) was obtained. This (10 mmol) was added to fluorosulfonyldifluoroacetic acid methyl ester (1
00 mmol), copper iodide (10 mmol) and 20 ml of dimethylformamide were added to obtain a mixture, which was stirred at 90 ° C. for 2 hours. 100 m of water in the resulting reactant
l, and extracted with 100 ml of toluene.
1 × 3). After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel gel column chromatography (eluent: heptane), followed by recrystallization (ethanol 10 ml × 2) to give the title compound. 5.5 mmol (55% yield) were obtained. The various spectral data of this well supported its structure. The phase transition point was CI point: 11.7 ° C.

According to the method of Example 1, the following compounds of Group I (Nos. 2 to 18) were prepared. No. 21-Trifluoromethyl-2-fluoro-4- (2- (4-butylcyclohexyl) ethyl) benzene 31-Trifluoromethyl-2-fluoro-4- (2- (4-pentylcyclohexyl) ethyl) benzene C- Point I: 21.4 ° C 41-Trifluoromethyl-2-fluoro-4- (2- (4-hexylcyclohexyl) ethyl) benzene 51-Trifluoromethyl-2-fluoro-4- (2- (4-heptylci) Clohexyl) ethyl) benzene 6 1-Trifluoromethyl-2-fluoro-4- (2- (4-octylcyclohexyl) ethyl) benzene 7 1-Trifluoromethyl-2-fluoro-4- (4- (4-propylcyclohexyl) Butyl) benzene 81-trifluoromethyl-2-fluoro-4- (4- (4-butyl (Cyclohexyl) butyl) benzene 9 1-trifluoromethyl-2-fluoro-4- (4- (4-pentylcyclohexyl) butyl) benzene 10 1-trifluoromethyl-2-fluoro-4- (4- (4-hexylcyclohexyl) ) Butyl) benzene 11 1-Trifluoromethyl-2-fluoro-4- (4- (4-heptylcyclohexyl) butyl) benzene 12 1-Trifluoromethyl-2-fluoro-4- (4- (4-octylcyclohexyl) butyl ) Benzene 13 1-trifluoromethoxy-2-fluoro-4- (2- (4-propylcyclohexyl) ethyl) benzene 14 1-trifluoromethoxy-2-fluoro-4- (2- (4-butylcyclohexyl) ethyl ) Benzene 15 1-trifluoromethoxy 2-fluoro-4- (2- (4-pentylcyclohexyl) ethyl) benzene 16 1-trifluoromethoxy-2-fluoro-4- (2- (4-hexylcyclohexyl) ethyl) benzene 17 1-trifluoromethoxy 2-fluoro-4- (2- (4-heptylcyclohexyl) ethyl) benzene 18 1-trifluoromethoxy-2-fluoro-4- (2- (4-octylcyclohexyl) ethyl) benzene

Example 2 1-trifluoromethoxy-2-fluoro-4- (2-
(4- (2- (4-propylcyclohexyl) ethyl)
Cyclohexyl) ethyl) benzene (in the formula (1), R ₁ = propyl group, m = n = p = 1, ring A is 1,4
- _{cyclohexylene, X 1 = X 2 = X} 4 = hydrogen atom, X ₃ =
Production of compound (No. 19) wherein fluorine atom and Y ₁ = trifluoromethoxy group

4- (2) prepared according to the above-mentioned preparation example of aldehyde (22) as a raw material of the compound of the present invention (Group 2).
-(4-Propylcyclohexyl) ethyl) cyclohexylacetaldehyde (50 mmol) and THF 50m
to a mixture of 3-fluoro-4-trifluoromethoxybromobenzene (55 mmol), magnesium (5
5 mmol) and a Grignard reagent prepared from 80 ml of THF were added dropwise at 0 ° C. or lower, and the mixture was stirred at room temperature for 3 hours.
00 ml × 2). The extract was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. 100 ml of toluene and 1 g of p-toluenesulfonic acid monohydrate were added to the obtained residue, and the mixture was refluxed for 4 hours while removing generated water. After allowing to cool, the reaction product was transferred to a separating funnel, and water (100 m
1 × 3), dried over anhydrous magnesium sulfate,
The solvent was then distilled off under reduced pressure to give crude 1-trifluoromethoxy-2-fluoro-4- (2- (4- (2-
(4-Propylcyclohexyl) ethyl) cyclohexyl) ethenyl) benzene (43 mmol) was obtained.

