JPWO2020026583A1 - Liquid crystal compounds, liquid crystal compositions, and liquid crystal display elements having a benzothiazole ring and a CF2O binding group. - Google Patents

Abstract

The challenges are high stability to heat and light, high transparency (or high upper limit temperature), low lower limit temperature of liquid crystal phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant, It is an object of the present invention to provide a liquid crystal compound satisfying at least one of physical properties such as good compatibility with other liquid crystal compounds, a liquid crystal composition containing this compound, and a liquid crystal display element containing this composition. The means is a compound represented by the formula (1), a liquid crystal composition containing this compound, and a liquid crystal display element containing this composition. In formula (1), R1 is hydrogen, alkyl, etc .; rings A1, A2, and A3 are independently 1,4-phenylene, a ring represented by formula (A0), and at least one. The ring is a ring represented by the formula (A0); Z1, Z2 and Z3 are independently single bonds, -C≡C-, etc.; L1, L2, and L3 are independently hydrogen, fluorine. And so on; a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0, 1, 2, or 3.

Description

The present invention relates to liquid crystal compounds, liquid crystal compositions and liquid crystal display devices. More specifically, the present invention relates _{to a liquid crystal compound having a benzothiazole ring and a CF 2} O bonding group, a liquid crystal composition containing this compound and having a nematic phase, and a liquid crystal display element containing this composition.

Liquid crystal display elements are widely used in displays such as personal computers and televisions. This device utilizes physical properties such as optical anisotropy and dielectric anisotropy of a liquid crystal compound. The operation modes of the liquid crystal display element include PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (bistable twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. There are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and PSA (polymer sustained alignment). In the PSA mode device, a liquid crystal composition containing a polymer is used. In this composition, the orientation of the liquid crystal molecules can be controlled by the polymer.

In such a liquid crystal display element, a liquid crystal composition having appropriate physical properties is used. In order to further improve the characteristics of the device, it is preferable that the liquid crystal compound contained in this composition has the physical properties shown in the following (1) to (8). (1) High stability to heat and light, (2) High transparency, (3) Low lower limit temperature of liquid crystal phase, (4) Small viscosity (η), (5) Appropriate optical anisotropy (Δn), (6) Large dielectric anisotropy (Δε), (7) Appropriate elastic constant (K), (8) Good compatibility with other liquid crystal compounds.

The effects of the physical properties of the liquid crystal compound on the characteristics of the device are as follows. A compound having high stability to heat and light, as in (1), increases the voltage holding ratio of the device. This prolongs the life of the device. A compound having a high transparency point as in (2) widens the usable temperature range of the device. As in (3), a compound having a low lower limit temperature of the liquid crystal phase such as a nematic phase or a smectic phase, particularly a low lower limit temperature of the nematic phase also expands the usable temperature range of the device. A compound having a low viscosity as in (4) shortens the response time of the device.

Depending on the design of the device, a compound having an appropriate optical anisotropy, that is, a large optical anisotropy or a small optical anisotropy, as in (5) is required. When the response time is shortened by reducing the cell gap of the device, a compound having a large optical anisotropy is suitable. A compound having a large dielectric anisotropy as in (6) lowers the threshold voltage of the device. This reduces the power consumption of the element. On the other hand, a compound having a small dielectric anisotropy shortens the response time of the device by lowering the viscosity of the composition. This compound extends the usable temperature range of the device by raising the upper temperature limit of the nematic phase.

Regarding (7), the compound having a large elastic constant shortens the response time of the device. Compounds with a small elastic constant lower the threshold voltage of the device. Therefore, an appropriate elastic constant is required according to the characteristics to be improved. A compound having good compatibility with other liquid crystal compounds as in (8) is preferable. This is because liquid crystal compounds having different physical characteristics are mixed to adjust the physical characteristics of the composition.

So far, various liquid crystal compounds having a large dielectric anisotropy have been synthesized. Various liquid crystal compounds having large optical anisotropy have also been synthesized. This is because new compounds are expected to have good physical properties that conventional compounds do not have. This is because the novel compound may impart an appropriate balance to at least two physical characteristics in the composition. Under these circumstances, a compound having good physical properties and an appropriate balance with respect to the above physical properties (1) to (8) is desired.

Paragraph 0054 of Patent Document 1 describes the following compounds.

Japanese Unexamined Patent Publication No. 2001-3053 International Publication No. 1996/011897

The first challenge is high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, small viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal compound that satisfies at least one of physical characteristics such as an appropriate elastic constant and good compatibility with other liquid crystal compounds. It is to provide a compound having a large dielectric anisotropy as compared with a similar compound. The second challenge is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical characteristics such as a large specific resistance and an appropriate elastic constant. The challenge is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics. A third challenge is a liquid crystal display that contains this composition and has a wide temperature range in which the device can be used, short response times, large voltage retention, low threshold voltage, large contrast ratio, small flicker ratio, and long life. It is to provide an element.

式（１）において、
Ｒ^１は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
環Ａ^１、Ａ^２、およびＡ^３は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、２，６，７−トリオキサビシクロ［２．２．２］オクタン−１，４−ジイル、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、１，２−シクロプロピレン、１，３−シクロペンチレン、式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり、環Ａ^１、Ａ^２、およびＡ^３において、少なくとも１つの環は式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり；

Ｚ^１およびＺ^２は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｓ−、−ＳＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＦ＝ＣＦ−であり；
Ｌ^１、Ｌ^２、およびＬ^３は独立して、水素、塩素、フッ素、ＯＣＦ_３またはＣＦ_３であるが、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３であり；
ａおよびｂは独立して、０、１、２、または３であり、ａとｂの和は０、１、２、または３である。The present invention relates to a compound represented by the formula (1), a liquid crystal composition containing this compound, and a liquid crystal display device containing this composition.

In equation (1)
R ¹ is hydrogen or an alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−, and at least one −CH ₂ CH ₂ − May be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Rings A ¹ , A ² , and A ³ independently have 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen replaced with fluorine or chlorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, naphthalene -2,6-diyl, naphthalene in which at least one hydrogen is replaced with fluorine or chlorine-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-Diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, ^{ring of formula (A 0} ), or at least one ^{A ring represented by the formula (A 0} ) in which hydrogen is replaced with fluorine or chlorine, and in rings A ¹ , A ² and A ³ , at least one ring is a ring represented by the ^{formula (A 0).} Or a ring represented ^{by the formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine;

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH _{2- , -CH 2 S -, - SCH} 2 -, - CF 2 O -, - OCF 2 -, or a -CF = CF-;
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0, 1, 2, or 3.

The first advantages are high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal compound that satisfies at least one of physical characteristics such as an appropriate elastic constant and good compatibility with other liquid crystal compounds. It is to provide a compound having a large dielectric anisotropy as compared with a similar compound. The second advantage is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical characteristics such as a large specific resistance and an appropriate elastic constant. This advantage is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics. The third advantage is that the liquid crystal display contains this composition and has a wide temperature range in which the device can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long life. It is to provide an element.

The usage of terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition", and "liquid crystal display element" may be abbreviated as "compound", "composition", and "element", respectively. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but adjusting the physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, and dielectric anisotropy. It is a general term for compounds added for the purpose of This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds with alkenyl are not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives are added to this composition for the purpose of further adjusting the physical characteristics. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers are added as needed. NS. The liquid crystal compounds and additives are mixed in such a procedure. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The ratio (addition amount) of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may also be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "transparency point" is the transition temperature of the liquid crystal phase-isotropic phase in the liquid crystal compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smetic phase, nematic phase, etc.) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature of the nematic phase-isotropic phase in the mixture or the liquid crystal composition of the liquid crystal compound and the mother liquid crystal, and may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test).

The compound represented by the formula (1) may be abbreviated as the compound (1). At least one compound selected from the group of compounds represented by the formula (1) may be abbreviated as the compound (1). "Compound (1)" means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. These rules also apply to compounds represented by other formulas. In equations (1) to (15), symbols such as ^{A 1} , B ¹ , and C ¹ enclosed in hexagons correspond to rings such as ^{ring A 1} , ring B ¹ , and ring C ^{1, respectively.} The hexagon represents a six-membered ring such as cyclohexane or benzene. The hexagon may represent a fused ring such as naphthalene or a crosslinked ring such as adamantane.

In the chemical formulas of the component compounds, with symbols of terminal groups R ¹¹ to a plurality of compounds. In these compounds, two groups represented by any two R ¹¹ may be may be the same or different. For example, there are cases where ^{R 11 of} compound (2) ^{is ethyl and R 11} of compound (3) is ethyl. ^{In some cases, R 11 of} compound (2) ^{is ethyl and R 11} of compound (3) is propyl. This rule also applies to symbols such as ^{R 12} , R ¹³ , and Z ^11. In the compound (8), when i is 2, two rings ^{D 1} are present. The two groups represented by two rings D ¹ in the compound may be the same or different. When i is greater than 2, also apply to any two rings D ^1. This rule also applies to other symbols.

The expression "at least one'A'" means that the number of'A's is arbitrary. The expression "at least one'A'may be replaced by'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When more than one, it means that their positions can be selected without limitation. This rule also applies to the expression "at least one'A' has been replaced by a'B'". The expression "at least one'A' may be replaced by'B','C',or'D'" is any'if any'A' is replaced by a'B'. If A'is replaced by'C', and any'A' is replaced by'D', then more than one'A'is'B','C', and / or'D' It means to include the case where it is replaced by at least two. For example, " _{alkyl in which at least one -CH 2} -may be replaced by -O- or -CH = CH-" includes alkyl, alkoxy, alkoxyalkyl, alkoxy, alkoxyalkenyl, alkenyloxyalkyl. It is not preferable that two consecutive −CH ₂₋ are replaced with −O− to become −O−O−. Alkyl such as in, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

"R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced by -O-. Often, in these groups, at least one hydrogen may be replaced by fluorine. " In this expression, "in these groups" may be interpreted literally. In this expression, "these groups" means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, "these groups" refers to all of the groups described prior to the term "in these groups". This common-sense interpretation also applies to the terms "in these monovalent groups" and "in these divalent groups". For example, "these monovalent groups" refers to all of the groups described prior to the term "in these monovalent groups".

Halogen means fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. For the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to raise the upper limit temperature. 2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

The present invention includes the following items.

式（１）において、
Ｒ^１は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
環Ａ^１、Ａ^２、およびＡ^３は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、２，６，７−トリオキサビシクロ［２．２．２］オクタン−１，４−ジイル、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、１，２−シクロプロピレン、１，３−シクロペンチレン、式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり、環Ａ^１、Ａ^２、およびＡ^３において、少なくとも１つの環は式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり；

Ｚ^１およびＺ^２は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｓ−、−ＳＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＦ＝ＣＦ−であり；
Ｌ^１、Ｌ^２、およびＬ^３は独立して、水素、塩素、フッ素、ＯＣＦ_３またはＣＦ_３であるが、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３であり；
ａおよびｂは独立して、０、１、２、または３であり、ａとｂの和は０、１、２、または３である。Item 1. A compound represented by the formula (1).

In equation (1)
R ¹ is hydrogen or an alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−, and at least one −CH ₂ CH ₂ − May be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Rings A ¹ , A ² , and A ³ independently have 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen replaced with fluorine or chlorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, naphthalene -2,6-diyl, naphthalene in which at least one hydrogen is replaced with fluorine or chlorine-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-Diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, ^{ring of formula (A 0} ), or at least one ^{A ring represented by the formula (A 0} ) in which hydrogen is replaced with fluorine or chlorine, and in rings A ¹ , A ² and A ³ , at least one ring is a ring represented by the ^{formula (A 0).} Or a ring represented ^{by the formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine;

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH _{2- , -CH 2 S -, - SCH} 2 -, - CF 2 O -, - OCF 2 -, or a -CF = CF-;
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0, 1, 2, or 3.

