JP2002308814A - Compound having difluoroalkoxy at its terminal, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal compound large in the absolute value of Δε, relatively low in viscosity, having relatively large Δn and showing good compatibility even to a low temperature, a low voltage drivable composition and a liquid a crystal display element using the same. SOLUTION: The liquid crystal compound is represented by formula (1) (wherein, R<1> is an alkyl, R<2> is hydrogen, a halogen, cyano or alkyl, rings A<1> to A<3> are each independently trans-1,4-cyclohexylene, 1,4'-cyclohexenylene or 1,4-phenylene, Z<1> to Z<3> are each independently a single bond, -CH2 CH2 -, -CH2 O-, -OCH2 -, -COO-, -OCO-, -CH=CH, -CF2 O- or -OCF2 -, Y<1> to Y<3> are each independently hydrogen or fluorine but Y<1> is not fluorine, Y<2> is not hydrogen and Y<3> is not hydrogen and l and m are each independently 0 or 1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound having a difluoroalkoxy terminal, a liquid crystal composition containing the compound,
And a liquid crystal display device using the same. This compound is particularly useful as a component of a liquid crystal composition used in TN, STN, TFT, and OCB modes. Note that a liquid crystal composition and a liquid crystal display element may be referred to as a composition and an element, respectively. The compounds represented by formulas (1) to (12) may be referred to as compounds (1) to (12), respectively.

[0002]

BACKGROUND ART A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal composition. Depending on the display method of the element, twisted nematic (TN), dynamic scattering (DS),
Guest host (GH), orientation change (DAP), super twisted nematic (STN), voltage controlled birefringence (VCB, E
CB or TB), vertical alignment (VA), multi-domain vertical alignment (MVA), OCB, and the like. The properties of the composition required depend on these modes. In any case, it is stable against environmental factors such as moisture, air, heat and light, has a liquid crystal phase in a wide temperature range around room temperature, has a low viscosity, and has a low voltage for driving the element. Low is required for the composition. Further, characteristics such as optimum dielectric anisotropy (△ ε) and optimum refractive index anisotropy (△ n) are required according to the element. Since a single compound does not satisfy such properties, a composition in which a plurality of compounds are mixed is used. Therefore, the compounds need to have good compatibility. In particular, good compatibility at low temperatures is desired.

[0003] In recent years, as devices have been downsized and the driving voltage of the device has been low, a composition having a low threshold voltage has been required.
The threshold voltage (Vth) is represented by the following equation. (HJ Deuling, et al., Mol. Cryst. Liq. Cryst.,
27 (1975) 81) Vth = π (K / ε0 △ ε) ^{1/2 In} this equation, K is the elastic constant of the composition, and ε0 is the dielectric constant in a vacuum. As can be seen from the equation, there are two ways to reduce Vth, either increasing Δε or decreasing K. However, since it is difficult to control the elastic constant K of the composition, a composition having a large Δε is usually used. Under these circumstances, compounds having a large Δε have been actively developed.

In order to increase Δε of a compound, a group having a large dipole moment such as cyano or trifluoromethyl is used as a terminal group of the compound. Further, 1,4-phenylene substituted with fluorine is introduced into the skeleton. And
The direction of the dipole moment between the terminal group and the fluorinated phenylene is set to the same direction as the molecular long axis. However, as the number of fluorine atoms in the phenylene ring increases, the viscosity increases and the clearing point decreases. Therefore, it is difficult to increase Δε while suppressing an increase in viscosity and a decrease in clearing point.

[0005] Liquid crystal display elements have disadvantages such as (1) slow response speed and (2) narrow viewing angle compared to CRT.
A first method of improving the response speed involves mixing a large amount of a low-viscosity compound to lower the viscosity of the composition. Bicyclic compounds such as bicyclohexanes and phenylcyclohexanes have low viscosity. However, it is very difficult to find a compound having a lower viscosity than these compounds. Another method for improving the response speed is to reduce the thickness (hereinafter, may be abbreviated as d) of the liquid crystal cell in the device. However, when the display quality is taken into consideration, the proper value of the retardation (△ nd), which is the condition of the first minimum, must not be deviated (Appl. Phys. Lett., 38).
(7), 497). For this reason, a compound having a large Δn was required. As a compound showing a large Δn, for example, J. Mal
The following tolan derivatives (13) disclosed by thete et al.
There is. (In the formula, R represents alkyl.)

The tran derivative (13) has a Δn of about 0.2
It has good characteristics of being as large as 0, having a high clearing point, and having a relatively low viscosity. However, since they are deteriorated by ultraviolet irradiation and have a problem in reliability, they are hardly used for TFT-driven devices. On the other hand, among the compounds for driving a TFT, the following compounds (14) and (15) (JP-A-2-23)
No. 3626) and (16) (MJ Goulding et
al., Liq. Cryst., 1993, 14 (5), 1397) show a relatively large Δn.

The compounds (14) and (15) have 3,4,5-trifluorophenyl as a terminal group and have a large Δn and a large dielectric anisotropy (Δε). Δn of compound (16)
Is as large as 0.26, making it an attractive compound for increasing the Δn of the composition. However, the compound (1
4) to (16) show good characteristics, but the compatibility at low temperatures of -20 ° C or lower is not very good. Next, a method for improving the narrow viewing angle will be described. In-plane switching (IPS), vertical alignment (VA), multi-domain vertical alignment (MVA) to improve viewing angle,
New schemes such as OCB have been announced. For these devices, a composition having a negative Δε is used. The following compound (17) has been reported as a compound exhibiting a large negative Δε (V. Reiffenrath et al., Liq. Cryst., 5 (1), 159 (19)
89)).

This document discloses that Δε of compound (17) is-
4.1, disclosed negatively large, but at -20 ° C
The compatibility at low temperatures below is not very good. As described above, in order to improve the problems of the response speed and the viewing angle, which are the drawbacks of the liquid crystal display device, excellent characteristics, that is, a large positive or negative Δε, a low viscosity, and a relatively large Δn, Further, liquid crystal compounds exhibiting good phase solubility even at low temperatures have been desired. As a compound having a terminal group similar to that of the present application, the compound (A) is disclosed in DE4223501A1. (In the formula, R represents alkyl.)

The compound (A) has 1,1-difluoro-2-propenyloxy as a terminal group, but the above publication does not describe physical properties such as Δε. Since the direction of the dipole of fluorine substituted with 1,4-phenylene and the direction of the dipole of OCF ₂ are opposite, it is considered that Δε of the compound (A) is not large.

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art, to provide a large absolute value of Δε, a relatively small viscosity, a relatively large Δn, and a good compatibility even at a low temperature. The present invention provides a liquid crystal compound as described above. It is still another object of the present invention to provide a composition which can be driven at a low voltage in various display modes, and a liquid crystal display device using the composition.

[0010]

Means for Solving the Problems The present inventors diligently studied to achieve the above object. As a result, the following compound (1) having phenylene substituted with difluoroalkoxy at the terminal was found. Furthermore, they have found that a composition containing the compound (1) is most suitable for driving a device at a low voltage, and have completed the present invention. The present invention is the first
It is represented by the following items.

1. A compound represented by the following formula (1). Wherein R ¹ represents alkyl having 1 to 20 carbons, wherein any non-adjacent methylene may be replaced by oxygen or sulfur; R ² is hydrogen, halogen, cyano or C ¹ to C 20 Wherein any non-adjacent methylene is -CH
= CH-, oxygen or sulfur may be replaced, in this alkyl any hydrogen may be replaced by halogen; ring A ¹ , ring A ² and ring A ³ are each independently trans-1,4 -Cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, wherein any non-adjacent methylene in trans-1,4-cyclohexylene and 1,4-cyclohexenylene is replaced by oxygen or sulfur Any non-adjacent ＝ CH— in 1,4-phenylene may be replaced by nitrogen and hydrogen may be replaced by halogen;
Z ¹ , Z ² and Z ³ each independently represent a single bond, —CH ₂ CH
_{2 -, - CH 2 O -} , - OCH 2 -, - COO -, - OC
O -, - CH = CH - , - CF 2 O- or -OCF ₂ -
Y ¹ , Y ² and Y ³ each independently represent hydrogen or fluorine, but Y ¹ is fluorine, Y ² is hydrogen, and Y ³ is not hydrogen; l and m are each independently To indicate 0 or 1).

2. The compound is represented by the formula (1) where l = m
2. The compound according to item 1, which is a compound represented by the following formula (1-1) wherein = 0. 3. In the formula (1-1), the second ring A ¹ is 1,4-phenylene in which hydrogen may be replaced by halogen.
Item. 4. In the formula (1-1), the third group in which Z ¹ is a single bond
Item.

5. The compound is represented by the formula (1) where l = m
2. The compound according to item 1, which is a compound represented by the following formula (1-2) wherein = 0. 6. 6. The compound according to claim 5, wherein in the formula (1-2), the ring A ¹ and the ring A ² are 1,4-phenylene in which hydrogen may be replaced by halogen. 7. 7. The compound according to claim 6, wherein in formula (1-2), Z ¹ and Z ² are a single bond.

8. The compound is represented by the formula (1) where l = m
= 0, a compound represented by the following formula (1-3).
A compound according to claim 1.9. In the formula (1-3), the ring A¹, Ring A^TwoAnd ring A
^ThreeIs a 1,4-phenyl group in which hydrogen may be replaced by halogen.
9. The compound according to item 8, which is phenylene. 10. In the formula (1-3), Z¹, Z^TwoAnd Z^ThreeBut
Each independently -CH_TwoCH _Two-, -CH_TwoO-, -OCH_Two
Or a compound according to item 9, which is a single bond. 11. In equation (1), Y¹And Y^TwoIs fluorine, Y^ThreeBut
2. The compound according to item 1, which is hydrogen. 12. In equation (1), Y¹Item 1 wherein is hydrogen
Listed compound. 13. Item 13. The compound according to any one of Items 1 to 12
A liquid crystal composition containing at least one.

14. As the first component, items 1 to 12
Item, and at least one compound selected from the compound group represented by the following formulas (2), (3) and (4) as a second component. Liquid crystal composition. (Wherein R ³ represents alkyl having 1 to 10 carbons, and any non-adjacent —CH ₂ — in the alkyl may be replaced by oxygen or —CH ＝ CH—, and in this alkyl, any hydrogen is Optionally substituted with fluorine;
X ¹ is fluorine, chlorine, —OCF ₃ —, —OCF ₂ H, —CF
_{3, -CF 2 H, -CFH 2} , -OCF 2 CF 2 H or -O
CF ₂ shows the CFHCF _3; L ¹ and L ² each independently represents a hydrogen or fluorine; Z ⁴ and Z ⁵ are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - COO -, - CF _{2
O -, - OCF 2 -,} - CH = CH- or a single bond; ring A and ring B each independently trans-1,
4-cyclohexylene, 1,3-dioxane-2,5-
Diyl or 1,4-phenylene in which ring hydrogen may be replaced by fluorine, and ring C is trans-1,4-
Cyclohexylene or 1,4-phenylene wherein hydrogen on the ring may be replaced by fluorine).