This (43 mmol) was added to ethanol 5
A mixture containing 0 ml, 50 ml of ethyl acetate and 2 g of 5% palladium on carbon as a catalyst was stirred under a hydrogen atmosphere for 3 hours. After the catalyst was filtered off, the solvent was distilled off. The residue thus obtained was subjected to silica gel column chromatography (eluent: heptane), and then recrystallized (ethanol 1).
0 ml × 2) to give the title compound 16.5 mm
ol, yield 33%). The various spectral data of this well supported its structure. The phase transition point is C
-N point: 50.3 ° C, NI point: 101.7 ° C.

According to the method of Example 2, the following second group of compounds (Nos. 20 to 38) were produced. No. 20 1-trifluoromethyl-2-fluoro-4- (2- (4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 21 1-trifluoromethyl-2-fluoro-4- (2 -(4- (2- (4-butylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 22 1-trifluoromethyl-2-fluoro-4- (2- (4- (2- (4-pentylcyclohexyl) ethyl) Cyclohexyl) ethyl) benzene 23 1-trifluoromethyl-2-fluoro-4- (2- (4- (2- (4-hexylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 24 1-trifluoromethyl-2-fluoro -4- (2- (4- (2- (4-heptylcyclohexyl) ethyl) cyclohexyl) ethyl ) Benzene 25 1-trifluoromethoxy-2-fluoro-4- (2- (4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene CN point: 50.3 ° C, N- I point: 101.7 ° C. 25 1-trifluoromethoxy-2-fluoro-4- (2- (4- (2- (4-butylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 26 1-trifluoromethoxy-2 -Fluoro-4- (2- (4- (2- (4-pentylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 27 1-trifluoromethoxy-2-fluoro-4- (2- (4- (2- (4-hexylcyclohexyl) ethyl) cyclohexyl) ethyl) benzen 28 1-trifluoromethoxy-2-fluoro-4- (2- (4 -(2- (4-heptylcyclohexyl) ethyl) cyclohexyl) ethyl) benzen 29 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2- (4-propylcyclohexyl) ethyl) Cyclohexyl) ethyl) benzene Zen CI point: 88.9 ° C., NI point: 81.9 ° C. 30 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2- ( 4-butylcyclohexyl) ethyl) cyclohexyl) ethyl) benzen 31 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2- (4-pentylcyclohexyl) ethyl) cyclohexyl) ethyl) benzen Then 32 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2- (4-hexylcyclohexyl) ethyl) cyclo) Sil) ethyl) benzene 33 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2- (4-heptylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 34 1-trifluoromethoxy -2,6-difluoro-4- (2- (4- (2- (4-propylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 35 1-trifluoromethoxy-2,6-difluoro-4- (2- ( 4- (2- (4-butylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 36 1-trifluoromethoxy-2,6-difluoro-4- (2- (4- (2- (4-pentylcyclohexyl) ethyl) ) Cyclohexyl) ethyl) benzene 37 1-trifluoromethoxy-2,6-difluoro-4- (2- (4- (2- (4-hexylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene 38 1-trifluoromethoxy-2,6-difluoro-4- (2- (4- (2- (4-heptylcyclohexyl) ethyl) cyclohexyl) Ethyl) benzene

Example 3 4 '-(2- (4-propylcyclohexyl) ethyl)
-3-fluoro-4-trifluoromethoxybiphenyl (in the formula (1), R ₁ = propyl group, m = n = 1,
p = 0, ring A is 1,4-phenylene, X ₁ = X ₂ = X ₄ =
Production of compound (No. 39) in which a hydrogen atom, X ₃ = fluorine atom and Y ₁ = trifluoromethoxy group