式（１Ａ）から（１Ｅ）において、
Ｒ^１は、水素、炭素数１から１５のアルキル、炭素数１から１４のアルコキシ、炭素数２から１５のアルケニル、炭素数２から１４のアルケニルオキシ、炭素数１から１４のアルキルチオ、または炭素数２から１４のアルケニルチオであり；
環Ａ^１、Ａ^２、およびＡ^３は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、２，６，７−トリオキサビシクロ［２．２．２］オクタン−１，４−ジイル、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、１，２−シクロプロピレン、１，３−シクロペンチレン、式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり、環Ａ^１、Ａ^２、およびＡ^３において、少なくとも１つの環は式（Ａ^０）で表される環、または少なくとも１つの水素がフッ素または塩素で置き換えられた式（Ａ^０）で表される環であり；

Ｚ^１およびＺ^２は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｓ−、−ＳＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＦ＝ＣＦ−であり；
Ｌ^１、Ｌ^２、およびＬ^３は独立して、水素、塩素、フッ素、ＯＣＦ_３またはＣＦ_３であるが、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３である。Item 2. Item 2. The compound according to Item 1, which is represented by the formulas (1A) to (1E).

In formulas (1A) to (1E)
R ¹ is hydrogen, an alkyl having 1 to 15 carbon atoms, an alkoxy having 1 to 14 carbon atoms, an alkenyl having 2 to 15 carbon atoms, an alkenyloxy having 2 to 14 carbon atoms, an alkylthio having 1 to 14 carbon atoms, or a carbon number of carbon atoms. 2 to 14 alkenylthios;
Rings A ¹ , A ² , and A ³ independently have 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen replaced with fluorine or chlorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, naphthalene -2,6-diyl, naphthalene in which at least one hydrogen is replaced with fluorine or chlorine-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-Diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, ^{ring of formula (A 0} ), or at least one ^{A ring represented by the formula (A 0} ) in which hydrogen is replaced with fluorine or chlorine, and in rings A ¹ , A ² and A ³ , at least one ring is a ring represented by the ^{formula (A 0).} Or a ring represented ^{by the formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine;

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH _{2- , -CH 2 S -, - SCH} 2 -, - CF 2 O -, - OCF 2 -, or a -CF = CF-;
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ .

式（１Ａ−１）から（１Ｅ−４）において、
Ｒ^１は、炭素数１から１５のアルキル、炭素数１から１４のアルコキシ、炭素数２から１５のアルケニル、または炭素数２から１４のアルケニルオキシであり；
環Ａ^１、Ａ^２、およびＡ^３は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素で置き換えられたナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、ピリジン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１およびＺ^２は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｓ−、−ＳＣＨ_２−、−ＣＦ_２Ｏ−、または−ＯＣＦ_２−であり；
Ｌ^１、Ｌ^２、およびＬ^３は独立して、水素、フッ素、ＯＣＦ_３またはＣＦ_３であるが、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３である。Item 3. Item 2. The compound according to Item 1, which is represented by the formulas (1A-1) to (1E-4).

In formulas (1A-1) to (1E-4),
R ¹ is an alkyl having 1 to 15 carbons, an alkoxy having 1 to 14 carbons, an alkenyl having 2 to 15 carbons, or an alkenyloxy having 2 to 14 carbons;
Rings A ¹ , A ² , and A ³ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and 1,4- in which at least one hydrogen is replaced by fluorine. Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine, deca Hydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C ≡ C-, -CH ₂ O-, -OCH _2- , -CH ₂ S-,- SCH _2- , -CF ₂ O-, or -OCF _2- ;
L ¹ , L ² , and L ³ are independently hydrogen, fluorine, OCF ₃ or CF ₃ , but at least one is fluorine, OFF ₃ or CF ₃ .

Item 4. In the formulas (1A-1) to (1E-4) described in Item 3, R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 9 carbon atoms, or a carbon number of carbon atoms. a 2 to 9 alkenyloxy, ring ^{a 1} is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, tetrahydro Pyrim-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, 1,3-difluoronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, independently rings ^{a 2} and ^{a 3,} 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, naphthalene -2,6-diyl, 1,3-difluoronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, with Z ¹ and Z ² being independent and simple. Bond, -C ≡ C-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- , L ¹ is fluorine, OCF ₃ or CF ₃ , and L ² and L ³ are independent. Item 3. The compound according to Item 3, which is hydrogen or fluorine.

式（１Ａ−１ａ）から（１Ｅ−４ａ）において、
Ｒ^１は、炭素数１から１０のアルキル、炭素数１から９のアルコキシ、炭素数２から１０のアルケニル、または炭素数２から９のアルケニルオキシであり、；
Ｌ^１は、水素、フッ素、ＯＣＦ_３またはＣＦ_３であり、Ｌ^２およびＬ^３が独立して、水素またはフッ素であり、Ｌ^１、Ｌ^２、およびＬ^３において、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３であり；
Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、Ｙ^５、およびＹ^６は独立して、水素またはフッ素である。Item 5. Item 2. The compound according to Item 1, which is represented by the formulas (1A-1a) to (1E-4a).

In formulas (1A-1a) to (1E-4a),
R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms;
L ¹ is hydrogen, fluorine, OCF ₃ or CF ₃ , L ² and L ³ are independently hydrogen or fluorine, and in L ¹ , L ² , and L ³ , at least one is fluorine, OFF. ₃ or CF ₃ ;
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen or fluorine.

Item 6. ^{Item 5. The compound according to Item 5, wherein L 1} , L ² , and L ³ are fluorine in the formulas (1A-1a) to (1E-4a) according to Item 5.

式（１Ａ−１ｂ）から（１Ｃ−３ｃ）において、
Ｒ^１は、炭素数１から１０のアルキル、炭素数１から９のアルコキシ、炭素数２から１０のアルケニル、または炭素数２から９のアルケニルオキシであり、；
Ｌ^１は、水素、フッ素、ＯＣＦ_３またはＣＦ_３であり、Ｌ^２およびＬ^３が独立して、水素またはフッ素であり、Ｌ^１、Ｌ^２、およびＬ^３において、少なくとも１つはフッ素、ＯＣＦ_３またはＣＦ_３であり；
Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはフッ素である。Item 7. Item 2. The compound according to Item 1, represented by the formulas (1A-1b) to (1C-3c).

In formulas (1A-1b) to (1C-3c),
R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms;
L ¹ is hydrogen, fluorine, OCF ₃ or CF ₃ , L ² and L ³ are independently hydrogen or fluorine, and in L ¹ , L ² , and L ³ , at least one is fluorine, OFF. ₃ or CF ₃ ;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or fluorine.

Item 8. ^{Item 7. The compound according to Item 7, wherein L 1} , L ² , and L ³ are fluorine in the formulas (1A-1b) to (1C-3c) according to Item 7.

Item 9. A liquid crystal composition containing at least one compound according to any one of Items 1 to 8.

式（２）から（４）において、
Ｒ^１１およびＲ^１２は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｂ^１、環Ｂ^２、環Ｂ^３、および環Ｂ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２、およびＺ^１３は独立して、単結合、−ＣＯＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−である。Item 10. Item 9. The liquid crystal composition according to Item 9, further comprising at least one compound selected from the group of compounds represented by the formulas (2) to (4).

In equations (2) to (4)
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, in these groups, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are independently single-bonded, -COO-, -CH ₂ CH _2- , -CH = CH-, or -C≡C-.

式（５）から（７）において、
Ｒ^１３は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１１は、フッ素、塩素、−ＯＣＦ₃、−ＯＣＨＦ₂、−ＣＦ₃、−ＣＨＦ₂、−ＣＨ₂Ｆ、−ＯＣＦ₂ＣＨＦ₂、または−ＯＣＦ₂ＣＨＦＣＦ₃であり；
環Ｃ^１、環Ｃ^２、および環Ｃ^３は独立して、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１４、Ｚ^１５、およびＺ^１６は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−（ＣＨ_２）_４−であり；
Ｌ^１１およびＬ^１２は独立して、水素またはフッ素である。Item 11. Item 9. The liquid crystal composition according to Item 9 or 10, further containing at least one compound selected from the group of compounds represented by the formulas (5) to (7).

In equations (5) to (7)
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced by fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, and 1,4-phenylene, tetrahydropyran-2 in which at least one hydrogen is replaced by fluorine. , 5-Diyl, 1,3-dioxane-2,5-Diyl, or pyrimidine-2,5-Diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH _{2 CH 2 -, - CH = CH} -, - C≡C-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

式（８）において、
Ｒ^１４は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｄ^１は、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１７は、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−Ｃ≡Ｃ−であり；
Ｌ^１３およびＬ^１４は独立して、水素またはフッ素であり；
ｉは、１、２、３、または４である。Item 12. Item 8. The liquid crystal composition according to any one of Items 9 to 11, further containing at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced by fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2. , 5-Dioxane, or pyrimidine-2,5-Dioxane;
Z ¹⁷ is a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , or -C ≡ C-. Is;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.

式（１１）から（１９）において、
Ｒ^１５、Ｒ^１６、およびＲ^１７は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく、そしてＲ^１７は、水素またはフッ素であってもよく；
環Ｅ^１、環Ｅ^２、環Ｅ^３、および環Ｅ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
環Ｅ^５および環Ｅ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１８、Ｚ^１９、Ｚ^２０、およびＺ^２１は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＯＣＨ_２ＣＨ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり；
Ｌ^１５およびＬ^１６は独立して、フッ素または塩素であり；
Ｓ^１１は、水素またはメチルであり；
Ｘは、−ＣＨＦ−または−ＣＦ_２−であり；
ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、ｔは、１、２、または３である。Item 13. Item 6. The liquid crystal composition according to any one of Items 9 to 12, further containing at least one compound selected from the group of compounds represented by the formulas (11) to (19).

In equations (11) to (19),
R ¹⁵ , R ¹⁶ and R ¹⁷ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced, in these groups at least one hydrogen may be replaced with fluorine, and R ¹⁷ may be hydrogen or fluorine;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen with fluorine. 1,4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{E 5} and ring ^{E 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ²¹ are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ OCH ₂ CH _2- , or -OCF ₂ CH ₂ CH _2- ;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.

Item 14. At least one additive selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. Item 8. The liquid crystal composition according to any one of Items 9 to 13, which is further contained.

Item 15. A liquid crystal display element containing the liquid crystal composition according to any one of Items 9 to 14.

Item 16. Item 15. The liquid crystal display element according to Item 15, wherein the liquid crystal composition according to any one of Items 9 to 14 is encapsulated in a capsule.

Item 17. Item 15. The liquid crystal display element according to Item 15, wherein the liquid crystal composition according to any one of Items 9 to 14 is used for a lens used for switching between 2D and 3D.

The present invention also includes the following sections. (A) One selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. The composition described above further comprising two, or at least three additives. (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is 2 or more, the above liquid crystal composition. (C) The operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, VA mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is the active matrix (AM) method. , The above liquid crystal display element.

Aspects of compound (1), a method for synthesizing compound (1), a liquid crystal composition, and a liquid crystal display element will be described in order.