15. As the first component, items 1 to 12
And at least one compound selected from the group of compounds represented by the following formulas (5) and (6) as a second component:
Containing liquid crystal composition. (Wherein, R ⁴ and R ⁵ each independently represent alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CHＣＨCH—, In this alkyl any hydrogen may be replaced by fluorine; X ² is -CN or -C≡C
Ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,
Represents 5-diyl or pyrimidine-2,5-diyl;
Ring E is trans-1,4-cyclohexylene, 1,4-phenylene in which ring hydrogen may be replaced by fluorine,
Or pyrimidine-2,5-diyl; ring F represents trans-1,4-cyclohexylene or 1,4-phenylene; Z ⁶ represents — (CH ₂ ) ₂ —, —COO—, —CF
L ³ , L ⁴ and L ⁵ each independently represent hydrogen or fluorine; b, c represents ₂ O—, —OCF ₂ — or a single bond;
And d each independently represent 0 or 1.)

16. As the first component, items 1 to 12
The compound contains at least one compound according to any one of the above items, and as a second component, at least one compound selected from the compound group represented by the following formulas (7), (8) and (9) Liquid crystal composition containing. (Wherein R ⁶ and R ⁷ each independently represent an alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CH ＝ CH—, In this alkyl any hydrogen may be replaced by fluorine; Ring G and Ring I are each independently trans-1,4-cyclohexylene or 1,4
L ⁶ and L ⁷ each independently represent hydrogen or fluorine, but not simultaneously hydrogen;
Z ⁷ and Z ⁸ are each independently — (CH ₂ ) ₂ —, —COO
-Or a single bond).

17. As the first component, items 1 to 12
Item 14. The compound according to any one of items 14 to 14, which comprises at least one compound according to any one of the above items,
And at least one compound selected from the group of compounds represented by (4), and as the third component, selected from the group of compounds represented by the following formulas (10), (11) and (12) A liquid crystal composition containing at least one compound. (Wherein R ⁸ and R ⁹ each independently represent an alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CHＣＨCH—, Any hydrogen in this alkyl may be replaced by fluorine; Ring J, Ring K and Ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or ring hydrogen. Represents 1,4-phenylene which may be replaced by fluorine; Z ⁹ and Z ¹⁰ are each independently -C≡C-, -COO-,-
(CH _{2) 2} -, - shows a CH = CH- or a single bond).

18. As the first component, items 1 to 12
Item, and at least one compound selected from the compound group represented by formulas (5) and (6) according to item 15 is contained as the second component. A liquid crystal composition comprising, as a third component, at least one compound selected from the group of compounds represented by formulas (10), (11) and (12) according to claim 17. 19. As a first component, at least one compound according to any one of Items 1 to 12 is contained, and as a second component, a compound represented by formulas (7), (8), and (9) described in Item 16 Item 17 comprises at least one compound selected from the group consisting of the compounds represented by the formula (1)
0) A liquid crystal composition containing at least one compound selected from the group of compounds represented by (11) and (12).

20. As the first component, items 1 to 12
Item 14. The compound according to any one of items 14 to 14, which comprises at least one compound according to any one of the above items,
And at least one compound selected from the group of compounds represented by (4), and as the third component, a compound selected from the group of compounds represented by formulas (5) and (6) described in Item 15 The compound of formula (10), (11) and (1) according to item 17 containing at least one component and serving as a fourth component.
A liquid crystal composition containing at least one compound selected from the compound group represented by 2). 21. 21. The liquid crystal composition according to any one of items 13 to 20, further comprising at least one optically active compound. 22. A liquid crystal display device comprising the liquid crystal composition according to any one of items 13 to 21. Compound (1)-
(12) may be an analog composed of isotopes of each element since there is no significant difference in properties.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (1) of the present invention is characterized by having phenylene substituted with difluoroalkoxy at the terminal. Compound (1) has a large absolute value of Δε.
In the compound (1), Y ¹ is hydrogen, and Y ² and Y ³
Compounds in which at least one is fluorine show a very large Δε. Y ¹ and Y ² are fluorine, and Y ³
Are negatively large Δε. Compound (1) has a higher clearing point than a compound in which difluoroalkoxy is replaced by alkyl having the same chain length,
n is relatively large, the viscosity is equal to or less than that, and shows good compatibility at low temperatures. Therefore, it is suitable as a component of the composition for the purpose of high-speed response described in the section of the background art or the composition for VA and MVA systems with a high viewing angle.
Compound (1) is represented by compounds (1-1) to (1-3).

[0022]

Wherein R ¹ , R ² , ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² , Z ³ , Y ¹ , Y ² and Y ³ have the same meaning as described above. The bicyclic compound (1-1) has a relatively large absolute value of Δε, a low viscosity, and extremely good low-temperature compatibility. This compound reduces the viscosity while maintaining the absolute value of Δε of the composition, thus providing a composition for a fast response. The tricyclic compound (1-2) has a large absolute value of Δε, and has a relatively wide temperature range showing a liquid crystal phase. This compound increases the absolute value of Δε without lowering the clearing point of the composition, thus providing a composition for low voltage driving. A compound in which ring A ¹ and ring A ² are 1,4-phenylene in which hydrogen may be substituted with halogen exhibits a large Δε and a large Δn, and gives a composition for high-speed response. The tetracyclic compound (1-3) has a large absolute value of Δε and has a wide temperature range in which a liquid crystal phase is exhibited. This compound increases the absolute value of Δε of the composition and extends the temperature range of the liquid crystal phase to a higher temperature. A compound in which at least one of Y ¹ , Y ² and Y ³ is fluorine has excellent low-temperature compatibility.

R ¹ is, for example, a group having 1 to 20 carbon atoms such as alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkoxyalkyl, alkylthio and alkylthioalkyl. More specifically, methyl, ethyl, propyl,
Isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy,
Propoxy, butoxy, pentoxy, heptyloxy,
Octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, methylthiomethyl, ethylthiomethyl, propylthiomethyl Butylthiomethyl, methylthioethyl, ethylthioethyl, propylthioethyl, methylthiopropyl, ethylthiopropyl, propylthiopropyl and the like.

R ² is specifically exemplified by hydrogen,
Halogen, cyano, and alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, alkenyl, alkenyloxy, alkenylthio,
It is a group having 1 to 20 carbon atoms such as fluorine-substituted alkyl, fluorine-substituted alkoxy, fluorine-substituted alkenyl, fluorine-substituted alkenyloxy, and fluorine-substituted alkenylthio.

More specifically, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Methoxy, ethoxy, propoxy, butoxy, pentoxy, heptyloxy, octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, methylthio, ethylthio, propylthio,
Butylthio, pentylthio, hexylthio, heptylthio, octylthio, methylthiomethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, methylthioethyl, ethylthioethyl, propylthioethyl, methylthiopropyl, ethylthiopropyl, propylthiopropyl, vinyl, -Propenyl, 1-butenyl, 1
-Pentenyl, 3-butenyl, 3-pentenyl, allyloxy,

Trifluoromethyl, fluoromethyl, 2
-Fluoroethyl, difluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-fluoroethyl, 3-fluoropropyl,
-Fluorobutyl, 5-fluoropentyl, fluoromethoxy, trifluoromethoxy, difluoromethoxy,
Pentafluoroethoxy, 1,1,2,2-tetrafluoroethoxy, heptafluoropropoxy, 1,1,
2,3,3,3-hexafluoropropoxy, trifluoromethoxymethyl, 2-fluoroethenyl, 2,2-
Difluoroethenyl, 1,2,2-trifluoroethenyl, 3-fluoro-1-butenyl, 4-fluoro-1-
Butenyl, trifluoromethylthio, difluoromethylthio, 1,1,2,2-tetrafluoroethylthio,
2,2,2-trifluoroethylthio and the like. Preferred examples of the ring A ¹ , ring A ² and ring A ³ are those represented by formulas (r-1) to
It is a ring of (r-24).

[0028]

The composition of the present invention may comprise only the first component containing at least one compound (1), but as the second component, at least one compound selected from the compounds (2), (3) and (4) (Hereinafter, referred to as a second component A) and / or a mixture of at least one compound selected from the compounds (5) and (6) (hereinafter, referred to as a second component B) is preferable. Threshold voltage, temperature range of liquid crystal phase,
At least one compound selected from compounds (7), (8) and (9) may be added as a third component for the purpose of adjusting the refractive index anisotropy, dielectric anisotropy, viscosity and the like. The composition comprises at least one compound (1) in an amount of 0.1%.
It is preferable to contain it in a proportion of up to 99% by weight in order to exhibit excellent characteristics.

Of the second component A, preferred examples of the compound (2) are the compounds (2-1) to (2-9), and preferred examples of the compound (3) are the compounds (3-1) to ( 3-97), and preferred examples of compound (4) are compounds (4-1) to (4-
33).

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

(In the formula, R ³ and X ¹ have the same meanings as described above.) Compounds (2) to (4) have a positive dielectric anisotropy and have thermal stability and chemical stability. Very good, mainly T
Used for FT compositions. When preparing a composition for a TFT, the amount of these compounds used is in the range of 1 to 99% by weight, preferably 10% by weight, based on the total weight of the composition.
９７97% by weight, more preferably 40-95% by weight. Compounds (10) to (1) for the purpose of adjusting the viscosity of the composition
2) may be added. Preferred examples of the compounds (5) and (6) among the second component B are compounds (5-
1) to (5-58) and compounds (6-1) to (6-)
3).

[0039]

[0040]

[0041]

(In the formula, R ⁴ , R ⁵ and X ² have the same meanings as described above.) Compounds (5) and (6) have a positive dielectric anisotropy and a very large value. Therefore, it is mainly used for compositions for STN and TN. These compounds are used particularly for the purpose of lowering the threshold voltage of the composition. It is also used for the purpose of adjusting viscosity and refractive index anisotropy, expanding the temperature range of the liquid crystal phase, and improving steepness. When preparing a composition for STN or TN, the amount of compound (5) and (6) used is in the range of 0.1 to 99.9% by weight. Preferably 10-97% by weight, more preferably 40%
~ 95% by weight. A third component described below may be added for the purpose of adjusting the threshold voltage, the temperature range of the liquid crystal phase, the refractive index anisotropy, the dielectric anisotropy, the viscosity, and the like. When adjusting a composition having a negative dielectric anisotropy for the vertical alignment mode (VA mode), at least one compound (hereinafter, a second C component) selected from compounds (7) to (9) is used. Mixing is preferred. Preferred examples of the compounds (7) to (9) include compounds (7-1) to (7-3) and compound (8-
1) to (8-5) and compounds (9-1) to (9-3)
It is.

