Compound, liquid crystal composition and liquid crystal display element

Abstract

This compound is represented by formula (1). R1 and R2 are each C1-C15 alkyl or the like; Ra is hydrogen or the like; a ring A1 and a ring A2 are each 1,4-cyclohexylene, 1,4-phenylene, or the like; a ring N1 and a ring N2 are each 1,2-cyclopropylene, 1,3-cyclopentylene, or the like; Z1, Z2, Z3, and Z4 are each a single bond or the like; L1, L2, L3, L4, L5, and L6 are each fluorine or the like; and l and o are each 0 or 1 and m and n are each 0, 1, or 2.

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal compound having a carbazole ring, a liquid crystal composition, and a liquid crystal display device. More specifically, the present invention relates to a liquid crystal compound having a carbazole ring and negative dielectric anisotropy, a liquid crystal composition containing the compound, and a liquid crystal display device including the composition. [Background technology]

[0002] LCDs are classified based on the operating mode of the liquid crystal molecules, including phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). LCDs are classified based on their driving method, into passive matrix (PM) and active matrix (AM). PMs are further divided into static and multiplex, while AMs are further divided into thin film transistor (TFT) and metal insulator metal (MIM).

[0003] A liquid crystal composition is sealed in this device. The physical properties of this composition are related to the device's characteristics. Examples of the composition's physical properties include stability to heat and light, the temperature range of the nematic phase, viscosity, optical anisotropy, dielectric anisotropy, resistivity, and elastic constant. The composition is prepared by mixing many liquid crystal compounds. Required physical properties of the compound include high stability to environments such as water, air, heat, and light, a wide temperature range of the liquid crystal phase, low viscosity, appropriate optical anisotropy, large dielectric anisotropy, appropriate elastic constant, and good compatibility with other liquid crystal compounds. Compounds with a high maximum temperature of the nematic phase are preferred. Compounds with a low minimum temperature of the liquid crystal phase, such as the nematic phase or smectic phase, are preferred. Compounds with low viscosity contribute to the device's short response time. The appropriate value of the optical anisotropy depends on the type of device operation mode. To drive the device at a low voltage, compounds with large positive or negative dielectric anisotropy are preferred. To prepare a composition, compounds with good compatibility with other liquid crystal compounds are preferred. Since the device may be used at temperatures below freezing, compounds having good compatibility at low temperatures are preferred.

[0004] Numerous liquid crystal compounds have been synthesized to date. The development of new liquid crystal compounds continues to this day. This is because new compounds are expected to have excellent physical properties not found in conventional compounds. This is because new compounds may impart an appropriate balance to at least two physical properties in a composition. There have been few reports of compounds containing the following divalent groups. In the following divalent groups, X is hydrogen or a substituent.

[0005] [ka]

[0006] For example, in Patent Document 1, compounds numbered 53, 54, and 56 are disclosed in Table 4 on page 41, and compounds numbered 125 and 127 are disclosed in Table 8 on page 45.

[0007] [ka]

[0008] Patent Document 2 discloses Compound II-a of Example 3 on page 10 and Compound III-a of Example 7 on page 14.

[0009] [ka] [Prior art documents] [Patent documents]

[0010] [Patent Document 1] International Publication No. 2007 / 018168 [Patent Document 2] International Publication No. 2017 / 084231 Summary of the Invention [Problem to be solved by the invention]

[0011] The first object is to provide a liquid crystal compound that satisfies at least one of the following physical properties: high stability against heat and light, a high clearing point (or a high maximum temperature of the nematic phase), a low minimum temperature of the liquid crystal phase, a low viscosity, suitable optical anisotropy, a large negative dielectric anisotropy, suitable elastic constants, and good compatibility with other liquid crystal compounds. The second object is to provide a liquid crystal composition containing this compound and that satisfies at least one of the following physical properties: high stability against heat and light, a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a low viscosity, suitable optical anisotropy, a large negative dielectric anisotropy, a large resistivity, and suitable elastic constants. The third object is to provide a liquid crystal display device that contains this composition and that has a wide usable temperature range, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifespan. [Means for solving the problem]

[0012] The present invention relates to a compound represented by formula (1), a liquid crystal composition containing this compound, and a liquid crystal display device containing this liquid crystal composition.