1. 1. Embodiments compounds of the present invention compounds (1) (1) has a benzothiazole ring and a CF 2 _O bonding group. Compound (1) is characterized by having a large dielectric anisotropy as compared with similar compounds. A preferred example of compound (1) will be described. Preferred examples of terminal groups R ¹ , rings A ¹ , A ² , and A ³ , binding groups Z ¹ and Z ² , and substituents L ¹ , L ² , and L ³ in compound (1) are compound (1). It also applies to the subexpressions of. In compound (1), the physical properties can be arbitrarily adjusted by appropriately combining these groups. Since there is no significant difference in the physical properties of the compounds, the compound (1) ^{may contain more isotopes such as 2} H (deuterium) and ¹³ C than the amount of the natural abundance ratio. The definition of the symbol of compound (1) is as described in Item 1.

In formula (1), R ¹ is hydrogen or an alkyl having 1 to 15 carbon atoms, in which at least one -CH _2- may be replaced by -O- or -S-, at least 1 One -CH ₂ CH _2- may be replaced by -CH = CH-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine.

Examples of R ¹ are hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxy, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl, alkylthio, alkylthioalkyl, alkenylthio, alkenylthioalkyl, and alkylthioalkenyl. Preferred R ¹ is alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxy, alkenyloxy, alkenyloxyalkyl, or alkoxyalkenyl. More preferred R ¹ is alkyl, alkoxy, alkoxyalkyl, alkenyl, or alkenyloxy. Particularly preferred R ¹ is alkyl or alkenyl. The most preferred R ¹ is alkyl.

Preferred alkyls are -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , -C ₆ H ₁₃ , or -C ₇ H ₁₅ .

Preferred alkoxys are -OCH ₃ , -OC ₂ H ₅ , -OC ₃ H ₇ , -OC ₄ H ₉ , -OC ₅ H ₁₁ , -OC ₆ H ₁₃ , or -OC ₇ H ₁₅ .

Preferred _{alkoxyalkyl, -CH 2 OCH 3, -CH 2} OC 2 H 5, -CH 2 OC 3 H 7, - (CH 2) 2 -OCH 3, - (CH 2) 2 -OC 2 H 5, - (CH ₂ ) _2- OC ₃ H ₇ ,-(CH ₂ ) _3- OCH ₃ ,-(CH ₂ ) _4- OCH ₃ , or-(CH ₂ ) _5- OCH ₃ .

Preferred alkenyl is -CH = CH ₂ , -CH = CHCH ₃ , -CH ₂ CH = CH ₂ , -CH = CHC ₂ H ₅ , -CH ₂ CH = CHCH ₃ ,-(CH ₂ ) ₂ -CH = CH. ₂ , -CH = CHC ₃ H ₇ , -CH ₂ CH = CHC ₂ H ₅ ,-(CH ₂ ) _2- CH = CHCH ₃ , or-(CH ₂ ) ₃ -CH = CH ₂ .

Preferred alkenyloxys are -OCH ₂ CH = CH ₂ , -OCH ₂ CH = CHCH ₃ , or -OCH ₂ CH = CHC ₂ H ₅ .

Preferred ^{R 1} is _{hydrogen, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 11, -C 6 H 13, -OCH 3, -OC 2 H 5 , -OC ₃ H ₇ , -OC ₄ H ₉ , -OC ₅ H ₁₁ , -CH ₂ OCH ₃ , -CH = CH ₂ , -CH = CHCH ₃ ,-(CH ₂ ) ₂ -CH = CH ₂ ,- CH ₂ CH = CHC ₂ H ₅ , − (CH ₂ ) ₂ −CH = CHCH ₃ , −OCH ₂ CH = CH ₂ , −OCH ₂ CH = CHCH ₃ , or −OCH ₂ CH = CHC ₂ H ₅ . Further preferred ^{R 1} _{is, -C 3 H 7, -C 4} H 9, -C 5 H 11, -C 6 H 13, - (CH 2) 2 -CH = CH 2, - (CH 2) 2 -CH = CHCH ₃ .

When R ¹ is linear, the temperature range of the liquid crystal phase is wide and the viscosity is low. When R ¹ is a branched chain, the compatibility with other liquid crystal compounds is good. Compounds in which R ¹ is optically active are useful as chiral dopants. By adding this compound to the composition, it is possible to prevent the reverse twisted domain generated in the liquid crystal display element. Compounds in which R ¹ is not optically active are useful as components of the composition. When R ¹ is alkenyl, the preferred configuration depends on the position of the double bond. Alkenyl compounds with a preferred configuration have a low viscosity, a high upper temperature limit or a wide temperature range of the liquid crystal phase.

The preferred configuration of -CH = CH- in alkenyl depends on the position of the double bond. -CH = CHCH ₃ , -CH = CHC ₂ H ₅ , -CH = CHC ₃ H ₇ , -CH = CHC ₄ H ₉ , -C ₂ H ₄ CH = CHCH ₃ , and -C ₂ H ₄ CH = CHC ₂ trans configuration is preferred in the odd position alkenyl having a double bond such as H _5. The cis configuration is preferred for even-numbered double bonds such as _{−CH 2} CH = CHCH ₃ , −CH ₂ CH = CHC ₂ H ₅ , and −CH ₂ CH = CHC ₃ H _7. Alkenyl compounds with a preferred configuration have high clear spots or a wide temperature range of liquid crystal phases. More details are given in Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327.

In formula (1), rings A ¹ , A ² , and A ³ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen is fluorine or chlorine. 1,4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1 replaced by , 4-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,6-Diyl in which at least one hydrogen is replaced with fluorine or chlorine, Decahydronaphthalene-2,6-Diyl, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, represented by the ^{formula (A 0)} A ring, or a ring represented by ^{formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine ^{, in rings A 1} , A ² , and A ³ , at least one ring is formula (A ⁰ ). A ring represented by, or a ring represented by the formula (A ⁰ ) in which at least one hydrogen is replaced with fluorine or chlorine.

Preferred rings A ¹ , A ² , or A ³ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2, 6-Difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, is a ring represented by the formula ring represented by (a ⁰⁾ or at least one hydrogen is replaced by fluorine formula, (a ^0). More preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, tetrahydropyran-2. , 5-Diyl, or a ring represented by the ^{formula (A 0).} Particularly preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or the formula (A). It is a ring represented by ^0).

When rings A ¹ , A ² or A ³ are 1,4-cyclohexylene, the transparency point is high and the viscosity is low. When rings A ¹ , A ² , or A ³ are 1,4-phenylene, or when at least one hydrogen is 1,4-phenylene replaced by fluorine, the optical anisotropy is high and the orientation is high. The oriental order parameter is relatively large. When rings A ¹ , A ² , or A ³ are 1,4-phenylene in which at least one hydrogen is replaced with fluorine, or ^{a ring represented by the formula (A 0} ), the dielectric anisotropy is large. ..

In equation (1), Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O. _{-, - OCH 2 -, -} CH 2 S -, - SCH 2 -, - CF 2 O -, - OCF 2 -, or -CF = CF-.

Preferred Z ¹ and Z ² are single bonds, -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, or -OCF _2- . More preferred Z ¹ and Z ² are single bonds, -C≡C-, or -CF ₂ O-. Particularly preferred Z ¹ and Z ² are single bonds or −C≡C−. The most preferred Z ¹ and Z ² are single bonds.

When Z ¹ and Z ² are single bonds, they have high chemical stability and low viscosity. When Z ¹ and Z ² are −C≡C−, the optical anisotropy is large.

In equation (1)
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ .

When L ¹ , L ² and L ³ are a combination of fluorine, OCF ₃ and CF ₃ , the dielectric anisotropy is large. When L ¹ is fluorine, OCF ₃ or CF ₃ , the dielectric anisotropy is particularly large. When L ¹ , L ² and L ³ are fluorine, the dielectric anisotropy is particularly large.

In formula (1), a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0, 1, 2, or 3.

When the sum of a and b is 0, the viscosity is small. When the sum of a and b is 2 or 3, the transparent point is high.

Examples of the preferred compound (1) are the compounds (1A) to (1E) described in Item 2. Examples of the more preferable compound (1) are the compounds (1A-1) to (1E-4) described in Item 3. Examples of the most preferable compound (1) are the compounds (1A-1a) to (1E-4a) described in Item 5 and the compounds (1A-1b) to (1C-3c) described in Item 7. ..

Compounds (1A-1a) and (1A-2a) are preferred from the standpoint of high stability to heat and light and low viscosity. Compounds (1B-1a) to (1C-3a) are preferable from the viewpoint of high transparency and good compatibility. Compounds (1D-1a) to (1E-4a) are preferable from the viewpoint of high transparency and large optical anisotropy.

2. Synthesis of Compound (1) A method for synthesizing compound (1) will be described. Compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. The methods for introducing the required end groups, rings and binding groups into the starting material are "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" (John Wiley & Sons). , Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Course" (Maruzen), etc.

2-1. Generation of Binding Group Z First, a scheme is shown with respect to the method of generating ^{Z 3} from the ^{binding group Z 1.} Next, the reactions described in the scheme according to the methods (1) to (11) will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group with at least one ring. The monovalent organic groups represented by the plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1J) correspond to compound (1).

(1) Generation of single bond A compound by reacting an arylboric acid (31) synthesized by a known method with a halide (32) in the presence of a catalyst such as carbonate and tetrakis (triphenylphosphine) palladium. (1A) is synthesized. This compound (1A) is prepared by reacting a halide (33) synthesized by a known method with n-butyllithium and then zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It is also synthesized by reacting (32).

(2) Production of -COO- The halide (33) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (34). Compound (1B) is synthesized by dehydrating compound (35) and carboxylic acid (34) synthesized by a known method in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). do.

(3) _{Production of -CF 2} O- Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain thionoester (36). The thionoester (36) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also synthesized by fluorinating thionoester (36) with DAST ((diethylamino) sulfur trifluoride). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. It is also possible to generate this linking group by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(4) Generation of -CH = CH- The halide (32) is treated with n-butyllithium and then reacted with a formamide such as DMF (N, N-dimethylformamide) to obtain an aldehyde (38). The phosphonium salt (37) synthesized by a known method is treated with a base such as potassium t-butoxide to generate phosphorus irid. This phosphorus irid is reacted with aldehyde (38) to synthesize compound (1D). Since a cis form is produced depending on the reaction conditions, the cis form is isomerized to a trans form by a known method if necessary.

(5) -CH ₂ CH _2- Production Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(6) _{Formation of − (CH 2} ) ₄ − Use a phosphonium salt (39) instead of the phosphonium salt (37), and prepare a compound having _{− (CH 2} ) _{2 −CH = CH − according to the method of method (4).} obtain. This is catalytically hydrogenated to synthesize compound (1F).

(7) -CH ₂ CH = CHCH _2- formation A compound according to the method (4), using a phosphonium salt (40) instead of the phosphonium salt (37) and an aldehyde (41) instead of the aldehyde (38). (1G) is synthesized. Since a trans form is produced depending on the reaction conditions, the trans form is isomerized to a cis form by a known method if necessary.

(8) Production of -C≡C- After reacting the halide (33) with 2-methyl-3-butyne-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions. Deprotection with to give compound (42). In the presence of a catalyst of dichloropalladium and copper halide, compound (42) is reacted with a halide (32) to synthesize compound (1H).

(9) Production of -CF = CF- The halide (33) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (43). The halide (32) is treated with n-butyllithium and then reacted with the compound (43) to synthesize the compound (1I).

(10) _{Production of −OCH 2} -The aldehyde (38) is reduced with a reducing agent such as sodium borohydride to obtain compound (44). The compound (44) is bromide with hydrobromic acid or the like to obtain a bromide (45). In the presence of a base such as potassium carbonate, the bromide (45) is reacted with the compound (46) to synthesize the compound (1J).