[0043]

(Wherein, R ⁶ and R ⁷ have the same meanings as described above). Compounds (7) to (9) have a negative dielectric anisotropy. Since compound (7) is bicyclic, it mainly has a threshold voltage,
It is used for adjusting viscosity or refractive index anisotropy.
Compound (8) is used for the purpose of increasing the clearing point to increase the range of the liquid crystal phase, reducing the threshold voltage, and increasing the refractive index anisotropy. Compound (7)-
(9) It is mainly used for a composition for a VA mode having a negative dielectric anisotropy. Increasing the amount of use decreases the threshold voltage of the composition but increases the viscosity. Therefore, it is preferable to add a small amount as long as the required value of the threshold voltage is satisfied. However, since the absolute value of the dielectric anisotropy is 5 or less, if it is less than 40% by weight, it may not be driven at a low voltage. The amount of the compounds (7) to (9) used is preferably 40% by weight or more for VA mode, but is preferably 50 to 95% by weight. For the purpose of controlling the elastic constant and the voltage transmittance curve, the compounds (7) to (9) may be added to a composition having a positive dielectric anisotropy. In this case, the use amount of the compounds (7) to (9) is preferably 30% by weight or less. Compound (1) among the third components of the composition
Preferred examples of the compounds (0) to (12) are compounds (10-1)
To (10-11), compounds (11-1) to (11-1)
2) and compounds (12-1) to (12-6).

[0045]

[0046]

(In the formula, R ⁸ and R ⁹ have the same meaning as described above.) Compounds (10) to (12) have a small absolute value of dielectric anisotropy and are almost neutral. Compound (10) is used mainly for adjusting the viscosity or the refractive index anisotropy. Compounds (11) and (12) are used for the purpose of increasing the clearing point to extend the range of the liquid crystal phase, or adjusting the refractive index anisotropy. Increasing the amount of the compounds (10) to (11) increases the threshold voltage of the composition and lowers the viscosity. Therefore, it is desirable to use a large amount as long as the required threshold voltage is satisfied. When preparing a composition for a TFT, the amount of the compounds (10) to (12) used is preferably 40% by weight or less, more preferably 35% by weight or less. When adjusting the composition for STN or TN, the amount of the compounds (10) to (12) used is preferably 70% by weight or less, more preferably 60% by weight or less.

The composition is prepared by mixing the compounds of the respective components and dissolving each other by heating. The composition is added with an appropriate additive depending on the purpose to adjust the properties. Such additives are well known to those skilled in the art. A chiral dopant or the like is added for the purpose of inducing a helical structure of the liquid crystal to give a twist and prevent reverse twist. Examples of the chiral dopant include the following optically active compounds.

[0049]

The pitch of the twist is adjusted by adding a chiral dopant. The twist pitch is preferably adjusted in the range of 40 to 200 μm for a composition for TFT and TN. For a composition for STN, it is preferable to adjust the composition to a range of 6 to 20 μm. Bistable TN (Bista
In the case of the ble TN) mode, it is preferable to adjust the thickness to a range of 1.5 to 4 μm. At least two kinds of chiral dopants may be added for the purpose of adjusting the temperature dependence of the pitch. If dichroic dyes such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone and tetrazine are added, G
It can also be used as a composition for Form H. The composition of the present invention can be used for NCAP prepared by microencapsulating nematic liquid crystal or polymer dispersed liquid crystal display device (PDLC) prepared by forming a three-dimensional network polymer in liquid crystal.
D) For example, a polymer network liquid crystal display device (PN
LCD). Furthermore, birefringence control (EC
It can also be used for B) type and DS type. Compound (1) can be obtained, for example, in the fourth edition of Experimental Chemistry Course (Maruzen), Organic Synthesis
(John Wiley & Sons, Inc) or Organic Reactions (J
ohn Wiley & Sons, Inc.), or by appropriately selecting and combining methods described in known documents and the like.

For example, compound (1) is disclosed in
According to the method disclosed in No. 4016, the ester derivative (18) is converted into the thioester derivative (19) with Lawesson's reagent (Fieser 13, 38), and then converted to (19) diethylaminosulfur trifluoride (hereinafter abbreviated as DAST). Or JP-A-5-5-2
HF in the presence of an oxidizing agent such as N-bromosuccinimide (hereinafter abbreviated as NBS) according to the method disclosed in US Pat.
Fluorination by the action of pyridine;

[0052] (Wherein, R ¹ , R ² , ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² ,
Z ³ , Y ¹ , Y ² , Y ³ , l and m have the same meaning as described above. )

Compound (1) can also be suitably produced by the following method. After adjusting the Grignard reagent from the halide (20) according to the method described in JP-A-10-17544, a dithiocarboxylic acid derivative (21) is produced by the action of carbon disulfide. Then, thioester derivative (19) can be produced by reacting (21) with sodium hydride in the presence of phenol derivative (22) and further oxidizing it with iodine. By subjecting (19) thus obtained to fluorination by the action of HF-pyridine in the presence of an oxidizing agent such as NBS, the desired compound (1) can be produced.

[0054] (Wherein, R ¹ , R ² , ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² ,
Z ³ , Y ¹ , Y ² , Y ³ , l and m have the same meaning as described above. X represents chlorine or bromine. )

The phenol derivative (22) used above
Are described in, for example, the method of RL Kidwell (Org. Synth., V, 9
18 (1973)), a boronic ester derivative is prepared by reacting a trialkyl borate with a Grignard reagent prepared from the benzene derivative (23), and this is oxidized with a peroxide such as hydrogen peroxide or peracetic acid. It can be manufactured by the following. (Wherein, R ² , ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² , Z ³ ,
Y ¹ , Y ² , Y ³ , l and m have the same meaning as described above. R ¹⁰ represents alkyl, X represents chlorine or bromine. )

[0056]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, Cr indicates a crystal, N indicates a nematic phase, and Iso indicates an isotropic liquid. Example 1 4- (1,1-difluoropropoxy) -4′-fluorobiphenyl (in the formula (1), l = m = 0, R ¹ is ethyl, ring A ¹ is 1,4-phenylene, and Z ¹ is Single bond, Y
Production of Compound (Compound No. 7) in which ¹ , Y ² and Y ³ are both hydrogen and R ² is fluorine

Step 1 In a 500 ml three-necked flask equipped with a stirrer and a thermometer, 4'-fluoro-4-hydroxybiphenyl 1 was placed under a nitrogen atmosphere.
0.0 g (53.1 mmol), 11.5 g (55.8 mmol) of N, N'-dicyclohexylcarbodiimide, 0.7 g (5.5 mmol) of 4-dimethylaminopyridine, 4.1 g (55.8 mmol) of propionic acid, and 150 ml of dichloromethane are mixed and mixed at room temperature. Stirred for 16 hours. After adding 100 ml of water to the reaction solution, the insolubles were separated by filtration,
The filtrate was concentrated under reduced pressure. The concentrated residue was dissolved in 300 ml and washed with water (250 ml × 3 times). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure, and the concentrated residue was purified by silica gel column chromatography using a developing solvent of toluene to obtain 12.6 g of (4′-fluorobiphenyl) propionate as colorless crystals.

Step 2 In a 500 ml flask equipped with a stirrer and a thermometer, 12.4 g of (4'-fluorobiphenyl) propionate obtained above (5
0.6 mmol), 40.9 g (101.2 mmol) of Lawesson's reagent and 150 ml of mesitylene were added, and the mixture was heated under reflux for 5 hours. 200 ml of water was added to the reaction solution, and the insoluble matter was collected by filtration. After that, 200 ml of toluene was added to the filtrate and extracted. The extract layer was washed twice with 200 ml of water, 100 ml of a saturated aqueous solution of sodium hydrogen carbonate and 200 ml of water. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the concentrated residue was subjected to toluene / heptane (2
0/80) The mixture was purified by silica gel column chromatography using a developing solvent to obtain 4.2 g of 4'-fluorobiphenyl = thione-O-propionate as orange crystals.

Step 3 In a 200 ml Teflon (registered trademark) flask equipped with a stirrer, a thermometer and a dropping funnel, under a nitrogen atmosphere, under NBS
8.7 g (48.4 mmol) was suspended in 30 ml of dichloromethane, cooled to −60 ° C. with a refrigerant while stirring, and 4 ml of 70% HF-pyridine was added. After the addition, the mixture was stirred for 15 minutes, and then a solution of 4.2 g (16.1 mmol) of (4′-fluorobiphenyl) thione-O-propionate obtained above in 40 ml of dichloromethane was added dropwise at −60 ° C. or lower. After dropping, raise the temperature to 0 ° C,
The mixture was further stirred for 1 hour. The reaction solution was saturated aqueous sodium carbonate
After putting into 300 ml, 100 ml of dichloromethane was added to perform extraction, and the extracted layer was washed three times with 150 ml of water, 50 ml of 6M hydrochloric acid, 150 ml of saturated aqueous sodium carbonate and 150 ml of water. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using a mixed solution of heptane / toluene (95/5) as a developing solvent, and further heptane / ethanol (1/1).
The mixture was recrystallized to obtain 1.5 g of the desired 4- (1,1-difluoropropoxy) -4′-fluorobiphenyl (colorless crystal). Cr 56.8 Iso

The spectral data strongly supported the structure. ^{1 H-NMR (δppm, CDCl} 3): 1.23 (t, J = 7.48, 3H), 2.18-
2.28 (m, 2H), 7.15 (bt, 2H), 7.2−7.3 (m, 2H), 7.5−
7.6 (m, 4H). ¹⁹ F-NMR (δ ppm): −73.19 (t, J = 11.8 Hz, 2F, −CF ₂ O
−), −116.15−−116.2 (m, 1F, −C ₆ H ₄ −F). GC-MS (EI): 266 (M ⁺ , 33.2%), 188 (100), 159 (18.8), 1
33 (13.9)

Example 2 2,6-difluoro-4- (1,1-difluoropropo
Xy) -4 ″ -pentylterphenyl (smell of formula (1)
And l = 1, m = 0, R¹Is ethyl, ring A¹And ring A^Two
Are 1,4-phenylene and Z¹And Z^TwoAre tied together
If Y¹Is hydrogen, Y ^TwoAnd Y^ThreeAre both fluorine, R^TwoBut
Of Compound (Compound No. 58)

Step 1 In a 500 ml three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, 19 g (250.0 mmol) of carbon disulfide was added to T under a nitrogen atmosphere.
Dissolve in 100 ml of HF, cool to 5 ° C. with stirring, and then add 100 ml of a solution of ethyl magnesium bromide in THF (1M).
(100 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours,
Then 100 ml of 6M hydrochloric acid was added. The reaction solution was extracted with 250 ml of diethyl ether, washed with water (200 ml × 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 9.8 g of dithiopropionic acid.