The 1-iodo-4-produced as a starting material for the third group compound according to the method described in WO 9014405 described above.
A mixture containing (2- (4-propylcyclohexyl) ethyl) benzene (50 mmol), 100 ml of THF and palladium chloride (1 mmol) is heated under reflux, and then 3-fluoro-4-trifluoromethoxybromobenzene (55 mmol) and magnesium (55 mmol).
And a Grignard reagent prepared from 80 ml of THF was added dropwise over 1 hour, and the mixture was further refluxed for 1 hour. After allowing to cool, 200 ml of 6 M hydrochloric acid was added to the reaction product, and toluene (100 m
1 × 2). The extract was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained residue is subjected to silica gel column chromatography (eluent: heptane).
After that, purification was performed by recrystallization (ethanol 10 ml × 2) to obtain 39 mmol (yield 78%) of the title compound. The various spectral data of this well supported its structure. Further, the phase transition point is the CN point: 64.9 ° C.,
NI point: 87.9 ° C.

According to the method of Example 3, the following third group of compounds (Nos. 40 to 48) were produced. No. 40 4 '-(2- (4-propylcyclohexyl) ethyl) -3-fluoro-4-trifluoromethylbiphenyl CI point: 88.5 ° C 41 4'-(2- (4-butylcyclohexyl) ethyl) -3-Fluoro-4-trifluoromethylbiphenyl 42 4 '-(2- (4-pentylcyclohexyl) ethyl) -3-fluoro-4-trifluoromethylbiphenyl 43 4'-(2- (4-hexylcyclohexyl) Ethyl) -3-fluoro-4-trifluoromethylbiphenyl 44 4 ′-(2- (4-heptylcyclohexyl) ethyl) -3-fluoro-4-trifluoromethylbiphenyl 45 4 ′-(2- (4-butyl Cyclohexyl) ethyl) -3-fluoro-4-trifluoromethoxybiphenyl 46 4 ′-(2- (4-pentylci) (Rohexyl) ethyl) -3-fluoro-4-trifluoromethoxybiphenyl 474 '-(2- (4-hexylcyclohexyl) ethyl) -3-fluoro-4-trifluoromethoxybiphenyl 484'-(2- (4 -Heptylcyclohexyl) ethyl) -3-fluoro-4-trifluoromethoxybiphenyl

Example 4 1-trifluoromethoxy-2-fluoro-4- (2-
(2-fluoro-4- (4-propylcyclohexyl)
Phenyl) ethyl) benzene (in the formula (1), R ₁
= Propyl group, m = 0, n = p = 1, ring A is 1,4-phenylene, X ₁ = X ₃ = fluorine atom, X ₂ = X ₄ = hydrogen atom, Y ₁ = trifluoromethoxy group Compound (N
o. 49)) Manufacturing

After heating a mixture of 2-fluoro-4- (4-propylcyclohexyl) phenylacetic acid (100 mmol) and thionyl chloride (150 mmol) under reflux for 3 hours, excess thionyl chloride was removed under reduced pressure of an aspirator to obtain a crude product. An acidification product (100 mmol) was obtained. To a mixture of this acidification product (100 mmol), iron acetylacetone (5 mmol) and 300 ml of dry toluene, 3-fluoro-4-trifluoromethoxybromobenzene (110 mmol), magnesium (110 mm)
ol) and a Grignard reagent prepared from 100 ml of THF were added dropwise at −50 ° C. or lower, and the mixture was further stirred at the same temperature for 1 hour. The obtained reaction product was added to 200 ml of 6M hydrochloric acid, and then extracted with toluene (100 ml × 2). The extract was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained residue was recrystallized from 50 ml of ethanol to give 1-trifluoromethoxy-2-fluoro-4- (1-
Oxo-2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethyl) benzene (70 mmol
1) was obtained.