[0013] [ka]

[0014] In formula (1), R 1 is hydrogen or alkyl having 1 to 15 carbon atoms, and this R 1 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; R 2 is hydrogen, fluorine, chlorine, -C≡N, -C≡CC≡N, or alkyl having 1 to 15 carbon atoms, and this R 2 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and the ring A 1 and ring A 2 wherein at least one -CH2- may be replaced by -O-, and at least one -(CH2)2- may be replaced by -CH=CH-; Ring N 1 and ring N 2are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, benzo[b]thiophene-2,6-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 9H-xanthene-2,6-diyl, or 9H-fluorene-2,7-diyl, and the ring N 1 and ring N 2 wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and Z 1 , Z 2 , Z 3 , and Z 4 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are independently hydrogen, fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; L5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , and L 4 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; L 1 , L 2 , L 3 , and L 4 When both are hydrogen, L 5 and L 6 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; l and o are independently 0 or 1, m and n are independently 0, 1, or 2, and the sum of l, m, n, and o is an integer from 0 to 4; When l is 0, R 1 cannot be hydrogen, and when o is 0, R 2 never becomes hydrogen. [Effects of the Invention]

[0015] The first advantage is to provide a liquid crystal compound that satisfies at least one of the following physical properties: high stability against heat and light, a high clearing point (or a high maximum temperature of the nematic phase), a low minimum temperature of the liquid crystal phase, a small viscosity, suitable optical anisotropy, a large negative dielectric anisotropy, suitable elastic constants, and good compatibility with other liquid crystal compounds. The second advantage is to provide a liquid crystal composition that contains the compound and satisfies at least one of the following physical properties: high stability against heat and light, a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, suitable optical anisotropy, a large negative dielectric anisotropy, a large resistivity, and suitable elastic constants. This advantage is to provide a liquid crystal composition that has an appropriate balance of at least two physical properties. The third advantage is that a liquid crystal display device containing this composition can be provided, which has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifespan. DETAILED DESCRIPTION OF THE INVENTION

[0016] The terms used in this specification are as follows. The terms "liquid crystal compound," "liquid crystal composition," and "liquid crystal display element" may be abbreviated as "compound," "composition," and "element," respectively. "Liquid crystal compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds that do not have a liquid crystal phase but are added to adjust the physical properties of the composition, such as the upper and lower limits of temperature, viscosity, and dielectric anisotropy. These compounds have a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene and have a rod-like molecular structure. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules. "Polymerizable compound" is a compound added to form a polymer in the composition. Liquid crystal compounds containing alkenyl are not polymerizable in this sense.

[0017] Liquid crystal compositions are prepared by mixing multiple liquid crystal compounds. Additives are added to these compositions to further adjust their physical properties. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents are added as needed. Liquid crystal compounds and additives are mixed in this manner. The proportion (content) of the liquid crystal compound, even when an additive is added, is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition without the additive. The proportion (addition amount) of the additive is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition without the additive. In other words, the proportion of the liquid crystal compound or additive is calculated based on the total weight of the liquid crystal compound. Parts per million (ppm) by weight is sometimes used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.

[0018] The "clearing point" refers to the liquid crystal phase-isotropic phase transition temperature of a liquid crystal compound. The "lower limit temperature of the liquid crystal phase" refers to the transition temperature between a solid and a liquid crystal phase (such as a smectic or nematic phase) of a liquid crystal compound. The "highest limit temperature of the nematic phase" refers to the nematic-isotropic phase transition temperature of a liquid crystal composition or a mixture of a liquid crystal compound and a base liquid crystal. This is sometimes abbreviated as "highest limit temperature." The expression "increasing the dielectric anisotropy" refers to a positive increase in the dielectric anisotropy of a composition with positive dielectric anisotropy, and a negative increase in the dielectric anisotropy of a composition with negative dielectric anisotropy. The expression "large voltage holding ratio" refers to a device that has a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and that maintains a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after prolonged use. The characteristics of compositions and devices are sometimes examined before and after aging tests (including accelerated aging tests).