Step 2 In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, under a nitrogen atmosphere, sodium hydride (60% oil-based) 7.8
To a suspension of g (193.8 mmol) in THF (50 ml) was added dropwise a solution of 12.0 g (92.3 mmol) of 3,5-difluorophenol in 50 ml of THF at room temperature while stirring. After stirring at room temperature for 30 minutes after the dropwise addition, 9.8 g of dithiopropionic acid obtained above (92.3 mmo
30 ml of a THF solution of l) was added dropwise. After the dropwise addition, the mixture was heated to 50 ° C. in a warm bath and stirred for 1 hour, and then 28.1 g of iodine (110.8 g
(mmol) in a THF solution (80 ml) was added dropwise.
Stirred for hours. After dropwise adding 150 ml of water to the reaction solution, the reaction product was extracted with 200 ml of diethyl ether, and the extracted layer was washed with water (150 ml ×
2) and dried over anhydrous magnesium sulfate. The extract was concentrated under reduced pressure, and the concentrated residue was purified by silica gel column chromatography with a developing solvent of heptane to obtain 13.2 g of 3,5-difluorophenylthione-O-propionate.

Step 3 In a 500 ml Teflon flask equipped with a stirrer, thermometer and dropping funnel, under a nitrogen atmosphere, 35.2 g of NBS (195.8
(mmol) was suspended in 100 ml of dichloromethane, cooled to −60 ° C. with a cooling medium with stirring, and 10 ml of 70% HF-pyridine was added. After the addition, the mixture was stirred for 15 minutes, then a solution of 13.2 g (65.3 mmol) of 3,5-difluorophenyl-thione-O-propionate obtained above in 50 ml of dichloromethane was added dropwise, and the mixture was further stirred at -10 ° C for 1 hour. After pouring the reaction solution into 500 ml of saturated sodium carbonate solution, 400 ml of dichloromethane was added and extracted, and the extracted layer was washed with 300 ml of saturated sodium carbonate solution,
Washed sequentially with water (300 ml × 3) and dried over anhydrous magnesium sulfate. After the extract was concentrated under reduced pressure, the concentrated residue was purified by silica gel column chromatography using heptane as a developing solvent to give 1,1-difluoropropoxy-3,5.
-8.7 g of difluorobenzene were obtained.

Step 4 In a 300 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 8.7 g (41.8 mmol) of 1,1-difluoropropoxy-3,5-difluorobenzene obtained above was added to T
After dissolving in 50 ml of HF and cooling to −65 ° C. with stirring, n
-Butyl lithium (1.6 M n-hexane solution) 31.4 ml (5
0.2 mmol) was added dropwise at -65 ° C or lower. After stirring at −65 ° C. or lower for 1 hour, 6.5 g (62.7 mmol) of trimethyl borate was added dropwise. After the addition, the temperature was raised to room temperature, and the mixture was further stirred for 4 hours. 100 ml of 6M hydrochloric acid was added to the reaction solution, and the reaction solution was extracted with 300 ml of diethyl ether. The extracted layer was washed with water (200 ml × 2) and dried over anhydrous magnesium sulfate. After the extract was concentrated under reduced pressure, the concentrated residue was washed with heptane to obtain 7.3 g of 1,1-difluoropropoxy-3,5-difluorophenylboric acid.

Step 5 In a 300 ml three-necked flask equipped with a stirrer and a condenser,
1,1-difluoropropoxy-3,5 obtained above
7.3 g (28.9 mmol) of difluorophenylboric acid, 10.1 g (28.9 mmol) of 4-pentyl-4′-iodobiphenyl, 8.0 g (57.8 mmol) of potassium carbonate, and 5% palladium on carbon catalyst 3
g, 30 ml of toluene, 30 ml of ethanol and 5 ml of water were mixed, and heated to reflux for 16 hours while stirring. The reaction solution was filtered to remove insolubles, and the filtrate was mixed with 200 ml of toluene and 200 ml of water.
Was added and extracted, and the extracted layer was washed twice with 200 ml of water.
The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the concentrated residue was purified by silica gel column chromatography using a mixed solution of heptane / toluene (90/10) as a developing solvent. By crystallization, the desired 2,6-difluoro-4-
4.2 g of (1,1-difluoropropoxy) -4 ″ -pentylterphenyl were obtained.

The spectral data strongly supported the structure. ¹ H-NMR (δ ppm, CDCl ₃ ): 0.95-0.98 (m, 3H), 1.22 (t, J
= 7.49Hz, 3H), 1.36-1.50 (m, 4H), 1.65-1.80 (m, 2
H), 2.19−2.31 (m, 2H), 2.65−2.70 (m, 2H), 6.9−7.0
. (m, 2H), 7.2-7.7 (m, 8H) 19 F-NMR (δppm): - 73.95 (t, J = 11.8Hz, 2F, -CF 2 O
−), −113.1 (m, 2F).

Example 3 4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1- (1,1-difluoroethoxy) -2,3-difluorobenzene (formula (1)
Wherein l = 1, m = 0, R ¹ is methyl, ring A ¹ and ring A ² are both trans-1,4-cyclohexylene, Z ¹
And Z ² are both a single bond, Y ¹ and Y ² are both fluorine,
Compounds in which Y ³ is hydrogen and R ² is n-propyl (compound N
o. 33)) Manufacturing

First step 4- (trans-4- () obtained by the method described in Liq. Cryst., 1989, 5 (1), 159 in a 500 ml three-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. Trans-4-propylcyclohexyl) cyclohexyl) -2,3-difluoromethoxybenzene 4.3 g (12.3 mmol) was added to dichloromethane 1
After dissolving in 50 ml and cooling to −40 ° C. or lower with stirring, 6.2 g (24.5 mmol) of boron tribromide was added dropwise. After the dropwise addition, the temperature was raised to room temperature, and the mixture was further stirred for 16 hours. 300 m of water
Then, 150 ml of dichloromethane was added for extraction, and the extracted layer was further washed with water (150 ml × 3) and dried over anhydrous magnesium sulfate. The extract was concentrated under reduced pressure to obtain 3.3 g of 4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2,3-difluorophenol as colorless crystals.

Step 2 In a 200-ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, the above obtained 4- (trans-
3.3 g of 4- (trans-4-propylcyclohexyl) cyclohexyl) -2,3-difluorophenol (9.9 m
mol) and 3 ml of pyridine were dissolved in 80 ml of toluene, and 1.2 g (15 mmol) of acetyl chloride was added dropwise with stirring at room temperature. After the dropwise addition, the mixture was stirred for 2 hours while maintaining the temperature at 50 ° C in a warm bath.
100 ml and 100 ml of toluene were added for extraction. The extract layer was washed sequentially with 50 ml of 3M hydrochloric acid, 100 ml of water, 100 ml of saturated aqueous sodium carbonate and water (100 ml × 2), and dried over anhydrous magnesium sulfate. The extract was concentrated under reduced pressure, and the concentrated residue was purified by silica gel column chromatography using a mixture of heptane / ethyl acetate (80/20) as a developing solvent to give 4- (trans-4- (trans) as colorless crystals. -4-
Propylcyclohexyl) cyclohexyl) -2,3-
3.6 g of difluorophenyl acetate was obtained.

Step 3 In a 100 ml flask equipped with a stirrer and a thermometer, 3.6 g of 4- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -2,3-difluorophenyl acetate obtained above ( 9.5 mmol), Lawesson's reagent 7.7 g
(19.0 mmol) and 50 ml of mesitylene were added, and the mixture was heated under reflux for 9 hours. 100 ml of water was added to the reaction solution, the insolubles were collected by filtration, and 100 ml of toluene was added to the filtrate for extraction. The extract layer was washed twice with 100 ml of water, 100 ml of a saturated aqueous solution of sodium hydrogen carbonate and 100 ml of water. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the concentrated residue was purified by silica gel column chromatography using heptane as a developing solvent to give 4- (trans-4- (trans-4) as orange crystals. -Propylcyclohexyl) cyclohexyl) -2,3-difluorophenylthione-O
-1.8 g of acetate was obtained.

Fourth Step In a 100 ml Teflon flask equipped with a stirrer, thermometer and dropping funnel, under a nitrogen atmosphere, 2.5 g of NBS (13.7 mm
ol) was suspended in 20 ml of dichloromethane, cooled to −60 ° C. with a refrigerant while stirring, and 2 ml of 70% HF-pyridine was added. The mixture was stirred for 15 minutes after the addition, and then the 4- (trans-4- (trans-4-propylcyclohexyl) obtained above) was obtained.
Cyclohexyl) -2,3-difluorophenylthione-O-acetate 1.8 g (4.6 mmol) in dichloromethane
20 ml was added dropwise at −60 ° C. or lower. After the dropwise addition, the temperature was raised to 0 ° C., and the mixture was further stirred for 1 hour. After pouring the reaction solution into 100 ml of saturated aqueous sodium carbonate solution, 50 ml of dichloromethane was added and extraction was performed. Then, the extracted layer was washed with 50 ml of water, 30 ml of 6M hydrochloric acid, and 50 ml of water.
Then, the mixture was washed twice with 50 ml of saturated aqueous sodium carbonate and 50 ml of water. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using a developing solvent of heptane, and then recrystallized from a heptane / ethanol (1/1) mixed solution to obtain the desired 4- (trans-4- (trans-4-propyl). 1.5 g of (cyclohexyl) cyclohexyl) -1- (1,1-difluoroethoxy) -2,3-difluorobenzene (colorless crystal) was obtained. This showed the following liquid crystal phase. Cr 62.0 N 86.1 Iso

The spectral data strongly supported the structure. ^{1 H-NMR (δppm, CDCl} 3): 1.23 (t, J = 7.48, 3H), 2.18-
2.28 (m, 2H), 7.15 (bt, 2H), 7.2−7.3 (m, 2H), 7.5−
7.6 (m, 4H). ¹⁹ F-NMR (δ ppm): −73.19 (t, J = 11.8 Hz, 2F, −CF ₂ O
−), −116.15−−116.2 (m, 1F, −C ₆ H ₄ −F). GC-MS (EI): 266 (M ⁺ , 33.2%), 188 (100), 159 (18.8), 1
33 (13.9)

Example 4 α, α-difluoro-2,6-difluoro-4- (4-
(1,1-difluoroethoxy) phenyl) benzyl =
3,4,5-trifluorophenyl ether (in the formula (1), l = 1, m = 0, R ¹ is methyl, ring A ¹
And ring A ² are both 3,5-difluoro-1,4-phenylene, Z ¹ is a single bond, Z ² is —CF ₂ O—, Y ¹ , Y ² and Y ³ are both hydrogen, and R ² is fluorine. Production of Certain Compound (Compound No. 395)

Step 1 In a 1-L three-necked flask equipped with a stirrer, a condenser and a thermometer, under a nitrogen atmosphere, 26.3 g (100.0 mmol) of 4-bromophenyl-benzyl-ether, 18.9 g of 3,5-difluorophenylboric acid g (120.0 mmol), potassium carbonate 27.6 g (200.0 m
mol), 3.0 g of a 5% palladium carbon catalyst, 100 ml of toluene and 100 ml of ethanol were mixed and heated under reflux for 8 hours. The reaction solution was filtered after filtering off insolubles, and extracted with 300 ml of toluene and 300 ml of water. Extraction layer with additional 300 ml of water
, And dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a concentrate. The concentrate was purified by silica gel column chromatography using heptane as a developing solvent to obtain 24.0 g of 3,5-difluoro-4′-biphenyl = benzyl = ether as colorless crystals.