This product (70 mmol) and ethanol 2
Sodium borohydride (70 mmol) was added to 00 ml of the mixture while maintaining the temperature at 10 ° C. or lower, and the mixture was further stirred at room temperature for 3 hours. To the obtained reaction product, 50 ml of 6M hydrochloric acid and 200 ml of water were added, and extracted with ethyl acetate (100 ml × 4). The solvent was distilled off under reduced pressure, and 1-trifluoromethoxy-2-fluoro-4- (1-hydroxy-2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethyl) benzene (as a residue) 65 mmol)
I got To this (65 mmol), add 100 m of toluene
l and 1.5 g of p-toluenesulfonic acid monohydrate were added,
The mixture was heated under reflux for 4 hours while removing generated water. After cooling, the reaction product was transferred to a separating funnel, washed with water (100 ml × 3), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude 1-trifluoromethoxy-2-fluoro-4- (1-hydroxy-2- (2-fluoro-4
-(4-Propylcyclohexyl) phenyl) ethenyl) benzene (59 mmol) was obtained.

This (59 mmol) and ethanol 7
A mixture of 0 ml, 60 ml of ethyl acetate and 3 g of 5% palladium on carbon as a catalyst was stirred under a hydrogen atmosphere for 4 hours. After the catalyst was filtered off, the solvent was distilled off, and the obtained residue was subjected to silica gel chromatography (eluent: heptane), and then purified by recrystallization (ethanol 25 ml × 2) to give 28 mmol of the title compound (yield). 48%). The various spectral data of this well supported its structure. The phase transition point was CI point: 43.8 ° C.

According to the method of Example 4, the following fourth group of compounds (Nos. 50 to 78) were produced. No. 50 1-trifluoromethyl-4- (2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethyl) benzene 51 1-trifluoromethyl-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 52 1-trifluoromethyl-4- (2- (2-fluoro-4- (4-pentylcyclohexyl) phenyl) ethyl) benzene 53 1-trifluoromethyl- 4- (2- (2-fluoro-4- (4-hexylcyclohexyl) phenyl) ethyl) benzene 54 1-trifluoromethyl-4- (2- (2-fluoro-4- (4-heptylcyclohexyl)) Phenyl) ethyl) benzene 55 1-trifluoromethoxy-4- (2- (2-fluoro-4- (4-propylcyclohexyl) ) Phenyl) ethyl) benzene 56 1-trifluoromethoxy-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 57 1-trifluoromethoxy-4- (2- ( 2-fluoro-4- (4-pentylcyclohexyl) phenyl) ethyl) benzene 58 1-Trifluoromethoxy-4- (2- (2-fluoro-4- (4-hexylcyclohexyl) phenyl) ethyl) benzene 59 1-trifluoromethoxy-4- (2- (2-fluoro-4- (4-heptylcyclohexyl) phenyl) ethyl) benzene

60 1-trifluoromethyl-2-fluoro-4- (2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethyl) benzene 61 1-trifluoromethyl-2-fluoro-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 62 1-trifluoromethyl-2-fluoro-4- (2- (2-fluoro-4- (4-pentylcyclohexyl) Phenyl) ethyl) benzene 63 1-trifluoromethyl-2-fluoro-4- (2- (2-fluoro-4- (4-hexylcyclohexyl) phenyl) ethyl) benzene 64 1-trifluoromethyl-2-fluoro- 4- (2- (2-fluoro-4- (4-heptylcyclohexyl) phenyl) ethyl) benzene CI Point: 43.8 ° C 65 1-trifluoromethoxy-2-fluoro-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 66 1-trifluoromethoxy-2-fluoro -4- (2- (2-Fluoro-4- (4-pentylcyclohexyl) phenyl) ethyl) benzene 67 1-trifluoromethoxy-2-fluoro-4- (2- (2-fluoro-4- (4- Hexylcyclohexyl) phenyl) ethyl) benzene 68 1-trifluoromethoxy-2-fluoro-4- (2- (2-fluoro-4- (4-heptylcyclohexyl) phenyl) ethyl) benzene 69 1-trifluoromethyl-2 , 6-Difluoro-4- (2- (2-fluoro-4- (4-propylcyclohexyl) phenyl) ethyl Benzene