(11) -CF ₂ CF _2- generation
Diketone (-COCO-) was fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst according to the method described in J. Am. Chem. Soc., 2001, 123, 5414.-(CF ₂ ). Obtain a compound having _2-.

2-2. Formation of rings A ¹ , A ² , and A ³ , such as 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene. As for the ring, the starting material is commercially available, or the production method is well known. For the formation of tetrahydropyran-2,5-diyl, refer to paragraphs 0084 to 0107 of JP2013-241397A. For the production of 1,3-dioxane-2,5-diyl, refer to paragraphs 096 to 0119 of JP2009-132927. For the formation of pyrimidine-2,5-diyl and pyridine-2,5-diyl, see paragraphs 0083-0094 of WO 2010/047260.

2-3. Method for synthesizing compound (1) An example of a method for synthesizing compound (1) is as follows. Sulfuric acid and sodium thiocyanate are allowed to act on the known compound aniline (51) and reacted with sulfuryl chloride to obtain aminobenzothiazole (52). Aminobenzothiazole (52) is reacted with phosphoric acid, sodium nitrite, and hypophosphorous acid to obtain benzothiazole (53). Bromide (54) synthesized by a known method with benzothiazole (53) is reacted in the presence of potassium carbonate, triphenylphosphine, palladium acetate, and copper (II) acetate monohydrate to compound (1). Is synthesized. In these compounds, ^{the definitions of symbols such as R 1} and ring A ¹ are the same as the definitions of the symbols described in Item 1.

3. 3. Liquid crystal composition 3-1. Ingredients Compounds The liquid crystal composition of the present invention will be described. This composition contains at least one compound (1) as component A. The composition may include two or more compounds (1). The component of the composition may be only the compound (1). The composition preferably contains at least one of the compound (1) in the range of 1% by weight to 99% by weight in order to exhibit excellent physical properties. In the composition having a positive dielectric anisotropy, the preferable content of the compound (1) is in the range of 5% by weight to 60% by weight. In the composition having a negative dielectric anisotropy, the preferable content of the compound (1) is 30% by weight or less.

This composition preferably contains compound (1) as component A, and further contains a liquid crystal compound selected from components B, C, D, and E shown in Table 1. When preparing this composition, it is preferable to select the components B, C, D, and E in consideration of the positive and negative values and the magnitude of the dielectric anisotropy. The composition may contain different liquid crystal compounds from compounds (1) to (8) and compounds (11) to (19). The composition may be free of such liquid crystal compounds.

Component B is a compound having two terminal groups such as alkyl. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). can. In these compounds, R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH _2- is -O. It may be replaced with −, and in these groups, at least one hydrogen may be replaced with fluorine.

Component B has a small dielectric anisotropy. Component B is close to neutral. Compound (2) has the effect of lowering the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have the effect of widening the temperature range of the nematic phase or adjusting the optical anisotropy by raising the upper limit temperature.

As the content of component B is increased, the viscosity of the composition decreases, but the dielectric anisotropy decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, it is preferable that the content is large. When preparing a composition for a mode such as IPS or VA, the content of the component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

Component C is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). .. In these compounds, R ¹³ is an alkyl with 1 to 10 carbons or an alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − may be replaced with -O-. In these groups, at least one hydrogen may be replaced with fluorine. X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ .

Component C has a positive dielectric anisotropy and very good stability to heat and light, and is therefore used when preparing compositions for modes such as IPS, FFS, and OCB. The content of component C is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. It is in the range of%. When the component C is added to a composition having a negative dielectric anisotropy, the content of the component C is preferably 30% by weight or less. By adding the component C, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component D is compound (8) whose right terminal group is -C≡N or -C≡C-C≡N. Preferred examples of the component D include compounds (8-1) to (8-64). In these compounds, R ¹⁴ is an alkyl with 1 to 10 carbons or an alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − may be replaced with -O-. In these groups, at least one hydrogen may be replaced with fluorine. X ¹² is −C≡N or −C≡C−C≡N.

Component D has a positive dielectric anisotropy and a large value, and is therefore used when preparing a composition for a mode such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.

When preparing a composition for a mode such as TN, the content of component D is preferably in the range of 1% by weight to 99% by weight, preferably from 10% by weight, based on the weight of the liquid crystal composition. It is in the range of 97% by weight, more preferably 40% by weight to 95% by weight. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component E is compounds (11) to (19). These compounds have phenylene in which the lateral position is replaced by two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component E are compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), compounds (14-). 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds (1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11). 18-1) to (18-3), and compound (19-1) can be mentioned. In these ^compounds, R ^{15, R 16,} and ^{R 17} are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one -CH ₂ - May be replaced with —O—, in these groups at least one hydrogen may be replaced with fluorine, and R ¹⁷ may be hydrogen or fluorine.

Component E has a large negative dielectric anisotropy. Component E is used when preparing compositions for modes such as IPS, VA, PSA and the like. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negatively large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about −5, the content is preferably 40% by weight or more in order to drive the voltage sufficiently.

Since the compound (11) of the component E is a bicyclic compound, it has the effects of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (12) and (13) are tricyclic compounds and the compound (14) is a tetracyclic compound, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. be. Compounds (15) to (19) have the effect of increasing the dielectric anisotropy.

When preparing a composition for a mode such as IPS, VA, PSA, the content of the component E is preferably 40% by weight or more, more preferably 50% by weight, based on the weight of the liquid crystal composition. In the range of 95% by weight. When the component E is added to the composition having a positive dielectric anisotropy, the content of the component E is preferably 30% by weight or less. By adding the component E, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Appropriate combination of components B, C, D, and E with compound (1) results in high stability to heat and light, high upper and lower temperature limits, low lower limit temperature, low viscosity, suitable optical anisotropy (ie, large optics). A liquid crystal composition that satisfies at least one of physical characteristics such as anisotropy (or small optical anisotropy), large modulus anisotropy, large specific resistance, and appropriate elastic constant (that is, large elastic constant or small elastic constant). Can be prepared. Devices containing such compositions have a wide temperature range in which the device can be used, short response times, high voltage retention, low threshold voltage, high contrast ratio, low flicker rate, and long lifetime.

If the element is used for a long time, flicker may occur on the display screen. The flicker rate (%) can be expressed by (| brightness when a positive voltage is applied-brightness when a negative voltage is applied |) / average brightness) × 100. An element having a flicker rate in the range of 0% to 1% is less likely to cause flicker on the display screen even if the element is used for a long time. It is presumed that this flicker is related to image burn-in and is caused by a difference between the potential of the positive frame and the potential of the negative frame when driven by alternating current. The composition containing the compound (1) is also useful for reducing the occurrence of flicker.

3-2. Additives The liquid crystal composition is prepared by a known method. For example, the constituent compounds are mixed and dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives are polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers and the like. Such additives are well known to those of skill in the art and are described in the literature.

In a liquid crystal display element having a PSA (polymer sustained alignment) mode, the composition contains a polymer. The polymerizable compound is added for the purpose of forming a polymer in the composition. A polymer is produced in the composition by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the polymerizable compound. By this method, an appropriate pre-tilt is achieved, so that the response time is shortened and the device with improved image burn-in is produced.

Preferred examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), and vinyl ketones. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

More preferred examples are compounds (M-1) to (M-18). In these compounds, R ²⁵ to R ³¹ are independently hydrogen or methyl; R ³² , R ³³ , and R ³⁴ are independently hydrogen or alkyl having 1 to 5 carbon atoms, R ³² , At ^{least one of R 33} , and R ³⁴ is an alkyl having 1 to 5 carbon atoms; v, w, and x are 0 or 1 independently; u and y are independently 1 to 10 It is an integer. L ²¹ to L ²⁶ are independently hydrogen or fluorine; L ²⁷ and L ²⁸ are independently hydrogen, fluorine, or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction conditions, the amount of residual polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPO, 1173, and 4265 from BASF's DaroCure series and 184,369,500,651,784,819,907,1300,1700,1800,1850 from the Irgacure series. , And 2959.

Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.

Polymerization can be carried out by adding a photoradical polymerization initiator to the liquid crystal composition and then irradiating it with ultraviolet rays in a state where an electric field is applied. However, unreacted polymerization initiators or degradation products of the polymerization initiators may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give a necessary twist angle. The spiral pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl having 1 to 10 carbon atoms. * Marks represent asymmetric carbon.

Antioxidants are effective in maintaining a large voltage retention. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); Irganox415, Irganox565, Irganox1010, Irganox1035, Irganox3114, and Irganox1098 (trade name: BASF). The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 328, and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.

Light stabilizers such as amines with steric hindrance are preferred for maintaining high voltage retention. Preferred examples of light stabilizers are the following compounds (AO-5), (AO-6), (AO-7), (AO-8), and (AO-9); Product name; BASF); LA-52, LA-57, LA-77Y, and LA-77G (trade name; ADEKA) can be mentioned. A heat stabilizer is also effective for maintaining a large voltage holding ratio, and Irgafos 168 (trade name; BASF) can be mentioned as a preferable example. Dichroic dyes such as azo dyes, anthraquinone dyes and the like are added to the composition to accommodate devices in GH (guest host) mode. Defoamers are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.

In compound (AO-1), R ⁴⁰ is an alkyl having 1 to 20 carbons, an alkoxy having 1 to 20 carbons, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ has 1 carbon. To 20 alkyl. In compounds (AO-2) and (AO-5), R ⁴² is an alkyl having 1 to 20 carbon atoms. In the compound ^{(AO-5), R 43} is hydrogen, methyl or O ^· (oxygen radical); ring ^{G 1} is 1,4-cyclohexylene or 1,4-phenylene; Compound (AO-7) and In (AO-8), ring G ² is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen has been replaced with fluorine; compound (AO-5),. In (AO-7) and (AO-8), z is 1, 2, or 3.

4. Liquid crystal display element The liquid crystal composition has an operation mode such as PC, TN, STN, OCB, PSA, and can be used for a liquid crystal display element driven by an active matrix method. This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS, and can also be used for a liquid crystal display element driven by a passive matrix method. These elements can be applied to any type of reflective type, transmissive type, and semitransparent type.

This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated. This composition can also be used in a polymer-dispersed liquid crystal display element (PDLCD) and a polymer network liquid crystal display element (PNLCD). In these compositions, a large amount of the polymerizable compound is added. On the other hand, when the proportion of the polymerizable compound is 10% by weight or less based on the weight of the liquid crystal composition, a liquid crystal display element in PSA mode is produced. The preferred proportion is in the range of 0.1% by weight to 2% by weight. A more preferable ratio is in the range of 0.2% by weight to 1.0% by weight. The PSA mode element can be driven by a drive system such as an active matrix system or a passive matrix system. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type.

1. 1. Examples of Compound (1) The present invention will be described in more detail by way of examples. The present invention is not limited by the examples, as the examples are typical. Compound (1) was synthesized by the following procedure. The synthesized compound was identified by a method such as NMR analysis. The physical characteristics of the compound or composition and the characteristics of the device were measured by the following methods.

NMR analysis: A DRX-500 manufactured by Bruker Biospin was used for the measurement. ^{1 In the 1} H-NMR measurement, the sample _{was dissolved in a deuterated solvent such as CDCl 3} and measured at room temperature, 500 MHz, and the number of integrations was 16 times. Tetramethylsilane was used as an internal standard. ^{19 In the} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sext means sextet, m means multiplet, and br means broad.

Gas chromatograph analysis: A GC-2010 type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. As the column, a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 mL / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. A GC Solution system manufactured by Shimadzu Corporation was used as the recorder.