Step 2 In a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 24.0 g of 3,5-difluoro-4'-biphenyl = benzyl = ether obtained in Step 1 under a nitrogen atmosphere.
(81.0 mmol) was dissolved in 200 ml of THF with stirring, and cooled to -65 ° C in an acetone-dry ice bath. Then n
-Butyl lithium (n-hexane solution 1.59M) 61ml (97.2m
mol) was added dropwise over 45 minutes so that the internal temperature was kept at -60 ° C or lower, followed by stirring at -65 ° C for 1 hour. Then, a solution of 33.9 g (162.0 mmol) of dibromodifluoromethane in 20 ml of THF was heated to −
After dropping over 30 minutes to maintain the temperature at 65 ° C or lower, the mixture was stirred at -65 ° C or lower for 1 hour. After the temperature was raised to room temperature, 100 ml of water and 200 ml of toluene were added for extraction. Extraction layer is 150ml of water 2
After washing twice, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 40.8 g of a tan concentrate. The resulting concentrate was purified by silica gel column chromatography using a toluene / heptane = 1/1 mixed solvent as a developing solvent, and 3,5-difluoro-4-bromodifluoromethyl-4′-biphenyl = benzyl was obtained as a colorless crystal. = Ether 32.2g
I got

Third Step In a 500 ml three-necked flask equipped with a stirrer, condenser and thermometer, under a nitrogen atmosphere, 3,5-difluoro-4-bromodifluoromethyl-4'-biphenyl obtained in the second step was obtained.
Benzyl ether 32.2 g (75.7 mmol), 3,4,5-trifluorophenol 8.6 g (58.3 mmol), potassium carbonate 1
4.6 g (105.9 mmol), tetrabutylammonium bromide
3.4 g (10.6 mmol), 100 ml of toluene and 5 ml of water were mixed and heated under reflux for 22 hours. The reaction mixture was extracted by adding 150 ml of water and 200 ml of toluene, and the extracted layer was washed twice with 150 ml of water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a concentrate. The concentrate is toluene / heptane =
The mixture was purified by silica gel column chromatography using a 2/3 mixed solvent as a developing solvent, and recrystallized twice from a mixed solvent of heptane / toluene = 8/2 to obtain α, α-difluoro-2,6 as colorless crystals. -Difluoro-4-
(4- (benzyloxy) phenyl) benzyl = 3
15.2 g of 4,5-trifluorophenyl ether were obtained.

Fourth Step In a 1 L autoclave, the α, α-difluoro-2,6-difluoro-4- (4- (benzyloxy) phenyl) benzyl obtained in the third step is 3,4,5-trifluorophenyl = 150 g of ethyl acetate in 15.2 g (30.9 mmol) of ether
l, 100 ml of toluene was added and dissolved, 3 g of a 5% palladium carbon catalyst was added, and the mixture was stirred at a hydrogen pressure of 0.8 MPa at room temperature for 8 hours. The reaction solution was filtered to separate the catalyst, and concentrated under reduced pressure to obtain α, α-difluoro-2,6-difluoro-4-as a concentrate.
12.9 g of (4-hydroxyphenyl) benzyl = 3,4,5-trifluorophenyl = ether was obtained.

Step 5 In a 200 ml eggplant-shaped flask equipped with a dropping funnel, under a nitrogen atmosphere, the α, α-difluoro-2,6-difluoro-4- (4-hydroxyphenyl) benzyl obtained in Step 4 was used.
3,4,5-trifluorophenyl ether 12.4 g (3
0.8 mmol) was dissolved in 50 ml of toluene, and 3.7 g of pyridine (46.2
3.2 g of acetyl chloride (40.1 mmol) while stirring.
l) was added dropwise at room temperature. Stir at room temperature for 2 hours after dropping,
The reaction solution was poured into 100 ml of water to complete the reaction. Toluene 100
After extraction by adding ml, the extracted layer was further washed twice with 100 ml of water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using toluene as a developing solvent, and further recrystallized from a mixed solvent of heptane / methanol = 7/3 to obtain α, α-difluoro-2,6-difluoro-4- as a colorless crystal.
(4-acetyloxyphenyl) benzyl = 3,4,5
11.9 g of trifluorophenyl ether were obtained.

Step 6 In a 300 ml flask equipped with a stirrer and thermometer, the α, α-difluoro-2,6-difluoro-4-
(4-acetyloxyphenyl) benzyl = 3,4,5
Trifluorophenyl ether 11.9 g (26.8 mmol),
Lawesson's reagent 13.0 g (32.2 mmol) and mesitylene 50 ml
Was added and heated to reflux for 6 hours. After cooling to room temperature,
The insolubles were separated and concentrated once with a vacuum pump. After dissolving the concentrate in 100 ml of toluene, heptane (100 ml) was added, the precipitated solid was collected by filtration again, and the filtrate was concentrated. Next, the concentrated residue was purified by silica gel column chromatography using a mixed solution of toluene / heptane = 3/2 as a developing solvent, and α, α-difluoro-2,6 was obtained as orange crystals.
4.6 g of -difluoro-4- (4-thioacetyloxyphenyl) benzyl = 3,4,5-trifluorophenyl = ether was obtained.

Step 7 In a 200 ml Teflon flask equipped with a stirrer, a thermometer and a dropping funnel, under a nitrogen atmosphere, 3.5 g of NBS (19.9 mm
ol) was suspended in 30 ml of dichloromethane, cooled to −60 ° C. with a refrigerant while stirring, and 5 ml of 70% HF-pyridine was added. After the addition, the mixture is stirred for 15 minutes, and then the α, α obtained in the sixth step is obtained.
35 mL of a dichloromethane solution of -difluoro-2,6-difluoro-4- (4-thioacetyloxyphenyl) benzyl = 3,4,5-trifluorophenyl = ether (4.6 g, 9.9 mmol) was added dropwise at -60 ° C or lower. did. After the dropwise addition, the temperature was raised to 0 ° C., and the mixture was further stirred for 1 hour. After pouring the reaction mixture into 300 ml of saturated aqueous sodium carbonate solution, 100 ml of dichloromethane was added and extraction was performed.
Washed twice with 0 ml, 100 ml of saturated aqueous sodium carbonate and 100 ml of water. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrated residue was heptane / toluene = 9/1
Was purified by silica gel column chromatography using a mixture of the above as a developing solvent, and then heptane / ethanol = 7.
/ 3 mixture was recrystallized to obtain the desired α, α-difluoro-2,6-difluoro-4- (4- (1,1-difluoroethoxy) phenyl) benzyl = 3,4,5-trifluorophenyl = 1.1 g of ether (colorless crystals) was obtained. Cr 75.5 Iso

The spectral data strongly supported the structure. ^{1 H-NMR (δppm, CDCl} 3): 1.96 (t, J = 13.3, 3H), 6.95-
7.1 (m, 2H), 7.19 (d, J = 10.3, 2H), 7.29 (d, J = 8.6, 2
. H), 7.51-7.55 (m, 2H) 19 F-NMR (δppm): - 62.16 (t, J = 26.1, 2F, -CF 2 O-),
−65.33 (q, J = 14.0, 2F, CH ₃ CF ₂ O−), −110.63−−11
0.77 (m, 2F), −132.90−−133.23 (m, 2F), −163.59−
−163.71 (m, 1F).

On the basis of the descriptions in Examples 1 to 4 and the detailed description of the invention, the following compound No. 1 to No. 66
5 and No. 5 667-No. 761 can be manufactured. In addition, the compounds obtained in Examples 1 to 4 are shown again.

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

Example 5 A nematic liquid crystal composition containing a cyanophenylcyclohexane compound (hereinafter sometimes referred to as composition A) has the following characteristics. 4- (4-propylcyclohexyl) benzonitrile 24% 4- (4-pentylcyclohexyl) benzonitrile 36% 4- (4-heptylcyclohexyl) benzonitrile 25% 4- (4- (4-pentylcyclohexyl) phenyl) benzo Nitrile 15% Clearing point (TNI): 71.7 ° C., threshold voltage (Vth) at a cell thickness of 8.8 μm: 1.78 V, Δε: 11.
0, Δn: 0.137, viscosity at 20 ° C. (η): 2
6.3 mPa · s. 85% by weight of this composition A and 4- (1,1-difluoropropoxy)-obtained in Example 1
A composition comprising 4% by weight of 4′-fluorobiphenyl (Compound No. 7) was prepared. Its properties were as follows: Clearing point (TNI): 56.8 ° C., cell thickness 8.
Threshold voltage (Vth) at 8 μm: 1.53 V, Δ
ε: 10.8 Δn: 0.130, viscosity at 20 ° C. (η): 23.5 mPa · s. Compound No. calculated by the extrapolation method from the mixing ratio of the compounds and the two physical property values. The physical properties of No. 7 were as follows. Clearing point (TNI): -2
7.6 ° C, Δε: 9.7, Δn: 0.090, viscosity (η) at 20 ° C: 0.8 mPa · s. This composition is
After storage in a freezer at 20 ° C. for 20 days, there was no change such as precipitation of crystals.

Example 6 85% by weight of the above composition A and α, obtained in Example 4
α-difluoro-2,6-difluoro-4- (4-
(1,1-difluoroethoxy) phenyl) benzyl =
A composition comprising 3,4,5-trifluorophenyl ether (compound No. 395) at 15% by weight was prepared. Its properties were as follows: Clearing point (TN
I): threshold voltage (Vth) at 61.9 ° C., cell thickness 8.8 μm: 1.49 V, Δε: 13.6, Δn: 0.
134, viscosity at 20 ° C. (η): 31.1 mPa ·
s. The above compound No. calculated by the extrapolation method from the mixing ratio of the compounds and the two physical property values 395 were as follows. Clearing point (TNI): 6.4 ° C, Δε: 2
6.6, Δn: 0.117, viscosity (η) at 20 ° C .: 50.4 mPa · s. This composition was stored in a freezer at −20 ° C. for 20 days, but there was no change such as precipitation of crystals.

The following use examples 1 to 33 are shown as examples of the nematic liquid crystal composition of the present invention. The compounds which are components of the composition are indicated by symbols of a left terminal group, a bonding group, a ring structure and a right terminal group according to the rules shown in Table 1 below.

[0125]

No. 1 attached to the compound of Use Example Is the same as that shown in the embodiment. The content of the compound means% by weight unless otherwise specified. The characteristic data of the usage example is
TNI (nematic-isotropic liquid transition temperature or clearing point), η (viscosity: measurement temperature 20.0 ° C), Δn (refractive index anisotropy value: measurement temperature 25.0 ° C), Δε (dielectric anisotropy) Property value: measurement temperature 25.0 ° C.) and Vth (threshold voltage:
(Measuring temperature 25.0 ° C.).