70 1 1-trifluoromethyl-2,6-difluoro-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 71 1-trifluoromethyl-2,6 -Difluoro-4- (2- (2-fluoro-4- (4-pentylcyclohexyl) phenyl) ethyl) benzene 72 1-trifluoromethyl-2,6-difluoro-4- (2- (2-fluoro -4- (4-hexylcyclohexyl) phenyl) ethyl) benzene 73 1-trifluoromethyl-2,6-difluoro-4- (2- (2-fluoro-4- (4-heptylcyclohexyl) phenyl) ethyl) Benzene 74 1-trifluoromethoxy-2,6-difluoro-4- (2- (2-fluoro-4- (4-propylcyclohexyl) Enyl) ethyl) benzene 75 1-trifluoromethoxy-2,6-difluoro-4- (2- (2-fluoro-4- (4-butylcyclohexyl) phenyl) ethyl) benzene 76 1-trifluoromethoxy-2 , 6-Difluoro-4- (2- (2-fluoro-4- (4-pentylcyclohexyl) phenyl) ethyl) benzene 77 1-trifluoromethoxy-2,6-difluoro-4- (2- (2- Fluoro-4- (4-hexylcyclohexyl) phenyl) ethyl) benzene 78 1-Trifluoromethoxy-2,6-difluoro-4- (2- (2-fluoro-4- (4-heptylcyclohexyl) phenyl) Ethyl) benzene

Example 5 (Use Example 1) 4- (4-Propylcyclohexyl) benzonitrile 24% by weight 4- (4-Pentylcyclohexyl) benzonitrile 36% by weight 4- (4-heptylcyclohexyl) benzonitrile 25% by weight A liquid crystal composition A comprising 15% by weight of 4- (4-propylphenyl) benzonitrile was prepared. Its clearing point is 72.4 ° C., Δε is 11.0, Δn is 0.137, 20
The viscosity at 2 ° C. was 27.0 mPa · s, and V _th at a cell thickness of 9 μm was 1.78 V. This liquid crystal composition A (85
% By weight) of the compound 1-trifluoromethoxy-2-fluoro-4- (2- (4-
Propylcyclohexyl) ethyl) benzene (No.
When 1) was mixed at 15% by weight to prepare a liquid crystal composition A1-1, the clearing point was 49.3 ° C., and Δ △ was 10.5.
(Extrapolated value 7.7), Δn is 0.117 (extrapolated value 0.00)
4), the viscosity at 20 ° C. is 24.8 mPa · s (extrapolated value 12.3 mPa · s), V _th at a cell thickness of 8.7 μm is 1.35 V, and VHR is 99.8 at 100 ° C.
%Met. This composition A1-1 was left in a freezer at -20 ° C. for 60 days, but no crystal precipitation was observed.

Example 6 (Use Example 2) No. 1 was replaced with Compound No. 1. A liquid crystal composition A1-2 was obtained in the same manner as in Example 5, except that 1-trifluoromethyl-2-fluoro-4- (2- (4-pentylcyclohexyl) ethyl) benzene was used. Physical properties of this product were as follows: Δε: 10.6, Δn: 0.120, viscosity: 2
It was 5.2 mPa · s (extrapolated value: 19.6 mPa · s).

Example 7 (Use Example 3) No. 1 was replaced with Compound No. 1. 19-trifluoromethoxy-2-fluoro-4- (2- (4- (2- (4
-Propylcyclohexyl) ethyl) cyclohexyl)
A liquid crystal composition A2-1 was obtained in the same manner as in Example 5 except that (ethyl) benzene was used. The physical properties of this product are
ε: 10.4, Δn: 0.128, viscosity: 25.9 mP
a · s, V _th : 1.74 V

Example 8 (Use Example 4) No. 1 was replaced with Compound No. 1. 1-trifluoromethyl-2,6-difluoro-4- (2- (4- (2-
A liquid crystal composition A2-2 was obtained in the same manner as in Example 5, except that (4-propylcyclohexyl) ethyl) cyclohexyl) ethyl) benzene was used. Physical properties of this
Δε: 11.6, Δn: 0.127, viscosity: 35.0 m
Pa · s, V _th : 1.70 V