Gas chromatograph mass spectrometry: A QP-2010 Ultra type gas chromatograph mass spectrometer manufactured by Shimadzu Corporation was used for the measurement. As the column, a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 ml / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., the temperature of the ion source was set to 200 ° C., the ionization voltage was set to 70 eV, and the emission current was set to 150 uA. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. A GCMS solution system manufactured by Shimadzu Corporation was used as the recorder.

HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. The eluate used was an appropriate mixture of acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm. The sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

Ultraviolet-visible spectroscopic analysis: A PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.

Measurement sample: When measuring the phase structure and transition temperature (transparency point, melting point, polymerization start temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, and dielectric anisotropy of the nematic phase, a mixture of the compound and the mother liquid crystal was used as a sample.

When a sample in which the compound was mixed with the mother liquid crystal display was used, the extrapolation value was calculated by the following equation, and this value was described. <Extrapolation value> = (100 x <measured value of sample>-<weight% of mother liquid crystal> x <measured value of mother liquid crystal>) / <weight% of compound>.

Mother liquid crystal display (A): When the dielectric anisotropy of the compound was zero or positive, the following mother liquid crystal display (A) was used. The ratio of each component was expressed in% by weight.

The ratio of the compound to the mother liquid crystal display (A) was 15% by weight: 85% by weight. When crystals (or smectic phase) are precipitated at this ratio at 25 ° C., the ratio of the compound to the mother liquid crystal (A) is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99. The sample was measured at a rate at which crystals (or smectic phase) did not precipitate at 25 ° C. by changing in the order of% by weight. Unless otherwise specified, the ratio of the compound to the mother liquid crystal display (A) was 15% by weight: 85% by weight.

Measurement method: The physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA). A modified method was also used. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Phase structure: A sample was placed on a hot plate (FP-52 type hot stage manufactured by METTLER CORPORATION) of a melting point measuring device equipped with a polarizing microscope. The phase state and its change were observed with a polarizing microscope while heating this sample at a rate of 3 ° C./min to identify the type of phase.

(2) Transition temperature (° C.): A scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, X-DSC7000 was used for the measurement. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or the exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature. The melting point and polymerization start temperature of the compound were also measured using this device. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point".

The crystal was represented as C. When the crystals can be distinguished into two types, each is represented _{as C 1} or C _2. The smectic phase was represented as S and the nematic phase was represented as N. Smectic A phase, a smectic B phase, a smectic C phase, and if can be distinguished phases such as smectic F phase, represented respectively _{S A,} S B, _{S C,} and the _{S F.} The liquid (isotropic) was represented as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

(3) Compatibility of compounds: A sample in which a mother liquid crystal and a compound are mixed so that the ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, or 1% by weight. Was prepared. Samples were placed in glass bottles and stored in a freezer at -20 ° C or -30 ° C for a period of time. It was observed whether the nematic phase of the sample was maintained or whether crystals (or smectic phase) were precipitated. The conditions under which the nematic phase was maintained were used as a measure of compatibility. The proportion of compounds and the temperature of the freezer may be changed as needed.

(4) Upper limit temperature of nematic phase ( _TNI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which a part of the sample changed from the nematic phase to the isotropic liquid was measured. When the sample was a mixture of compound (1) and the mother liquid crystal display, it was indicated by the _{TNI symbol.} When the sample was a mixture of compound (1) and a compound selected from compound (2) to compound (15), it was indicated by the symbol NI. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(5) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, the liquid crystal phase was observed. _{For example, TC} was described as <-20 ° C. when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(6) Viscosity (bulk viscosity; η; measured at 20 ° C.; mPa · s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

(7) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application of 16 V to 19.5 V was applied to this device in 0.5 V increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. From these measurements and the paper by M. Imai et al., Equation (8) on page 40, the values of rotational viscosity were obtained. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the element whose rotational viscosity was measured.

(8) Optical anisotropy (refractive index anisotropy; measured at 25 ° C.; Δn): The measurement was performed using light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index (n‖) was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation of Δn = n ‖ −n ⊥.

(9) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN device having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε ‖) of the liquid crystal molecule in the long axis direction was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured. The value of permittivity anisotropy was calculated from the equation Δε ＝ ε‖−ε⊥.

(10) Elastic constant (K; measured at 25 ° C.; pN): An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 V to 20 V was applied to this device, and the capacitance (C) and the applied voltage (V) were measured. These measured values were fitted using the equation (2.98) and equation (2.11) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the equation (2.99). The values of K ₁₁ and K ₃₃ were obtained from. _{Next, K 22} was calculated using the values of _{K 11} and K ₃₃ obtained earlier in the equation (3.18) on page 171. The elastic constant K is represented by the average value of _{K 11} , K ₂₂ , and K _{33 thus obtained.}

(11) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(12) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to this device at 25 ° C. to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(13) Voltage retention rate (VHR-2; measured at 80 ° C.;%): The voltage retention rate was measured by the above method except that the measurement was performed at 80 ° C. instead of 25 ° C. The results obtained are indicated by the symbol VHR-2.

(14) Specific resistance (ρ; measured at 25 ° C.; Ωcm): 1.0 mL of the sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) x (capacitance of container)} / {(DC current) x (vacuum permittivity)}.

(15) Response time (τ; measured at 25 ° C.; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A square wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The rise time (τr: rise time; millisecond) was the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) was the time required for the transmittance to change from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time obtained in this way.

(16) Flicker rate (measured at 25 ° C.;%): A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for the measurement. The light source was an LED. The sample was placed in an FFS element in a normally black mode in which the distance between the two glass substrates (cell gap) was 3.5 μm and the rubbing direction was antiparallel. This element was sealed with an UV curable adhesive. A voltage was applied to this device, and the voltage at which the amount of light transmitted through the device was maximized was measured. While applying this voltage to the element, the sensor unit was brought close to the element and the displayed flicker rate was read.

Ingredients: Solmix® A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), obtained from Japan Alcohol Trading Co., Ltd. ..

[Synthesis Example 1]
Synthesis of compound (1-3-7)

First step Under a nitrogen atmosphere, commercially available compound (S-1) (10.0 g, 74.0 mmol) and chlorobenzene (70 ml) were placed in a reactor and stirred. Sulfuric acid (3.99 g, 40.7 mmol) was slowly added thereto at a temperature of 20 ° C. or lower. Next, sodium thiocyanate (6.60 g, 81.4 mmol) was added, and the mixture was stirred at 100 ° C. for 3 hours. Further, sulfuryl chloride (13.4 g, 99.1 mmol) was added at 50 ° C. or lower, and the mixture was stirred at 50 ° C. for 2 hours. The reaction mixture was poured into water, the solution was concentrated under reduced pressure, and chlorobenzene was distilled off. The residue was cooled to 10 ° C., aqueous ammonia was added, and the mixture was extracted with dichloromethane. The organic layer was washed with water and the solution was concentrated under reduced pressure. The residue was dissolved in ethanol, activated carbon was added, and the mixture was stirred. The solution was filtered and then concentrated under reduced pressure to give compound (S-2) (14.1 g, 99% yield).

Second step Under a nitrogen atmosphere, compound (S-2) (14.2 g, 74.0 mmol) and phosphoric acid (284 ml) were placed in a reactor and stirred at −5 ° C. An aqueous solution prepared by dissolving sodium nitrite (30.6 g, 444 mmol) in water (99.6 ml) was added thereto, and the mixture was stirred at −5 ° C. for 2 hours. Further, hypophosphorous acid (213 ml) was added at −5 ° C., the temperature was raised to room temperature, and the mixture was stirred for 12 hours. The reaction mixture was poured into water and neutralized with sodium carbonate. The aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (heptane / ethyl acetate = 10/1, volume ratio) to compound (S-3) (5.21 g, yield 39.7%). ) Was obtained.

Step 3 Under a nitrogen atmosphere, compound (S-3) (2.50 g, 14.1 mmol), compound (S-4) synthesized by a known method (6.58 g, 16.9 mmol), palladium acetate (42. 2 mg, 0.19 mmol), cupric acetate monohydrate (0.751 g, 3.76 mmol), potassium carbonate (3.90 g, 28.2 mmol), triphenylphosphine (1.85 g, 7.05 mmol) and toluene (1.85 g, 7.05 mmol) 38 ml) was placed in a reactor and heated to reflux for 12 hours. The reaction mixture was filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (heptane / ethyl acetate = 20/1, volume ratio) and recrystallization (2-propanol / ethyl acetate = 10: 1, volume ratio), and the compound (1-3-7) was purified. ) (3.48 g, yield 50.8%) was obtained.

^{1 1} H-NMR (ppm; CDCl ₃ ): δ8.01 (d, J = 8.40Hz, 1H), 7.75-7.69 (m, 3H), 7.38 (dd, J = 8.38Hz) , J = 1.65Hz, 1H), 7.03-6.96 (m, 2H), 2.76 (t, J = 7.45Hz, 2H), 1.77-1.68 (m, 2H) , 0.98 (t, J = 7.45Hz, 3H).
Transition temperature: C 80.5 I.
Maximum temperature _(T NI) = 49.7 ℃; dielectric anisotropy (Δε) = 33.9; optical anisotropy (Δn) = 0.1837.

[Synthesis Example 2]
Synthesis of compound (1-7-5)

Step 1 Under a nitrogen atmosphere, compound (S-5) (7.00 g, 23.3 mmol), compound (S-6) synthesized by a known method (9.66 g, 22.2 mmol), tetrakis (triphenyl). Phosphine) palladium (0) (1.54 g, 1.33 mmol), potassium carbonate (9.65 g, 69.8 mmol), tetrabutylammonium tribromid (2.14 g, 6.65 mmol), 1-propanol (28 ml), And toluene (56 ml) was placed in a reactor and heated to reflux for 17 hours. The reaction mixture was filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (heptane / toluene = 4/1, volume ratio) to obtain compound (S-7) (6.75 g, yield 63.0%).

Second step Under a nitrogen atmosphere, compound (S-3) (1.50 g, 8.46 mmol), compound (S-7) (5.00 g, 10.3 mmol), palladium acetate (20.0 mg, 0.09 mmol) , Copper acetate monohydrate (0.35 g, 1.75 mmol), potassium carbonate (2.39 g, 17.3 mmol), triphenylphosphine (1.11 g, 4.23 mmol) and toluene (74 ml) into the reactor. It was put in and heated to reflux for 7 hours. The reaction mixture was filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (heptane / toluene = 1/1, volume ratio) and recrystallized (heptane / toluene = 4: 1, volume ratio), and compound (1-7-5) (3. 32 g, yield 61.6%) was obtained.

^{1 1} H-NMR (ppm; CDCl ₃ ): δ8.00 (d, J = 8.35 Hz, 1H), 7.98-7.93 (m, 2H), 7.74 (s, 1H), 7. 56 (t, J = 7.80Hz, 1H), 7.36 (dd, J = 8.30Hz, J = 1.55Hz, 1H), 7.32-7.25 (m, 2H), 7.04 -6.97 (m, 2H), 2.75 (t, J = 7.50Hz, 2H), 1.76-1.70 (m, 2H), 0.99 (t, J = 7.35Hz, 3H).
Transition _{temperature: C 104 S A 154 N 198} I.
Upper limit temperature (T _NI ) = 134 ° C.; Dielectric constant anisotropy (Δε) = 38.8; Optical anisotropy (Δn) = 0.2570.