Use Example 1 2CF2O-BB-F (No. 7) 10.0% 1V2-BEB (F, F) -C 5.0% 3-HB-C 15.0% 1-BTB-3 0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 11.0% 3-HHB-3 9.0% 3-H2BTB-2 4.0% 3-H2BTB -3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 6.0% 3-HB (F) TB-3 6.0% NI = 84.0 (° C) η = 12.3 (mPa · s) Δn = 0.158 Δε = 6.8 Vth = 21.5 (V) When 0.8 part by weight of CM33 is added to 100 parts by weight of the composition, the pitch is 11.1 µm. Met.

Use Example 2 2CF2O-B (F) BB-F (No. 62) 5.0% 2CF2O-BB (F) BF (No. 64) 5.0% 2CF2O-B (F) BB- OCF3 (No. 82) 5.0% 2O1-BEB (F) -C 5.0% 3O1-BEB (F) -C 15.0% 4O1-BEB (F) -C 13.0% 5O1-BEB ( F) -C 13.0% 2-HHB (F) -C 15.0% 3-HB (F) TB-2 4.0% 3-HB (F) TB-3 4.0% 3-HB ( F) TB-4 4.0% 3-HHB-1 8.0% 3-HHB-O1 4.0% NI = 76.9 (° C) η = 82.3 (mPa · s) Δn = 0.160 Δε = 30.3 Vth = 0.87 (V)

Use Example 3 2CF2O-B (F) BB-5 (No. 57) 6.0% 2CF2O-B (F, F) BB-5 (No. 58) 6.0% 5-PyB-F 4 3.0% 3-PyB (F) -F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0 % 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB- O8 3.0% 3-PyBB-F 6.0% 3-HHB-1 6.0% 3-HHB-3 8.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% NI = 87.7 (° C.) η = 45.8 (MPa · s) Δn = 0.199 Δε = 5.0 Vth = 2.56 (V)

Use Example 4 2CF2O-B (F) BB-Cl (No. 63) 6.0% 2CF2O-BB (F) B-Cl (No. 65) 6.0% 2CF2O-BB (F) B- 5 (No. 57) 5.0% 2CF2O-BB (F, F) B-5 (No. 58) 4.0% 3-GB-C 10.0% 4-GB-C 10.0% 2- BEB-C 12.0% 3-BEB-C 4.0% 3-PyB (F) -F 6.0% 3-HEB-O4 8.0% 5-HEB-5 5.0% 4-HEB- 5 5.0% 10-BEB-2 4.0% 3-HHB-1 6.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% NI = 76.8 (° C.) η = 51.5 (mPa · s) Δn = 0.160 Δε = 12.8 Vth = 1.22 (V)

Usage Example 5 2CF2O-BB (F, F) B (F) -F (No. 70) 3.0% 3-HB-C 18.0% 1O1-HB-C 10.0% 3-HB (F) -C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 1O1-HH-3 7.0% 2-BTB-O1 7.0% 3-HHB-1 7.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 8.0% 3-H2BTB-2 3.0% 3 -H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0% NI = 78.8 (° C) η = 18.9 (mPa S) Δn = 0.140 Δε = 8.5 Vth = 1.70 (V)

Use Example 6 2CF2O-B (F) BB-OCF3 (No. 82) 6.0% 2CF2O-BB (F) B-OCF3 (No. 84) 6.0% 2-BEB (F) -C 5.0% 3-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 10.0% 3-HH-EMe 10.0% 3-HB-O2 18.0% 7- HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0% 2O1-HBEB (F) -C 2.0% 3-HB ( F) EB (F) -C 2.0% 3-HBEB (F, F) -C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 13 2.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0% NI = 88.8 (° C.) η = 34.6 (mPa · s) Δn = 0.129 Δε = 22.0 Vth = 0.96 (V)

Use Example 7 2CF2O-B (F) BB-F (No. 62) 5.0% 2CF2O-BB (F) BF (No. 64) 5.0% 2CF2O-BB (F) B ( F, F) -F (No. 79) 5.0% 2CF2O-BB (F, F) B (F) -F (No. 70) 5.0% 2-BEB-C 12.0% 3-BEB -C 4.0% 4-BEB-C 6.0% 3-HB-C 8.0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0 % 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HHB-1 7.0% 3-HHB-O1 4.0% NI = 66.7 (° C) η = 32.5 (MPa · s) Δn = 0.121 Δε = 10.7 Vth = 1.29 (V)

Use Example 8 2CF2O-BB-F (No. 7) 12.0% 2CF2O-B (F, F) BB-5 (No. 58) 7.0% 2CF2O-BB (F, F) B- 5 (No. 60) 7.0% 2-HB-C 5.0% 3-HB-O2 15.0% 2-BTB-1 3.0% 3-HHB-1 8.0% 3-HHB- F 4.0% 3-HHB-O1 5.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB (F) -F 7.0% 3-HHB (F) -F 7.0% 5-HHB (F) -F 7.0% 3-HHB (F, F) -F 5.0% NI = 84.1 (° C) η = 28.1 (mPa · s) Δn = 0.110 Δε = 4.9 Vth = 2.46 (V)

Use Example 9 2CF2O-B (F) BB-F (No. 62) 5.0% 2CF2O-B (F) BB-Cl (No. 63) 5.0% 2CF2O-BB (F) B- F (No.64) 5.0% 2CF2O-BB (F) B-Cl (No.65) 5.0% 2CF2O-BB (F) BB-3 (No.484) 5.0% 2CF2O-BBB ( F) B-3 (No. 486) 4.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 4.0% 3-HB (F) -C5 2.0% 2-BTB-1 2.0% 3-HH-4 8.0% 3-HH-VFF 6.0% 2-HHB-C 3.0% 3-HHB-C 6.0% 3- HB (F) TB-2 8.0% 3-H2BTB-2 5.0% NI = 103.6 (° C.) η = 40.1 (mPa · s) Δn = 0.186 Δε = 8.8 Vth = 1.98 (V)

Use Example 10 2CF2O-B (F, F) BB-5 (No. 58) 4.0% 5-BEB (F) -C 5.0% V-HB-C 11.0% 5-PyB -C 6.0% 4-BB-3 11.0% 3-HH-2V 10.0% 5-HH-V 11.0% V-HHB-1 7.0% V2-HHB-1 15.0 % 3-HHB-1 5.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0% NI = 88.4 (° C.) η = 18.1 (mPa · s) Δn = 0. 120 Δε = 4.8 Vth = 2.36 (V)

Use Example 11 2CF2O-B (F) BB-5 (No. 57) 6.0% 2CF2O-BB (F) B-5 (No. 59) 5.0% V2-HB-TC 10.0 % 3-HB-TC 10.0% 3-HB-C 10.0% 5-HB-C 7.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB- O1 5.0% 3-HH-4 5.0% 3-HHB-1 10.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB (F) TB-2 3.0% 5-BTB (F) TB-3 10.0% NI = 95.6 (° C) η = 22.2 (mPa · s) Δn = 0.220 Δε = 6.9 Vth = 2.08 (V)

Use Example 12 2CF2O-BB (2F) BH-3 (No.474) 4.0% 2CF2O-BB (F) BH-3 (No.475) 4.0% 1V2-BEB (F, F) -C 6.0% 3-HB-C 18.0% 2-BTB-1 10.0% 5-HH-VFF 30.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 11.0 % 3-H2BTB-2 5.0% 3-HHB-1 4.0% NI = 87.3 (° C.) η = 15.9 (mPa · s) Δn = 0.131 Δε = 6.5 Vth = 2 .07 (V)

Use Example 13 1CF2O-BB (F, F) CF2OB (F, F) -F (No. 395) 3.0% 5-HBCF2OB (F, F) -C 3.0% 3-HB (F , F) CF2OB (F, F) -C 3.0% 3-HB-C 15.0% 2-BTB-1 10.0% 5-HH-VFF 30.0% 1-BHH-VFF 8.0 % 1-BHH-2VFF 11.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% NI = 82. 6 (° C.) η = 12.6 (mPa · s) Δn = 0.128 Δε = 4.9 Vth = 2.44 (V)

Use Example 14 2CF2O-BB-F (No. 7) 13.0% 2-HHB (F) -F 17.0% 3-HHB (F) -F 17.0% 5-HHB (F) -F 16.0% 2-H2HB (F) -F 10.0% 3-H2HB (F) -F 5.0% 5-H2HB (F) -F 10.0% 2-HBB (F) -F 6.0% 3-HBB (F) -F 6.0% NI = 84.7 (° C.) η = 21.7 (mPa · s) Δn = 0.099 Δε = 5.3 Vth = 2.15 ( V) The pitch when adding 0.3 parts by weight of CN to 100 parts by weight of the above composition was 78.7 μm.

Use Example 15 2CF2O-B (F) BB-F (No. 62) 5.0% 2CF2O-BB (F) BF (No. 64) 5.0% 5-HB-CL 16.0 % 3-HH-4 12.0% 3-HH-5 4.0% 3-HHB-F 4.0% 3-HHB-CL 3.0% 4-HHB-CL 4.0% 4-HHB ( F) -F 9.0% 5-HHB (F) -F 9.0% 7-HHB (F) -F 8.0% 5-HBB (F) -F 4.0% 5-HBBH-1O13 3.0% 3-HHBB (F, F) -F 2.0% 4-HHBB (F, F) -F 3.0% 5-HHBB (F, F) -F 3.0% 3-HH2BB (F , F) -F 3.0% 4-HH2BB (F, F) -F 3.0% NI = 112.2 (° C) η = 21.3 (mPa · s) Δn = 0.104 Δε = 4. 0 Vth = 2 63 (V)

Use Example 16 2CF2O-BB (F) B-OCF3 (No. 84) 7.0% 2CF2O-BB (F) B (F, F) -F (No. 79) 7.0% 2CF2O-BB (F, F) B (F) -F (No. 70) 7.0% 3-HHB (F, F) -F 9.0% 3-H2HB (F, F) -F 8.0% 4- H2HB (F, F) -F 8.0% 5-H2HB (F, F) -F 8.0% 5-HBB (F, F) -F 20.0% 3-H2BB (F, F) -F 10.0% 5-HHBB (F, F) -F 3.0% 5-HHEBB-F 2.0% 3-HH2BB (F, F) -F 3.0% 4-HBBH-1O1 4.0% 5-HBBH-1O1 4.0% NI = 100.8 (° C.) η = 39.6 (mPa · s) Δn = 0.122 Δε = 10.4 Vth = 1.63 (V) 100% of the above composition Pitch when the CM43L added 0.25 parts by weight parts was 64.4Myuemu.