Example 9 (Use Example 5) No. 1 was replaced with Compound No. 1. 40's 4 '-(2- (4
-Propylcyclohexyl) ethyl) -3-fluoro-
A liquid crystal composition A3-1 was obtained in the same manner as in Example 5, except that 4-trifluoromethylbiphenyl was used. The physical properties of this product were as follows: Δε: 11.3, Δn: 0.137, viscosity: 29.6 mPa · s (extrapolated value: 48.6 mPa · s).
s), V _th : 1.74 V

Example 10 (Use Example 6) No. 1 was replaced with Compound No. 1. 49 of 1-trifluoromethoxy-2-fluoro-4- (2- (2-fluoro-
A liquid crystal composition A4-1 was obtained in the same manner as in Example 5, except that 4- (4-propylcyclohexyl) phenyl) ethyl) benzene was used. The physical property value of this was Δ △: 1
1.1, Δn: 0.139, viscosity (extrapolated value): 37.4
mPa · s.

Comparative Example 1 As an example of a comparative compound having a structure similar to the compound of the present invention (No. 3) contained in the first group, the above-mentioned JP-T-63-5032 has been disclosed.
No. 26, a compound represented by the formula (c) (Comparative Compound 1), a compound described in the formula (d) described in JP-A-2-111834 (Comparative Compound 2), and a compound represented by the formula (2)
Compound represented by formula (e) described in No. 47 (Comparative compound 3)
Were determined, and their physical property values (clearing point (CI point), viscosity extrapolated from a liquid crystal composition prepared as described below) and Δε of a liquid crystal composition containing them were determined.

[0128]

Embedded image

For the preparation of the liquid crystal composition, each of the above comparative compounds was prepared as described in Nos. Example 6 except that compound 3 was used instead of compound 3.
Comparative liquid crystal composition B1-1,
B1-2 and B1-3 were obtained. The results were as follows (the results of the compound of No. 3 and the liquid crystal composition A1-2 (Example 6) are also shown).

Clearing point Extrapolated viscosity Δε (° C) (mPa · s) Compound of the present invention (No. 3) 21.4 19.6 A1-1 10.6 Comparative compound 1 10 20.8 B1-1 8.3 Comparative compound 2-30-8.2 B1-2 10.9 Comparative compound 30-12.2 B1-3 10.9

The following can be understood from the results. That is, the present invention No. Despite having a fluorine atom as a substituent on the side compared to Comparative Compound 1, Compound 3 has a 1,2-ethylene group introduced into the bonding group at the center of the molecule, resulting in a decrease in clearing point. In addition, no increase in extrapolated viscosity is observed, and an extremely large Δε is shown. Such an effect due to the introduction of a 1,2-ethylene group is based on conventional technical common sense,
For example, the comparative compound 2 having a 1,2-ethylene group introduced therein
This is completely different from the finding that the clearing point is lower and the extrapolated viscosity is also higher than that of the comparative compound 3 which is unlikely, and it is completely surprising.

Comparative Example 2 As a comparative compound having a structure similar to that of the compound of the present invention (No. 19) included in the second group, the above-mentioned JP-A-2-5011311
In the formula (b) described in (1), n = 3, and a 3-ring directly-linked compound represented by the formula (f) (Comparative Compound 4) was selected. Its phase transition temperature is C 39 SB 68 N 148.6 I.

[0133]

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This comparative compound 4 clearly shows strong smecticity. When this compound is used as a component, a smectic phase appears at a low temperature in the obtained liquid crystal composition, which is not preferable. In contrast, the compound of the present invention (No. 19) in which two 1,2-ethylene groups were introduced into the central bonding group did not show a smectic phase but only a nematic phase (see Example 2). Absent.