[Synthesis Example 3]
Synthesis of compound (1-7-25)

First step Compound (S-8) (28.7 g, 103 mmol) synthesized in the same manner as compound (S-2) under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (PTSA) (62.6 g,). 329 mmol) and acetonitrile (453 ml) were placed in the reactor and stirred at 0 ° C. An aqueous solution prepared by dissolving sodium nitrite (14.2 g, 206 mmol) and potassium iodide (42.7 g, 257 mmol) in water (150 ml) was added thereto, and the mixture was stirred at 0 ° C. for 30 minutes and raised to room temperature. After warming, the mixture was stirred for 7 hours. The reaction mixture was poured into water and neutralized with sodium bicarbonate. The aqueous layer was extracted with toluene, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (toluene) to give compound (S-9) (20.3 g, yield 59.6%).

Second step Under a nitrogen atmosphere, commercially available compound (S-5) (25.0 g, 83.1 mmol), commercially available compound (S-10) (8.98 g, 91.4 mmol), dichlorobis (triphenylphosphine) palladium (II). ) (0.583 g, 0.831 mmol), copper (I) iodide (0.158 g, 0.831 mmol), and triethylamine (175 ml) were placed in the reactor and stirred at room temperature for 2 hours. The reaction mixture was filtered and then concentrated under reduced pressure. Toluene was added to the residue, the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (heptane) to give compound (S-11) (22.5 g, yield 99.9%).

Step 3 Under a nitrogen atmosphere, compound (S-11) (22.5 g, 83.1 mmol), dichloromethane (113 ml), and methanol (113 ml) were placed in a reactor and stirred at 10 ° C. Potassium carbonate (13.8 g, 99.7 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water and neutralized with 1N-HCl aqueous solution. The aqueous layer was extracted with ethyl acetate, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (heptane) to give compound (S-12) (15.2 g, yield 91.7%).

Step 4 Under a nitrogen atmosphere, compound (S-9) (4.00 g, 12.1 mmol), compound (S-12) (4.81 g, 24.2 mmol), dichlorobis (triphenylphosphine) palladium (II) ( 0.170 g, 0.241 mmol), copper (I) iodide (0.0459 g, 0.241 mmol), dichloromethane (26 ml), and triethylamine (13 ml) were placed in a reactor and heated to reflux for 1 hour. The reaction mixture was filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (heptane / toluene = 2/1, volume ratio) and recrystallization (Solmix A-11), and the compound (S-13) (3.01 g, yield 61.9) was purified. %) Was obtained.

Step 5 Under a nitrogen atmosphere, compound (S-13) (0.439 g, 1.09 mmol), compound (S-6) synthesized by a known method (0.500 g, 1.15 mmol), Pd-132 ( 4.64 mg, 6.55 μmol), potassium carbonate (0.241 g, 1.75 mmol), tetrabutylammonium tribromide (0.106 g, 0.328 mmol), Solmix A-11 (0.44 ml), water (0). .88 ml) and toluene (2.6 ml) were placed in the reactor and heated to reflux for 1 hour. After filtering the reaction mixture, the reaction mixture was poured into water, the aqueous layer was extracted with toluene, the combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (heptane / toluene = 1/1, volume ratio) and recrystallization (heptane) to compound (1-7-25) (0. 400 g, yield 58.0%) was obtained.

^{1 1} H-NMR (ppm; CDCl ₃ ): δ8.00 (d, J = 8.40Hz, 1H), 7.69 (s, 1H), 7.54 (dd, J = 8.15Hz, J = 1) .35Hz, 1H), 7.51-7.44 (m, 2H), 7.38 (dd, J = 8.35Hz, J = 1.65Hz, 1H), 7.31-7.22 (m, 2H), 7.04-6.97 (m, 2H), 2.77 (t, J = 7.60Hz, 2H), 1.74-1.66 (m, 2H), 1.41-1. 28 (m, 4H), 0.91 (t, J = 6.85Hz, 3H).

[Comparative Example 1]
Comparison of physical characteristics The following compound (C-1) was selected as the comparative compound. This is because the rings of this compound are all 1,4-phenylene or 1,4-phenylene in which at least one hydrogen is replaced with fluorine, which is different from the compound of the present invention. This compound was synthesized according to the method described in WO 1996/011897.

^{1 1} H-NMR (ppm; CDCl ₃ ): δ7.54 (d, J = 8.10Hz, 2H), 7.52-7.46 (m, 2H), 7.42 (d, J = 12.2Hz) , 2H), 7.34-7.25 (m, 3H), 7.04-6.95 (m, 2H), 2.65 (t, J = 7.45Hz, 2H), 1.77-1 .64 (m, 2H), 0.98 (t, J = 7.35Hz, 3H).
Transition _{temperature: C 79.4 S A 82.3 N 128} I.
Maximum temperature _(T NI) = 96.4 ℃; dielectric anisotropy (Δε) = 34.0; optical anisotropy (Δn) = 0.210.

Table 2

Table 2 summarizes the physical characteristics of the compound (1-7-5) obtained in Synthesis Example 1 and the comparative compound (C-1). From Table 1, the compound (1-7-5) is _{good in that the upper limit temperature (TNI} ) is high, the dielectric anisotropy (Δε) is high, and the optical anisotropy (Δn) is high. Do you get it.

2. Synthesis of compound (1) Compound (1) is synthesized according to "2. Synthesis of compound (1)" and a synthesis example described above. Examples of such compounds include compounds (1-1-1) to (1-13-64) shown below.

2. Examples of Composition The present invention will be described in more detail by way of examples. The present invention is not limited by the examples, as the examples are typical. For example, the present invention includes, in addition to the composition of Examples, a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of Examples. The compounds in the use cases are represented by symbols based on the definitions in Table 3 below. In Table 3, the molecular configuration for 1,4-cyclohexylene is trans. In use cases, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (-) means a liquid crystal compound different from the compounds (1) to (15). The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the physical characteristics of the composition are summarized. The physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Usage example 1]
3-btaB (F, F) XB (F, F) -F (1-3-7) 5%

1-BB-3 (2-8) 6%
1-BB-5 (2-8) 7%
2-BTB-1 (2-10) 3%
3-HHB-1 (3-1) 7%
3-HHB-3 (3-1) 13%
3-HHB-O1 (3-1) 4%
3-HHB-F (6-1) 5%
2-HHB (F) -F (6-2) 6%
3-HHB (F) -F (6-2) 6%
5-HHB (F) -F (6-2) 6%
3-HHB (F, F) -F (6-3) 6%
3-HHEB-F (6-10) 5%
5-HHEB-F (6-10) 4%
2-HB-C (8-1) 5%
3-HB-C (8-1) 12%
NI = 95.1 ° C.; η = 20.1 mPa · s; Δn = 0.112; Δε = 6.4.

[Usage example 2]
3-btaB (F) B (F, F) XB (F, F) -F
(1-7-5) 3%

3-HH-4 (2-1) 10%
5-HB-O2 (2-5) 5%
7-HB-1 (2-5) 4%
5-HBB (F) B-2 (4-5) 4%
5-HBB (F) B-3 (4-5) 5%
3-HB-CL (5-2) 12%
3-HHB (F, F) -F (6-3) 4%
3-HBB (F, F) -F (6-24) 28%
5-HBB (F, F) -F (6-24) 25%
NI = 70.9 ° C; η = 22.5 mPa · s; Δn = 0.117; Δε = 6.8.

[Usage example 3]
5-btaTB (F) B (F, F) XB (F, F) -F
(1-7-25) 7%

1V2-HH-1 (2-1) 3%
1V2-HH-3 (2-1) 4%
7-HB (F, F) -F (5-4) 3%
2-HHB (F) -F (6-2) 8%
3-HHB (F) -F (6-2) 7%
5-HHB (F) -F (6-2) 9%
2-HBB-F (6-22) 4%
3-HBB-F (6-22) 3%
5-HBB-F (6-22) 4%
2-HBB (F) -F (6-23) 9%
3-HBB (F) -F (6-23) 9%
5-HBB (F) -F (6-23) 15%
3-HBB (F, F) -F (6-24) 5%
5-HBB (F, F) -F (6-24) 10%

[Usage example 4]
3-btaB (F, F) XB (F, F) -F (1-3-7) 6%
3-btaTB (F, F) XB (F, F) -F (1-3-23) 4%

2-HH-3 (2-1) 4%
3-HH-4 (2-1) 9%
1O1-HBBH-5 (4-1) 3%
5-HB-CL (5-2) 13%
3-HHB-F (6-1) 3%
3-HHB-CL (6-1) 3%
4-HHB-CL (6-1) 4%
3-HHB (F) -F (6-2) 8%
4-HHB (F) -F (6-2) 9%
5-HHB (F) -F (6-2) 8%
7-HHB (F) -F (6-2) 8%
5-HBB (F) -F (6-23) 4%
3-HHBB (F, F) -F (7-6) 2%
4-HHBB (F, F) -F (7-6) 3%
5-HHBB (F, F) -F (7-6) 3%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%

[Usage example 5]
5-btaB (F, F) XB (F) B (F, F) -F
(1-5-14) 6%

V-HBB-2 (3-4) 11%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 5%
3-HHB (F, F) -F (6-3) 8%
3-H2HB (F, F) -F (6-15) 7%
4-H2HB (F, F) -F (6-15) 6%
5-H2HB (F, F) -F (6-15) 7%
3-HBB (F, F) -F (6-24) 10%
5-HBB (F, F) -F (6-24) 18%
3-H2BB (F, F) -F (6-27) 8%
5-HHBB (F, F) -F (7-6) 4%
3-HH2BB (F, F) -F (7-15) 3%
5-HHEBB-F (7-17) 3%

[Usage example 6]
5-btaTB (F, F) XB (F) B (F, F) -F
(1-5-42) 4%

5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 3%
5-HB-F (5-2) 8%
6-HB-F (5-2) 8%
7-HB-F (5-2) 7%
2-HHB-OCF3 (6-1) 6%
3-HHB-OCF3 (6-1) 6%
4-HHB-OCF3 (6-1) 8%
5-HHB-OCF3 (6-1) 5%
3-HHB (F, F) -OCF2H (6-3) 5%
3-HHB (F, F) -OCF3 (6-3) 5%
3-HH2B-OCF3 (6-4) 4%
5-HH2B-OCF3 (6-4) 5%
3-HH2B (F) -F (6-5) 3%
3-HBB (F) -F (6-23) 10%
5-HBB (F) -F (6-23) 10%

[Usage example 7]
V2-BbtaXB (F, F) -F (1-3-43) 5%

2-HH-5 (2-1) 4%
3-HH-4 (2-1) 4%
5-B (F) BB-2 (3-8) 5%
5-HB-CL (5-2) 8%
3-HHB (F, F) -F (6-3) 8%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 5%
5-HHEB (F, F) -F (6-12) 3%
3-HBB (F, F) -F (6-24) 16%
5-HBB (F, F) -F (6-24) 18%
2-HBEB (F, F) -F (6-39) 3%
3-HBEB (F, F) -F (6-39) 4%
5-HBEB (F, F) -F (6-39) 3%
3-HHBB (F, F) -F (7-6) 4%

[Usage example 8]
4O-btaTB (F, F) XB (F, F) -F
(1-3-22) 8%

V2-HHB-1 (3-1) 5%
3-HB-CL (5-2) 5%
5-HB-CL (5-2) 4%
3-HHB-OCF3 (6-1) 5%
5-HHB (F) -F (6-2) 5%
V-HHB (F) -F (6-2) 4%
3-H2HB-OCF3 (6-13) 4%
5-H2HB (F, F) -F (6-15) 5%
5-H4HB-OCF3 (6-19) 13%
5-H4HB (F, F) -F (6-21) 7%
3-H4HB (F, F) -CF3 (6-21) 8%
5-H4HB (F, F) -CF3 (6-21) 8%
2-H2BB (F) -F (6-26) 5%
3-H2BB (F) -F (6-26) 8%
3-HBEB (F, F) -F (6-39) 6%