Use Example 17 2CF2O-BB-F (No. 7) 12.0% 2CF2O-B (F) BB-OCF3 (No. 82) 5.0% 6-HB-F 9.0% 7-HB -F 7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0 % 3-HHB (F, F) -OCF3 5.0% 3-HBB (F) -F 10.0% 5-HBB (F) -F 10.0% 3-HH2B (F) -F 3.0 % 3-HB (F) BH-3 3.0% 5-HBBH-3 3.0% 3-HHB (F, F) -OCF2H 4.0% NI = 84.6 (° C) η = 17.8 (MPa · s) Δn = 0.108 Δε = 5.7 Vth = 2.10 (V)

Use Example 18 2CF2O-B (F) BB-F (No. 62) 5.0% 2CF2O-B (F) BB-Cl (No. 63) 5.0% 2CF2O-BB (F) B- F (No. 64) 5.0% 2CF2O-BB (F) B-Cl (No. 65) 5.0% 5-HB-CL 11.0% 3-HH-4 8.0% 5-HBB ( 2. F, F) -F 15.0% 3-HHB (F, F) -F 8.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 0% 5-HHEB (F, F) -F 3.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 5.0% 5-HBEB (F, F) -F 3.0% 3-HHBB (F, F) -F 6.0% 3-HHB-1 5.0% NI = 88.4 (° C) η = 25.6 (mPa · s) Δn = 0.128 Δε = 8.6 Vth = 1.70 (V)

Usage Example 19 2CF2O-B (F) BB-OCF3 (No. 82) 8.0% 2CF2O-BB (F) B-OCF3 (No. 84) 8.0% 2CF2O-BB (F) B ( F, F) -F (No. 79) 8.0% 2CF2O-BB (F, F) B (F) -F (No. 70) 8.0% 3-HH-4 4.0% 3-H2HB (F, F) -F 10.0% 4-H2HB (F, F) -F 10.0% 5-H2HB (F, F) -F 8.0% 3-HBB (F, F) -F33 3.0% 3-HHBB (F, F) -F 3.0% NI = 60.4 (° C.) η = 35.2 (mPa · s) Δn = 0.121 Δε = 10.5 Vth = 1.30 (V)

Use Example 20 2CF2O-BB (2F) BH-3 (No.474) 2.0% 2CF2O-BB (F) BH-3 (No.475) 2.0% 7-HB (F, F) -F 5.0% 3-H2HB (F, F) -F 12.0% 4-H2HB (F, F) -F 10.0% 3-HHB (F, F) -F 10.0% 4- HHB (F, F) -F 5.0% 3-HBB (F, F) -F 10.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 3.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 5.0% 5-HBEB ( F, F) -F 3.0% 3-HGB (F, F) -F 15.0% 3-HHBB (F, F) -F 2.0% NI = 77.6 (° C) η = 34. 5 (mPa · s) Δn = 0. 88 Δε = 12.7 Vth = 1.41 (V)

Use Example 21 2CF2O-B (F) BB-5 (No. 57) 5.0% 5-H4HB (F, F) -F 7.0% 5-H4HB-OCF3 15.0% 3-H4HB (F, F) -CF3 8.0% 5-H4HB (F, F) -CF3 10.0% 3-HB-CL 6.0% 5-HB-CL 4.0% 2-H2BB (F)- F 5.0% 3-H2BB (F) -F 10.0% 5-H2HB (F, F) -F 5.0% 3-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0% V -HHB (F) -F 5.0% 3-HHB (F) -F 5.0% 3-HBEB (F, F) -F 5.0% NI = 68.9 (° C) η = 28.7 (MPa · s) Δn = 0.105 Δε = 8.1 Vth = 1.77 (V)

Use Example 22 2CF2O-B (F, F) BB-5 (No.58) 7.0% 2CF2O-BB (F, F) B-5 (No.60) 7.0% 5-HB- CL 17.0% 7-HB (F, F) -F 3.0% 3-HH-4 10.0% 3-HH-5 5.0% 3-HB-O2 15.0% 3-H2HB ( F, F) -F 5.0% 4-H2HB (F, F) -F 5.0% 3-HHB (F, F) -F 6.0% 5-HHB (F) -F 7.0% 3-HHB-1 8.0% 3-HHB-O1 5.0% NI = 70.2 (° C.) η = 23.5 (mPa · s) Δn = 0.092 Δε = 2.4 Vth = 2.4 45 (V)

Use Example 23 2CF2O-B (F) BB-5 (No. 57) 5.0% 2CF2O-BB (F) B-5 (No. 59) 5.0% 2CF2O-B (F) BB- F (No.62) 5.0% 2CF2O-BB (F) BF (No.64) 5.0% 2CF2O-BB (F) B (F, F) -F (No.79) 5.0 % 2CF2O-BB (F, F) B (F) -F (No.70) 5.0% 2CF2O-BB (F) BB-3 (No.484) 2.0% 2CF2O-BBB (F) B- 3 (No.486) 2.0% 5-HB-CL 4.0% 5-HHB (F) -F 9.0% 7-HHB (F) -F 9.0% 3-HHB (F, F ) -F 8.0% 4-HHB (F, F) -F 3.0% 3-H2HB (F, F) -F 12.0% 3-HBB (F, F) -F 2.0% 2 -HHBB (F, F) -F 2.0% 3-GHB (F, F) -F3 0% 4-GHB (F, F) -F 8.0% 5-GHB (F, F) -F 6.0% NI = 85.4 (° C.) η = 47.4 (mPa · s) Δn = 0.124 Δε = 8.8 Vth = 1.58 (V)

Usage Example 24 2CF2O-B (F) BB-OCF3 (No. 82) 7.0% 2CF2O-BB (F) B-OCF3 (No. 84) 7.0% 2CF2O-B (F, F) BB-5 (No. 58) 7.0% 2CF2O-BB (F, F) B-5 (No. 60) 7.0% 3-HHB (F) -F 8.0% 3-HHB (F, F F) -F 8.0% 3-HBB (F, F) -F 7.0% 3-H2HB (F, F) -F 10.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 2-HBEB (F, F) -F 2.0% 3-HBEB (F, F) -F 3.0% 3-GHB (F, F) -F 3.0% 4-GHB (F, F) -F 7.0% 5-GHB (F, F) -F 7.0% 3-HHBB (F, F) -F 4.0% NI = 84.2 (° C.) η = 49.6 (mPa · s) Δn = 0.123 Δε = 10.4 Vth = 1.43 (V)

Use Example 25 2CF2O-BB-F (No. 7) 4.0% 7-HB (F) -F 3.0% 5-HB-CL 3.0% 3-HH-4 9.0% 3-HH-EMe 23.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 5.0% 3-HHEB-F 8.0% 5-HHEB- F 8.0% 4-HGB (F, F) -F 5.0% 5-HGB (F, F) -F 6.0% 2-H2GB (F, F) -F 4.0% 3-H2GB (F, F) -F 5.0% 5-GHB (F, F) -F 7.0% NI = 80.3 (° C.) η = 20.2 (mPa · s) Δn = 0.067 Δε = 5.9 Vth = 1.89 (V)

Use Example 26 2CF2O-B (F) BB-Cl (No. 63) 6.0% 2CF2O-BB (F) B-Cl (No. 65) 6.0% 2CF2O-BB (F) B ( F, F) -F (No.79) 6.0% 2CF2O-BB (F, F) B (F) -F (No.70) 6.0% 2CF2O-BB (F) B-5 (No. 59) 6.0% 3-H2HB (F, F) -F 5.0% 5-H2HB (F, F) -F 5.0% 3-HBB (F, F) -F 30.0% 5- HBB (F) B-2 10.0% 5-HBB (F) B-3 10.0% 3-BB (F) B (F, F) -F 5.0% 5-B2B (F, F) B (F) -F 5.0% NI = 111.5 (° C.) η = 58.0 (mPa · s) Δn = 0.175 Δε = 10.9 Vth = 1.66 (V)

Use Example 27 2CF2O-B (F) BB-OCF3 (No. 82) 3.0% 2CF2O-BB (F) BH-3 (No. 475) 3.0% 3-HB (F, F) CF2OB (F, F) -F 11.0% 5-HB (F, F) CF2OB (F, F) -F 11.0% 5-HB-CL 7.0% 3-HH-4 14.0% 2-HH-5 4.0% 3-HHB-1 4.0% 3-HHEB-F 6.0% 5-HHEB-F 6.0% 3-HHB (F, F) -F 6.0% 3-HHEB (F, F) -F 8.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 2.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 3.0% 5-HBEB (F, F) -F 3.0% 3-HHBB (F, F) -F 3.0% NI = 83.7 (° C) η = 21.2 (mPa · s) Δn = 0.087 Δε = 8.0 Vth = 1.57 (V)

Usage Example 28 1CF2O-BB (F, F) CF2OB (F, F) -F (No.395) 20.0% 2CF2O-BB (F) B (F, F) -F (No.79) 5.0% 2CF2O-BB (F, F) B (F) -F (No. 70) 5.0% 2CF2O-BBB (F) B-3 (No.486) 3.0% 3-BB (F , F) CF2OB (F, F) -F 15.0% 3-HH-4 8.0% 3-HHB (F, F) -F 10.0% 3-H2HB (F, F) -F 9. 0% 3-HBB (F, F) -F 5.0% 3-HHBB (F, F) -F 3.0% 3-HH2BB (F, F) -F 4.0% 3-HHB-16 5.0% 5-HBBH-1O1 7.0% NI = 84.8 (° C.) η = 36.8 (mPa · s) Δn = 0.121 Δε = 13.3 Vth = 1.33 (V)

Use Example 29 1CF2O-B (2F, 3F) HH-3 (No.33) 7.0% 1CF2O-B (2F, 3F) HH-5 (No.34) 7.0% 3-HEB- O4 28.0% 4-HEB-O2 20.0% 5-HEB-O1 20.0% 3-HEB-O2 18.0% NI = 81.6 (° C) η = 23.2 (mPa · s) Δn = 0.091

Usage Example 30 1CF2O-B (2F, 3F) HH-3 (No.33) 7.0% 1CF2O-B (2F, 3F) HH-5 (No.34) 6.0% 2CF2O-B ( 2F, 3F) HH-3 (No. 35) 7.0% 2CF2O-B (2F, 3F) HH-5 (No. 36) 6.0% 3-HH-2 5.0% 3-HH-4 6.0% 3-HH-O1 4.0% 3-HH-O3 5.0% 5-HH-O1 4.0% 3-HB (2F, 3F) -O2 12.0% 5-HB (2F , 3F) -O2 11.0% 5-HHB (2F, 3F) -O2 3.0% 3-HHB (2F, 3F) -2 24.0% NI = 76.3 (° C) Δn = 0.073 Δε = −2.8

Use Example 31 2CF2O-B (2F, 3F) HH-5 (No. 36) 3.0% 3-HH-5 5.0% 3-HH-4 5.0% 3-HH-O16 0.0% 3-HH-O3 6.0% 3-HB-O1 5.0% 3-HB-O2 5.0% 3-HB (2F, 3F) -O2 10.0% 5-HB (2F, 3F) -O2 10.0% 3-HHB (2F, 3F) -O2 12.0% 5-HHB (2F, 3F) -O2 10.0% 3-HHB (2F, 3F) -2 4.0% 2-HHB (2F, 3F) -1 4.0% 3-HHEH-3 5.0% 3-HHEH-5 5.0% 4-HHEH-3 5.0% NI = 85.0 (° C.) Δn = 0.076 Δε = -3.2