[0019] A compound represented by formula (1) may be abbreviated as compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as compound (1). "Compound (1)" means one compound represented by 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 formulas (1) to (15), A surrounded by a hexagon 1 , B 1 , C 1 The symbols are ring A 1 , ring B 1 , ring C 1 Hexagons represent six-membered rings such as cyclohexane and benzene. Hexagons can also represent fused rings such as naphthalene or bridged rings such as adamantane.

[0020] In the chemical formula of the component compound, the terminal group R 11 The symbol R is used for several compounds. In these compounds, any two R 11 The two groups represented by may be the same or different. For example, R 11 is ethyl, and R 11 In some cases, R is ethyl. 11 is ethyl, and R 11 In some cases, R is propyl. 12 , R 13 , Z 11 In compound (15), when i is 2, the two rings E 1 In this compound, there are two rings E 1 The two groups represented by may be the same or different. When i is greater than 2, any two rings E 1 This rule also applies to other symbols.

[0021] The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be replaced with 'B'" means that when there is one 'A', the position of 'A' is arbitrary, and when there are two or more 'A's, the positions can be selected without restriction. This rule also applies to the expression "at least one 'A' is replaced with 'B'." The expression "at least one 'A' may be replaced with 'B', 'C', or 'D'" means that any 'A' is replaced with 'B', any 'A' is replaced with 'C', any 'A' is replaced with 'D', and further includes cases where multiple 'A's are replaced with at least two of 'B', 'C', and / or 'D'. For example, "an alkyl where at least one -CH2- may be replaced with -O- or -CH=CH-" includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, and alkenyloxyalkyl. It is not preferable that two consecutive -CH2- are replaced by -O- to form -OO-. It is also not preferable that -CH2- in the methyl portion (-CH2-H) of an alkyl group is replaced by -O- to form -OH.

[0022] "R 11 and R 12 are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in this alkyl and alkenyl, at least one -CH2- may be replaced with -O-, and in these groups, at least one hydrogen may be replaced with fluorine." In this expression, "in these groups" may be interpreted literally. In this expression, "these groups" means alkyl, alkenyl, alkoxy, alkenyloxy, etc. In other words, "these groups" represents all of the groups described before 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" represents all of the groups described before the term "in these monovalent groups."

[0023] Halogen refers to fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine. Fluorine is even more preferred. The alkyl of the liquid crystal compound is linear or branched, and does not include cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The stereochemistry of 1,4-cyclohexylene is preferably trans rather than cis to increase the maximum temperature. 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, the fluorine atom may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups formed by removing two hydrogen atoms from the ring, such as tetrahydropyran-2,5-diyl.

[0024] [ka]

[0025] The present invention includes the following items.

[0026] Item 1. A compound represented by formula (1).

[0027] [ka]

[0028] In formula (1), R 1 is hydrogen or alkyl having 1 to 15 carbon atoms, and this R 1 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; R 2is hydrogen, fluorine, chlorine, -C≡N, -C≡CC≡N, or alkyl having 1 to 15 carbon atoms, and this R 2 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and the ring A 1 and ring A 2 wherein at least one -CH2- may be replaced by -O-, and at least one -(CH2)2- may be replaced by -CH=CH-; Ring N 1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, benzo[b]thiophene-2,6-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 9H-xanthene-2,6-diyl, or 9H-fluorene-2,7-diyl, and the ring N 1 and ring N 2wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and Z 1 , Z 2 , Z 3 , and Z 4 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are independently hydrogen, fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; L 5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , and L 4 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; L 1 , L 2 , L 3 , and L 4 When both are hydrogen, L 5 and L 6 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; l and o are independently 0 or 1, m and n are independently 0, 1, or 2, and the sum of l, m, n, and o is an integer from 0 to 4; When l is 0, R 1 cannot be hydrogen, and when o is 0, R 2 never becomes hydrogen.