[Usage example 9]
5-btaTB (F) B (F, F) XB (F, F) -F
(1-7-25) 6%
5-btaB (F) B (F, F) XB (F, F) -CF3
(1-7-19) 5%

3-HH-4 (2-1) 9%
3-HH-5 (2-1) 4%
3-HB-O2 (2-5) 12%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 5%
5-HB-CL (5-2) 15%
7-HB (F, F) -F (5-4) 3%
2-HHB (F) -F (6-2) 5%
3-HHB (F) -F (6-2) 7%
5-HHB (F) -F (6-2) 5%
3-HHB (F, F) -F (6-3) 6%
3-H2HB (F, F) -F (6-15) 6%
4-H2HB (F, F) -F (6-15) 5%

[Usage example 10]
3-btaB (F, F) XB (F, F) -F (1-3-7) 5%
5-btaB (F, F) XB (F) B (F, F) -F
(1-5-14) 4%
5-btaTB (F, F) XB (F) B (F, F) -F
(1-5-42) 5%

3-HH-4 (2-1) 8%
3-HH-5 (2-1) 8%
3-HHB-1 (3-1) 11%
5-HB-CL (5-2) 3%
7-HB (F) -F (5-3) 6%
2-HHB (F, F) -F (6-3) 4%
3-HHB (F, F) -F (6-3) 4%
3-HHEB-F (6-10) 8%
5-HHEB-F (6-10) 7%
3-HHEB (F, F) -F (6-12) 8%
4-HHEB (F, F) -F (6-12) 4%
3-GHB (F, F) -F (6-109) 4%
4-GHB (F, F) -F (6-109) 5%
5-GHB (F, F) -F (6-109) 6%

[Usage example 11]
3-btaB (F) B (F, F) XB (F, F) -F
(1-7-5) 6%

3-HH-VFF (2-1) 5%
5-HH-VFF (2-1) 22%
2-BTB-1 (2-10) 9%
3-HHB-1 (3-1) 5%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 10%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%
3-HB-C (8-1) 16%
1V2-BEB (F, F) -C (8-15) 6%
NI = 86.7 ° C; η = 18.2 mPa · s; Δn = 0.139; Δε = 8.5.

[Usage example 12]
5-btaTB (F) B (F, F) XB (F, F) -F
(1-7-25) 4%

3-HH-V (2-1) 33%
3-HH-V1 (2-1) 4%
5-HH-V (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
2-BB (F) B-3 (3-6) 5%
3-HHEH-5 (3-13) 3%
1V2-BB-F (5-1) 4%
3-BB (F, F) XB (F, F) -F (6-97) 8%
3-BB (2F, 3F) XB (F, F) -F (6-114) 3%
3-HHBB (F, F) -F (7-6) 3%
3-HBBXB (F, F) -F (7-32) 4%
5-HB (F) B (F, F) XB (F, F) -F
(7-41) 5%
3-BB (F) B (F, F) XB (F, F) -F
(7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F
(7-47) 4%
5-BB (F) B (F, F) XB (F, F) -F
(7-47) 3%

[Usage example 13]
3-btaTB (F, F) XB (F, F) -F
(1-3-23) 3%

3-HH-V (2-1) 29%
3-HH-V1 (2-1) 7%
V-HH-V1 (2-1) 6%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
1-BB (F) B-2V (3-6) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 5%
3-HHXB (F, F) -CF3 (6-100) 3%
3-GB (F, F) XB (F, F) -F (6-113) 4%
3-GB (F) B (F, F) -F (6-116) 4%
3-HHBB (F, F) -F (7-6) 3%
3-BB (F) B (F, F) XB (F, F) -F
(7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F
(7-47) 6%
5-BB (F) B (F, F) XB (F, F) -F
(7-47) 4%
3-GB (F) B (F, F) XB (F, F) -F
(7-57) 4%

[Usage example 14]
3-btaTB (F, F) XB (F, F) -F
(1-3-23) 4%
5-btaB (F, F) XB (F) B (F, F) -F
(1-5-14) 3%

3-HH-V (2-1) 24%
3-HH-V1 (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
3-HBB-2 (3-4) 5%
V2-BB (F) B-1 (3-6) 5%
3-HHEH-3 (3-13) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 4%
3-GB (F, F) XB (F, F) -F (6-113) 3%
3-HHBB (F, F) -F (7-6) 3%
3-HBB (F, F) XB (F, F) -F (7-38) 3%
3-BB (F) B (F, F) XB (F) -F (7-46) 4%
4-BB (F) B (F, F) XB (F, F) -F
(7-47) 3%
5-BB (F) B (F, F) XB (F, F) -F
(7-47) 5%
3-GB (F) B (F, F) XB (F, F) -F
(7-57) 3%
4-GB (F) B (F, F) XB (F, F) -F
(7-57) 4%
5-GB (F) B (F, F) XB (F, F) -F
(7-57) 3%

[Usage example 15]
5-btaTB (F, F) XB (F) B (F, F) -F
(1-5-42) 5%

3-HH-V (2-1) 30%
3-HH-V1 (2-1) 4%
3-HHB-1 (3-1) 5%
V-HHB-1 (3-1) 4%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-5 (3-13) 3%
3-HHEBH-3 (4-6) 4%
1V2-BB-F (5-1) 4%
3-BB (F) B (F, F) -F (6-69) 3%
3-BB (F, F) XB (F, F) -F (6-97) 5%
3-HHBB (F, F) -F (7-6) 3%
5-HB (F) B (F, F) XB (F, F) -F
(7-41) 4%
3-BB (F, F) XB (F) B (F, F) -F
(7-56) 4%
4-BB (F) B (F, F) XB (F, F) -F
(7-47) 4%
5-BB (F) B (F, F) XB (F, F) -F
(7-47) 3%
2-dhBB (F, F) XB (F, F) -F
(7-50) 2%
3-dhBB (F, F) XB (F, F) -F
(7-50) 3%
3-GBB (F) B (F, F) -F (7-55) 3%
4-GBB (F) B (F, F) -F (7-55) 3%

[Usage example 16]
V2-BbtaXB (F, F) -F (1-3-43) 3%

3-HH-V (2-1) 32%
3-HH-V1 (2-1) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (5-1) 4%
3-BB (F) B (F, F) -CF3 (6-69) 3%
3-BB (F, F) XB (F, F) -F (6-97) 5%
3-HHXB (F, F) -F (6-100) 5%
3-GB (F, F) XB (F, F) -F (6-113) 3%
3-GB (F) B (F) -F (6-115) 3%
3-HHBB (F, F) -F (7-6) 3%
5-HB (F) B (F, F) XB (F, F) -F
(7-41) 4%
3-GB (F) B (F, F) XB (F, F) -F
(7-57) 3%
3-GBB (F, F) XB (F, F) -F (7-58) 3%
4-GBB (F, F) XB (F, F) -F (7-58) 4%
5-GBB (F, F) XB (F, F) -F (7-58) 3%
3-GB (F) B (F) B (F) -F (7-59) 3%

[Usage example 17]
4O-btaTB (F, F) XB (F, F) -F
(1-3-22) 4%

3-HH-4 (2-1) 6%
3-HB-O1 (2-5) 13%
3-HHB-1 (3-1) 5%
3-HB (2F, 3F) -O2 (11-1) 12%
5-HB (2F, 3F) -O2 (11-1) 11%
2-HHB (2F, 3F) -1 (12-1) 12%
3-HHB (2F, 3F) -1 (12-1) 12%
3-HHB (2F, 3F) -O2 (12-1) 12%
5-HHB (2F, 3F) -O2 (12-1) 13%

[Usage example 18]
5-btaB (F) B (F, F) XB (F, F) -CF3 (1-7-19) 3%

2-HH-5 (2-1) 3%
3-HH-4 (2-1) 12%
3-HH-5 (2-1) 4%
3-HB-O2 (2-5) 10%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 4%
3-HHB-O1 (3-1) 3%
3-H2B (2F, 3F) -O2 (11-4) 14%
5-H2B (2F, 3F) -O2 (11-4) 15%
2-HBB (2F, 3F) -O2 (12-7) 4%
3-HBB (2F, 3F) -O2 (12-7) 10%
5-HBB (2F, 3F) -O2 (12-7) 9%
3-HHB (2F, 3Cl) -O2 (12-12) 6%

[Usage example 19]
3-btaB (F, F) XB (F, F) -F (1-3-7) 6%

2-HH-3 (2-1) 18%
2-HH-5 (2-1) 4%
3-HH-4 (2-1) 8%
3-HB-O2 (2-5) 3%
1-BB-3 (2-8) 8%
3-HHB-1 (3-1) 5%
3-HHB-O1 (3-1) 3%
5-B (F) BB-2 (3-8) 3%
3-BB (2F, 3F) -O2 (11-3) 9%
5-BB (2F, 3F) -O2 (11-3) 5%
2-HH1OB (2F, 3F) -O2 (12-5) 10%
3-HH1OB (2F, 3F) -O2 (12-5) 18%

[Usage example 20]
3-btaB (F) B (F, F) XB (F, F) -F
(1-7-5) 4%

2-HH-3 (2-1) 13%
5-HB-O2 (2-5) 5%
7-HB-1 (2-5) 8%
5-HBB (F) B-2 (4-5) 10%
5-HBB (F) B-3 (4-5) 9%
3-HB (2F, 3F) -O2 (11-1) 17%
5-HB (2F, 3F) -O2 (11-1) 16%
3-HHB (2F, 3Cl) -O2 (12-12) 4%
4-HHB (2F, 3Cl) -O2 (12-12) 4%
5-HHB (2F, 3Cl) -O2 (12-12) 5%
3-HH1OCro (7F, 8F) -5 (16-6) 5%

[Usage example 21]
5-btaTB (F) B (F, F) XB (F, F) -F
(1-7-25) 3%

3-HH-V (2-1) 25%
1-BB-3 (2-8) 9%
3-HHB-1 (3-1) 8%
5-B (F) BB-2 (3-8) 7%
3-BB (2F, 3F) -O2 (11-3) 14%
2-HH1OB (2F, 3F) -O2 (12-5) 20%
3-HH1OB (2F, 3F) -O2 (12-5) 14%

[Usage example 22]
3-btaTB (F, F) XB (F, F) -F (1-3-23) 4%

2-HH-3 (2-1) 6%
3-HH-V1 (2-1) 9%
4-HH-V (2-1) 3%
1V2-HH-1 (2-1) 7%
1V2-HH-3 (2-1) 6%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 2%
3-BB (2F, 3F) -O2 (11-3) 8%
5-BB (2F, 3F) -O2 (11-3) 4%
3-H1OB (2F, 3F) -O2 (11-5) 7%
3-HDhB (2F, 3F) -O2 (12-3) 7%
2-HH1OB (2F, 3F) -O2 (12-5) 8%
3-HH1OB (2F, 3F) -O2 (12-5) 15%
2-BB (2F, 3F) B-3 (13-1) 11%

[Usage example 23]
5-btaB (F, F) XB (F) B (F, F) -F (1-5-14) 6%

3-HH-4 (2-1) 5%
3-HH-VFF (2-1) 4%
3-HB-O1 (2-5) 13%
1-BB-5 (2-8) 3%
3-HHB-1 (3-1) 6%
V-HB (2F, 3F) -O2 (11-1) 4%
5-HB (2F, 3F) -O2 (11-1) 10%
2-HHB (2F, 3F) -1 (12-1) 12%
3-HHB (2F, 3F) -1 (12-1) 11%
3-HHB (2F, 3F) -O2 (12-1) 13%
5-HHB (2F, 3F) -O2 (12-1) 13%