Comparative Example 3 As a comparative compound having the same structure as the compound of the present invention (No. 40) included in the third group, except that the substitution position of the fluorine atom was changed from the terminal phenylene to the central phenylene,
iq. Cryst. , 18 (4), 665 (1995)
And a compound represented by the formula (g) (Comparative Compound 5). The physical properties and Δε and Δn of the liquid crystal composition (B3-1) containing the same were determined in the same manner as in Comparative Example 1. The results were as follows. Clearing point: 8
0.4 ° C, extrapolated viscosity: 52.0 mPa · s, Δε: 1
1.0, Δn: 0.138

[0136]

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The compound of the present invention (No. 40) is known to have a clearing point as high as about 8 ° C. and a low viscosity as compared with Comparative Compound 5, and it has been determined from other studies that Δε, Δn and viscosity It has been revealed that the temperature dependency is small, the viscosity rise at low temperature is small, and the compatibility with other liquid crystal compounds is excellent.

Comparative Example 4 As a comparative compound having the same structure as the compound of the present invention (No. 49) included in the fourth group, except that the position of substitution of the fluorine atom was changed from the terminal phenylene to the central phenylene, the above-mentioned Liq. Cryst. , 18 (4), 665 (199
A compound disclosed in 5) and represented by the formula (k) (Comparative Compound 6) was selected. The physical properties and Δ も の and Δn of the liquid crystal composition (B4-1) containing the same were determined in the same manner as in Comparative Example 1. The results were as follows. Clearing point:
43 ° C., extrapolated viscosity: 52.0 mPa · s, Δε: 11.
0, Δn: 0.138

[0139]

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It is known that the compound of the present invention (No. 49) has a higher clearing point, Δε and Δn both higher than or equal to those of the comparative compound 6, and particularly low viscosity. In addition, a separate study has revealed that Δ 温度, Δn, and viscosity have small temperature dependence and excellent compatibility with other liquid crystal compounds.

[0141]

As described above, all of the compounds of the present invention have a wide nematic phase temperature range, lower viscosity, large positive Δε, high chemical stability, high compatibility with other liquid crystal compounds at low temperatures, It simultaneously satisfies various characteristics such as small temperature dependence on viscosity and Δε, extremely high specific resistance (high voltage holding ratio) and good UV stability, and is particularly suitable as a liquid crystal compound for TFT. Therefore, when the compound of the present invention is used as a component of a liquid crystal composition, in addition to the feature of being excellent in solubility with other liquid crystal materials, a six-membered ring of a molecular component, a substituent and / or a bonding group are added. By proper selection, a new liquid crystal composition having desired physical properties can be provided.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 19/42 C09K 19/42 G02F 1/13 500 G02F 1/13 500 (72) Inventor Etsuo Nakagawa 8890 Goi, Ichihara-shi, Chiba (56) References JP-A-7-179374 (JP, A) JP-A-7-165639 (JP, A) JP-A-7-138567 (JP, A) JP-A-7-62348 (JP, A) Table 5-500204 (JP, A) Special table 4-500682 (JP, A) Special table 4-500214 (JP, A) Special table 4-501576 (JP, A) Special table 4-500217 ( JP, A) (58) Fields surveyed (Int. Cl. ⁶ , DB name) C09K 19/30 C07C 13/18 C07C 25/18 C07C 43/21 C07C 43/225 C09K 19/42 G02F 1/13 CA ( STN)

Claims (9)