Use Example 32 1CF2O-B (2F, 3F) HH-3 (No.33) 5.0% 1CF2O-B (2F, 3F) HH-5 (No.34) 10.0% 2CF2O-B ( 2F, 3F) HH-3 (No. 35) 5.0% 2CF2O-B (2F, 3F) HH-5 (No. 36) 10.0% 3-HH-O1 8.0% 5-HH-O1 4.0% 3-HH-4 5.0% 3-HB (2F, 3F) -O2 16.0% 5-HB (2F, 3F) -O2 21.0% 2-HHB (2F, 3F)- 1 5.0% 3-HHB (2F, 3F) -1 7.0% 3-HHB (2F, 3F) -02 4.0% NI = 50.8 (° C) η = 26.4 (mPa · s) ) Δn = 0.069 Δε = -3.1

Use Example 33 2CF2O-B (2F, 3F) HH-3 (No. 35) 4.0% 2CF2O-BB-F (No. 7) 8.0% 2CF2O-BB (F) B-5 ( No. 59) 6.0% 3-HB-O2 20.0% 1O1-HH-3 6.0% 1O1-HH-5 5.0% 3-HH-EMe 12.0% 4-HEB-O19 0.0% 4-HEB-O2 7.0% 3-HHB-1 6.0% 4-HEB (2CN, 3CN) -O4 3.0% 6-HEB (2CN, 3CN) -O4 3.0% 3 -HEB (2CN, 3CN) -O5 4.0% 4-HEB (2CN, 3CN) -O5 3.0% 5-HEB (2CN, 3CN) -O5 2.0% 2-HBEB (2CN, 3CN)- O2 2.0% NI = 56.6 (° C.) η = 35.7 (mPa · s) Δn = 0.084 Δε = −4.3 th = 1.93 (V)

[0160]

The compound of the present invention has a large absolute value of Δε, a relatively small viscosity, a relatively large Δn, and shows good compatibility even at a low temperature. This compound is useful as a component of a liquid crystal composition in various display modes. When the composition of the present invention is used, a liquid crystal display device which can be driven at a low voltage can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 19/20 C09K 19/20 19/30 19/30 19/34 19/34 19/54 19/54 B G02F 1/13 500 G02F 1/13 500 (72) Inventor Yasuhiro Kubo 5-1, Goi Kaigan, Ichihara City, Chiba Prefecture Chisso Petrochemical Co., Ltd. Functional Materials Research Laboratory F-term (reference) 4H006 AA01 AB64 GP03 GP20 GP22 4H027 BB03 BB04 BC05 BD03 BD04 BD05 BD07 BD09 CB01 CC01 CC04 CD01 CD04 CE04 CE05 CG04 CG05 CH05 CL01 CL04 CL05 CM01 CM02 CM04 CM05 CN01 CN04 CN05 CP04 CP05 CQ04 CR01 CR04 CR05 CS04 CT01 CT02 CT03 CT04 CT05 CU01 CU04 CU05 CW01 CW04 DF01 DF04 DF01

Claims (22)

[Claims] 1. A compound represented by the following formula (1). Wherein R ¹ represents alkyl having 1 to 20 carbons, wherein any non-adjacent methylene may be replaced by oxygen or sulfur; R ² is hydrogen, halogen, cyano or C ¹ to C 20 Wherein any non-adjacent methylene is -CH
= CH-, oxygen or sulfur may be replaced, in this alkyl any hydrogen may be replaced by halogen; ring A ¹ , ring A ² and ring A ³ are each independently trans-1,4 -Cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, wherein any non-adjacent methylene in trans-1,4-cyclohexylene and 1,4-cyclohexenylene is replaced by oxygen or sulfur Any non-adjacent ＝ CH— in 1,4-phenylene may be replaced by nitrogen and hydrogen may be replaced by halogen;
Z ¹ , Z ² and Z ³ each independently represent a single bond, —CH ₂ CH
_{2 -, - CH 2 O -} , - OCH 2 -, - COO -, - OC
O -, - CH = CH - , - CF 2 O- or -OCF ₂ -
Y ¹ , Y ² and Y ³ each independently represent hydrogen or fluorine, but Y ¹ is fluorine, Y ² is hydrogen, and Y ³ is not hydrogen; l and m are each independently To indicate 0 or 1). 2. The compound according to claim 1, wherein l = m = 0 in formula (1).
The compound according to claim 1, which is a compound represented by the following formula (1-1): 3. The compound according to claim 2, wherein in the formula (1-1), ring A ¹ is 1,4-phenylene in which hydrogen may be replaced by halogen. 4. The compound according to claim 3, wherein in the formula (1-1), Z ¹ is a single bond. 5. The compound according to formula (1), wherein l = m = 0.
The compound according to claim 1, which is a compound represented by the following formula (1-2): 6. In the formula (1-2), the ring A ¹ and the ring A ² may be 1,4-, wherein hydrogen may be replaced by halogen.
The compound according to claim 5, which is phenylene. 7. The compound according to claim 6, wherein in formula (1-2), Z ¹ and Z ² are a single bond. 8. The compound according to formula (1), wherein l = m = 0.
The compound according to claim 1, which is a compound represented by the following formula (1-3): 9. The compound according to claim 8, wherein in formula (1-3), ring A ¹ , ring A ² and ring A ³ are 1,4-phenylene in which hydrogen may be replaced by halogen. 10. In the formula (1-3), Z ¹ , Z ² and Z ³ are each independently -CH ₂ CH _2- , -CH ₂ O-,-
OCH ₂ - or a compound of claim 9, wherein is a single bond. 11. The compound according to claim 1, wherein in formula (1), Y ¹ and Y ² are fluorine and Y ³ is hydrogen. 12. The compound according to claim ¹ , wherein in the formula (1), Y ¹ is hydrogen. 13. A liquid crystal composition containing at least one compound according to claim 1. Description: 14. A compound comprising at least one compound according to claim 1 as a first component, and a compound represented by the following formulas (2), (3) and (4) as a second component: At least one compound selected from the group of compounds represented by
Containing liquid crystal composition. (Wherein R ³ represents alkyl having 1 to 10 carbons, and any non-adjacent —CH ₂ — in the alkyl may be replaced by oxygen or —CH ＝ CH—, and in this alkyl, any hydrogen is Optionally substituted with fluorine;
X ¹ is fluorine, chlorine, —OCF ₃ —, —OCF ₂ H, —CF
_{3, -CF 2 H, -CFH 2} , -OCF 2 CF 2 H or -O
CF ₂ shows the CFHCF _3; L ¹ and L ² each independently represents a hydrogen or fluorine; Z ⁴ and Z ⁵ are each independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - COO -, - CF _{2
O -, - OCF 2 -,} - CH = CH- or a single bond; ring A and ring B each independently trans-1,
4-cyclohexylene, 1,3-dioxane-2,5-
Diyl or 1,4-phenylene in which ring hydrogen may be replaced by fluorine, and ring C is trans-1,4-
Cyclohexylene or 1,4-phenylene wherein hydrogen on the ring may be replaced by fluorine). 15. A compound group containing at least one compound according to any one of claims 1 to 12 as a first component, and a compound group represented by the following formulas (5) and (6) as a second component: A liquid crystal composition containing at least one compound selected from the group consisting of: (Wherein, R ⁴ and R ⁵ each independently represent alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CHＣＨCH—, In this alkyl any hydrogen may be replaced by fluorine; X ² is -CN or -C≡C
Ring D is trans-1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,
Represents 5-diyl or pyrimidine-2,5-diyl;
Ring E is trans-1,4-cyclohexylene, 1,4-phenylene in which ring hydrogen may be replaced by fluorine,
Or pyrimidine-2,5-diyl; ring F represents trans-1,4-cyclohexylene or 1,4-phenylene; Z ⁶ represents — (CH ₂ ) ₂ —, —COO—, —CF
L ³ , L ⁴ and L ⁵ each independently represent hydrogen or fluorine; b, c represents ₂ O—, —OCF ₂ — or a single bond;
And d each independently represent 0 or 1.) 16. A compound comprising at least one compound according to any one of claims 1 to 12 as a first component and the following formulas (7), (8) and (9) as a second component: A liquid crystal composition containing at least one compound selected from the group of compounds represented by (Wherein R ⁶ and R ⁷ each independently represent an alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CH ＝ CH—, In this alkyl any hydrogen may be replaced by fluorine; Ring G and Ring I are each independently trans-1,4-cyclohexylene or 1,4
L ⁶ and L ⁷ each independently represent hydrogen or fluorine, but not simultaneously hydrogen;
Z ⁷ and Z ⁸ are each independently — (CH ₂ ) ₂ —, —COO
-Or a single bond). 17. A compound comprising at least one compound according to any one of claims 1 to 12 as a first component, and formulas (2), (3) and (3) according to claim 14 as a second component. It contains at least one compound selected from the group of compounds represented by 4), and as a third component, the following formula (1)
0) A liquid crystal composition containing at least one compound selected from the group of compounds represented by (11) and (12). (Wherein R ⁸ and R ⁹ each independently represent an alkyl having 1 to 10 carbons, and in this alkyl, any non-adjacent —CH ₂ — may be replaced by oxygen or —CHＣＨCH—, Any hydrogen in this alkyl may be replaced by fluorine; Ring J, Ring K and Ring M are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or ring hydrogen. Represents 1,4-phenylene which may be replaced by fluorine; Z ⁹ and Z ¹⁰ are each independently -C≡C-, -COO-,-
(CH _{2) 2} -, - shows a CH = CH- or a single bond). (18) A first component containing at least one compound according to any one of (1) to (12), and a second component represented by formulas (5) and (6) according to (15). 18. The compound according to claim 17, comprising at least one compound selected from the group consisting of
0) A liquid crystal composition containing at least one compound selected from the group of compounds represented by (11) and (12). (19) The first component comprises at least one compound according to any one of (1) to (12), and the second component comprises formulas (7), (8) and (8) according to (16). It contains at least one compound selected from the compound group represented by 9), and is selected from the compound groups represented by formulas (10), (11) and (12) according to claim 17 as the third component. A liquid crystal composition containing at least one compound. 20. The first component contains at least one compound according to any one of claims 1 to 12, and the second component comprises formulas (2), (3) and (3) according to claim 14. At least one compound selected from the group of compounds represented by 4), and at least one compound selected from the group of compounds represented by formulas (5) and (6) according to claim 15 as the third component. And as the fourth component, the formulas (10), (11) and (1) according to claim 17.
A liquid crystal composition containing at least one compound selected from the compound group represented by 2). 21. The liquid crystal composition according to claim 13, further comprising at least one optically active compound. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 13 to 21.