[Usage example 24]
5-btaTB (F, F) XB (F) B (F, F) -F (1-5-42) 5%

2-HH-3 (2-1) 15%
7-HB-1 (2-5) 8%
5-HB-O2 (2-5) 7%
5-HBB (F) B-2 (4-5) 9%
5-HBB (F) B-3 (4-5) 10%
3-HB (2F, 3F) -O2 (11-1) 11%
5-HB (2F, 3F) -O2 (11-1) 11%
2-H1OB (2F, 3F) -O2 (11-5) 3%
3-H1OB (2F, 3F) -O2 (11-5) 3%
2OB (2F, 3F) B (F) -O2 (11-9) 3%
4O-B (2F, 3F) B (F) -O2 (11-9) 4%
V-HHB (2F, 3F) -O2 (12-1) 3%
V2-HHB (2F, 3F) -O2 (12-1) 3%
5-HHB (2F, 3Cl) -O2 (12-12) 2%
3-HH1OCro (7F, 8F) -5 (16-6) 3%

[Usage example 25]
V2-BbtaXB (F, F) -F (1-3-43) 3%

2-HH-5 (2-1) 3%
3-HH-4 (2-1) 14%
3-HH-5 (2-1) 3%
3-HB-O2 (2-5) 11%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 4%
3-HHB-O1 (3-1) 3%
3-DhB (2F, 3F) -O2 (11-2) 4%
2-BB (2F, 3F) -O2 (11-3) 8%
5-H2B (2F, 3F) -O2 (11-4) 10%
3-HH2B (2F, 3F) -O2 (12-4) 3%
V-HBB (2F, 3F) -O2 (12-7) 4%
3-HBB (2F, 3F) -O2 (12-7) 9%
5-HBB (2F, 3F) -O2 (12-7) 9%
3-HHB (2F, 3Cl) -O2 (12-12) 5%
2OB (2F, 3F) B (F) H-3 (12-19) 4%

[Usage example 26]
4O-btaTB (F, F) XB (F, F) -F
(1-3-22) 4%

2-HH-3 (2-1) 6%
3-HH-V1 (2-1) 9%
1V2-HH-1 (2-1) 7%
1V2-HH-3 (2-1) 7%
V-HHB-1 (3-1) 3%
V2-HHB-1 (3-1) 3%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 2%
V2-BB (2F, 3F) -O2 (11-3) 3%
5-BB (2F, 3F) -O2 (11-3) 4%
3-H1OB (2F, 3F) -O2 (11-5) 6%
3-HDhB (2F, 3F) -O2 (12-3) 7%
3-HH1OB (2F, 3F) -O2 (12-5) 18%
3-dhBB (2F, 3F) -O2 (12-9) 3%
3-HchB (2F, 3F) -O2 (12-18) 4%
2-BB (2F, 3F) B-3 (13-1) 11%

[Usage example 27]
5-btaB (F) B (F, F) XB (F, F) -CF3
(1-7-19) 3%

2-HH-3 (2-1) 20%
3-HH-4 (2-1) 8%
3-HB-O2 (2-5) 2%
1-BB-3 (2-8) 5%
3-HHB-1 (3-1) 3%
3-HHB-O1 (3-1) 3%
V-HBB-2 (3-4) 4%
5-B (F) BB-2 (3-8) 3%
3-BB (2F, 3F) -O2 (11-3) 9%
5-BB (2F, 3F) -O2 (11-3) 6%
2-HH1OB (2F, 3F) -O2 (12-5) 13%
3-HH1OB (2F, 3F) -O2 (12-5) 14%
3-HB (2F, 3F) B-2 (13-2) 3%
V-HH2BB (2F, 3F) -O2 (14-3) 4%

[Usage example 28]
3-btaB (F, F) XB (F, F) -F (1-3-7) 3%
3-btaB (F) B (F, F) XB (F, F) -F
(1-7-5) 3%

3-HH-V (2-1) 24%
1-BB-3 (2-8) 7%
3-HHB-1 (3-1) 7%
5-B (F) BB-2 (3-8) 5%
3-BB (2F, 3F) -O2 (11-3) 10%
2-HH1OB (2F, 3F) -O2 (12-5) 18%
3-HH1OB (2F, 3F) -O2 (12-5) 14%
5-HFLF4-3 (19-1) 5%
3-H2BBB (2F, 3F) -O2 (14-1) 4%

The liquid crystal compound of the present invention has good physical characteristics. Liquid crystal compositions containing this compound can be widely used in liquid crystal display elements used in personal computers, televisions, and the like.

Claims (17)

A compound represented by the formula (1).

In equation (1)
R ¹ is hydrogen or an alkyl having 1 to 15 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−, and at least one −CH ₂ CH ₂ − May be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Rings A ¹ , A ² , and A ³ independently have 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen replaced with fluorine or chlorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, naphthalene -2,6-diyl, naphthalene in which at least one hydrogen is replaced with fluorine or chlorine-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-Diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, ^{ring of formula (A 0} ), or at least one ^{A ring represented by the formula (A 0} ) in which hydrogen is replaced with fluorine or chlorine, and in rings A ¹ , A ² and A ³ , at least one ring is a ring represented by the ^{formula (A 0).} Or a ring represented ^{by the formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine;

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH _{2- , -CH 2 S -, - SCH} 2 -, - CF 2 O -, - OCF 2 -, or a -CF = CF-;
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0, 1, 2, or 3. The compound according to claim 1, which is represented by the formulas (1A) to (1E).

In formulas (1A) to (1E)
R ¹ is hydrogen, an alkyl having 1 to 15 carbon atoms, an alkoxy having 1 to 14 carbon atoms, an alkenyl having 2 to 15 carbon atoms, an alkenyloxy having 2 to 14 carbon atoms, an alkylthio having 1 to 14 carbon atoms, or a carbon number of carbon atoms. 2 to 14 alkenylthios;
Rings A ¹ , A ² , and A ³ independently have 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen replaced with fluorine or chlorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, naphthalene -2,6-diyl, naphthalene in which at least one hydrogen is replaced with fluorine or chlorine-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-Diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,2-cyclopropylene, 1,3-cyclopentylene, ^{ring of formula (A 0} ), or at least one ^{A ring represented by the formula (A 0} ) in which hydrogen is replaced with fluorine or chlorine, and in rings A ¹ , A ² and A ³ , at least one ring is a ring represented by the ^{formula (A 0).} Or a ring represented ^{by the formula (A 0} ) in which at least one hydrogen is replaced with fluorine or chlorine;

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH _{2- , -CH 2 S -, - SCH} 2 -, - CF 2 O -, - OCF 2 -, or a -CF = CF-;
L ¹ , L ² , and L ³ are independently hydrogen, chlorine, fluorine, OFF ₃ or CF ₃ , but at least one is fluorine, OCF ₃ or CF ₃ . The compound according to claim 1, which is represented by the formulas (1A-1) to (1E-4).

In formulas (1A-1) to (1E-4),
R ¹ is an alkyl having 1 to 15 carbons, an alkoxy having 1 to 14 carbons, an alkenyl having 2 to 15 carbons, or an alkenyloxy having 2 to 14 carbons;
Rings A ¹ , A ² , and A ³ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and 1,4- in which at least one hydrogen is replaced by fluorine. Phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine, deca Hydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C ≡ C-, -CH ₂ O-, -OCH _2- , -CH ₂ S-,- SCH _2- , -CF ₂ O-, or -OCF _2- ;
L ¹ , L ² , and L ³ are independently hydrogen, fluorine, OCF ₃ or CF ₃ , but at least one is fluorine, OFF ₃ or CF ₃ . In the formulas (1A-1) to (1E-4) according to claim 3, R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or carbon. between a few 2 9 alkenyloxy, ring ^{a 1} is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, 1,3-difluoronaphthalene-2,6-diyl, pyridine-2,5-diyl, or a pyrimidine-2,5-diyl, ring ^{a 2} and ^{a 3} are independently 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, Naphthalene-2,6-diyl, 1,3-difluoronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, with Z ¹ and Z ² independent. Single bond, -C ≡ C-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- , where L ¹ is fluorine, OCF ₃ or CF ₃ , and L ² and L ³ are. The compound according to claim 3, which is independently hydrogen or fluorine. The compound according to claim 1, which is represented by the formulas (1A-1a) to (1E-4a).

In formulas (1A-1a) to (1E-4a),
R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms;
L ¹ is hydrogen, fluorine, OCF ₃ or CF ₃ , L ² and L ³ are independently hydrogen or fluorine, and in L ¹ , L ² , and L ³ , at least one is fluorine, OFF. ₃ or CF ₃ ;
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen or fluorine. ^{The compound according to claim 5, wherein L 1} , L ² , and L ³ are fluorine in the formulas (1A-1a) to (1E-4a) according to claim 5. The compound according to claim 1, which is represented by the formulas (1A-1b) to (1C-3c).

In formulas (1A-1b) to (1C-3c),
R ¹ is an alkyl having 1 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms;
L ¹ is hydrogen, fluorine, OCF ₃ or CF ₃ , L ² and L ³ are independently hydrogen or fluorine, and in L ¹ , L ² , and L ³ , at least one is fluorine, OFF. ₃ or CF ₃ ;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or fluorine. ^{The compound according to claim 7, wherein L 1} , L ² , and L ³ are fluorine in the formulas (1A-1b) to (1C-3c) according to claim 7. A liquid crystal composition containing at least one compound according to any one of claims 1 to 8. The liquid crystal composition according to claim 9, further comprising at least one compound selected from the group of compounds represented by the formulas (2) to (4).

In equations (2) to (4)
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, in these groups, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are independently single-bonded, -COO-, -CH ₂ CH _2- , -CH = CH-, or -C≡C-. The liquid crystal composition according to claim 9 or 10, further comprising at least one compound selected from the group of compounds represented by the formulas (5) to (7).

In equations (5) to (7)
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced by fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, and 1,4-phenylene, tetrahydropyran-2 in which at least one hydrogen is replaced by fluorine. , 5-Diyl, 1,3-dioxane-2,5-Diyl, or pyrimidine-2,5-Diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH _{2 CH 2 -, - CH = CH} -, - C≡C-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine. The liquid crystal composition according to any one of claims 9 to 11, further containing at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced by fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2. , 5-Dioxane, or pyrimidine-2,5-Dioxane;
Z ¹⁷ is a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , or -C ≡ C-. Is;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4. The liquid crystal composition according to any one of claims 9 to 12, further containing at least one compound selected from the group of compounds represented by the formulas (11) to (19).

In equations (11) to (19),
R ¹⁵ , R ¹⁶ and R ¹⁷ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced, in these groups at least one hydrogen may be replaced with fluorine, and R ¹⁷ may be hydrogen or fluorine;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen with fluorine. 1,4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{E 5} and ring ^{E 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ²¹ are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ OCH ₂ CH _2- , or -OCF ₂ CH ₂ CH _2- ;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3. At least one additive selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. The liquid crystal composition according to any one of claims 9 to 13, further contained. A liquid crystal display device containing the liquid crystal composition according to any one of claims 9 to 14. The liquid crystal display element according to claim 15, wherein the liquid crystal composition according to any one of claims 9 to 14 is encapsulated in a capsule. The liquid crystal display element according to claim 15, wherein the liquid crystal composition according to any one of claims 9 to 14 is used for a lens used for switching between 2D and 3D.