(57) [Claims] 1. A compound of the general formula (1) (Wherein, R ₁ is an alkyl group having 1 to 10 carbon atoms, ring A is 1,4-phenylene , X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom or a fluorine atom, and Y ₁ is CF
₃ or OCF ₃ wherein m, n and p are each independently 1 or 0, but m + p = 1 and n =
When 1 and p = 0, X ₁ and X ₂ are at least
X is H and at least one of X ₃ and X ₄ is F
When n = 1 and X ₃ and X ₄ are both F, X ₁
Is H. )). 2. n is 0, m is 1, X ₃ is a fluorine atom, X ₄
The liquid crystal compound according to claim 1, wherein is a hydrogen atom. 3. The liquid crystal compound according to claim 1, wherein n is 1, m is 1, p is 0, X ₁ , X ₂ and X ₄ are all hydrogen atoms, and X ₃ is a fluorine atom. 4. The liquid crystal compound according to claim 1, wherein n is 1, m is 0, p is 1, X ₁ is a fluorine atom, and X ₂ is a hydrogen atom. 5. A liquid crystal composition characterized in that at least one liquid crystalline compound according to any one of claims 1-4. 6. The first component contains at least one liquid crystalline compound according to any one of claims 1 to 4 , and the second component has the general formula (2), (3) or (4). Formula 2 (Wherein, R ₂ represents an alkyl group having 1 to 10 carbon atoms;
₂ is a fluorine atom, a chlorine atom, OCF ₃ , OCF ₂ H, C
F ₃ , CF ₂ H or CFH ₂ , L ₁ , L ₂ , L
₃ and L ₄ each independently represent a hydrogen atom or a fluorine atom; Z ₁ and Z ₂ each independently represent-(C
H ₂ ) ₂ —, —CH ＝ CH— or a covalent bond;
Is 1 or 2. A liquid crystal composition comprising at least one compound selected from the group consisting of: As 7. first component, at least one liquid crystalline compound according to any one of claims 1-4 1, as a second component, the general formula (5), (6), (7) , (8)
And (9) (Wherein, R ₃ represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl group or alkenyl group is substituted by an oxygen atom. Ring B may be 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-2,5- Diyl, ring C
Represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, and ring D is 1,4-
Represents cyclohexylene or 1,4-phenylene;
_{3 - (CH 2) 2 -,} - COO- or indicates a covalent bond, _{L 5} and _{L 6} represents a hydrogen atom or a fluorine atom independently of one another, b and c, independently of one another 0 or 1 It is. ) (Wherein, R ₄ represents an alkyl group having 1 to 10 carbon atoms;
₇ represents a hydrogen atom or a fluorine atom, d is 0 or 1
It is. ) (Wherein, R ₅ represents an alkyl group having 1 to 10 carbon atoms, ring E and ring F independently represent 1,4-cyclohexylene or 1,4-phenylene, and Z ₄ and Z ₅ represent independently of each other -COO- or indicates a covalent bond, _{Z 6}
Represents -COO- or -C≡C-; L ₈ and L ₉
Represents a hydrogen atom or a fluorine atom independently of each other;
₃ is a fluorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF
₂ H or CFH ₂ , wherein Y ₃ is OCF ₃ , OCF
L for ₂ H, CF ₃ , CF ₂ H or CFH _2
8 and L ₉ both represent a hydrogen atom. e, f and g are each independently 0 or 1; ) (Wherein, R ₆ and R ₇ independently of one another have 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring H represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring I represents 1,4-cyclohexylene or 1,4-phenylene, and Z ₆ represents —C≡ C -, - COO -, - (CH 2) 2
-, -CH = CH-C≡C- or a covalent bond;
₇ represents -COO- or a covalent bond. ) (Wherein, R ₈ and R ₉ independently of one another have 1 to 1 carbon atoms)
0 represents an alkyl group or an alkenyl group having 2 to 10 carbon atoms. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring J represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring K is 1,4-cyclohexylene, and one or more hydrogen atoms on the ring are substituted with fluorine atoms Represents optionally 1,4-phenylene or pyrimidine-2,5-diyl, ring L represents 1,4-cyclohexylene or 1,4-phenylene, and Z ₈ and Z ₁₀ independently of one another -COO-,
— (CH ₂ ) ₂ — or a covalent bond, and Z ₉ is —CH
＝ CH—, —C≡C—, —COO— or a covalent bond, and h is 0 or 1. A liquid crystal composition comprising at least one compound selected from the group consisting of: 8. The first component contains at least one liquid crystal compound according to any one of claims 1 to 4 , and as a part of the second component, a compound represented by the general formula (2) according to claim 6 :
It contains at least one compound selected from the group consisting of (3) and (4), and as another portion of the second component,
Formula according to claim 7 (5), (6), (7),
A liquid crystal composition comprising at least one compound selected from the group consisting of (8) and (9). 9. A liquid crystal display device comprising the liquid crystal composition according to claim 5 .