[0029] Item 2. The compound according to Item 1, which is represented by formula (1-1) to formula (1-13).

[0030] [ka]

[0031] In formulas (1-1) to (1-13), R 1 is hydrogen, alkyl having 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, alkoxyalkyl having 2 to 14 carbon atoms, alkenyl having 2 to 15 carbon atoms, or alkenyloxy having 2 to 14 carbon atoms; R 2 is hydrogen, fluorine, chlorine, -CF3, -OCF3, -C≡N, alkyl having 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, alkoxyalkyl having 2 to 14 carbon atoms, alkenyl having 2 to 15 carbon atoms, or alkenyloxy having 2 to 14 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and the ring A 1 and ring A 2 wherein at least one -CH2- may be replaced by -O-, and at least one -(CH2)2- may be replaced by -CH=CH-; Ring N 1 and ring N 2are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, benzo[b]thiophene-2,6-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 9H-xanthene-2,6-diyl, or 9H-fluorene-2,7-diyl, and the ring N 1 and ring N 2 wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and Z 1 , Z 2 , Z 3 , and Z 4 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 1 , L 2 , L 3 , and L4 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; In formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9), formula (1-11), and formula (1-13), R 1 does not become hydrogen, and in formulas (1-1) to (1-5), (1-8), (1-9), (1-12), and (1-13), R 2 never becomes hydrogen.

[0032] Item 3. In the formulas (1-1) to (1-13), R 1 and R 2 are independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 is independently 1,2-cyclopropylene, 1,3-cyclobutylene, or 1,3-cyclopentylene; Ring N 1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, or benzo[b]thiophene-2,6-diyl, and in this ring N 1 and ring N 2wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond, -O-, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, -(CH)-, -(CH)COO-, -(CH)OCO-, -OCO(CH)-, -COO(CH)-, -(CH)CFO-, -(CH)OCF-, -OCF(CH)-, -CFO(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 1 , L 2 , L 3 , and L 4 at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; In formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9), formula (1-11), and formula (1-13), R 1 does not become hydrogen, and in formulas (1-1) to (1-5), (1-8), (1-9), (1-12), and (1-13), R 2 Item 3. The compound according to item 2, wherein is not hydrogen.

[0033] Item 4. The compound according to Item 1, which is represented by formulas (1-14) to (1-26).

[0034] [ka]

[0035] In equations (1-14) to (1-26), R 1 is hydrogen, alkyl having 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, alkoxyalkyl having 2 to 14 carbon atoms, alkenyl having 2 to 15 carbon atoms, or alkenyloxy having 2 to 14 carbon atoms; R 2 is hydrogen, fluorine, chlorine, -CF3, -OCF3, -C≡N, alkyl having 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, alkoxyalkyl having 2 to 14 carbon atoms, alkenyl having 2 to 15 carbon atoms, or alkenyloxy having 2 to 14 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and the ring A 1 and ring A 2 wherein at least one -CH2- may be replaced by -O-, and at least one -(CH2)2- may be replaced by -CH=CH-; Ring N 1 and ring N 2are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, benzo[b]thiophene-2,6-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 9H-xanthene-2,6-diyl, or 9H-fluorene-2,7-diyl, and the ring N 1 and ring N 2 wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and Z 1 , Z 2 , Z 3 , and Z 4 wherein at least one -CH2- may be replaced by -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine; L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 5 and L 6at least one of is fluorine, chlorine, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, —OCH2F, or —C≡N; In formulas (1-14), (1-16), (1-18), (1-20), (1-22), (1-24), and (1-26), R 1 does not become hydrogen, and in formulas (1-14) to (1-18), (1-21), (1-22), (1-25), and (1-26), R 2 never becomes hydrogen.

[0036] Item 5. In the above formulas (1-14) to (1-26), R 1 and R 2 are independently hydrogen, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Ring A 1 and ring A 2 is independently 1,2-cyclopropylene, 1,3-cyclobutylene, or 1,3-cyclopentylene; Ring N 1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, or benzo[b]thiophene-2,6-diyl, and in this ring N 1 and ring N 2wherein at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF3, —CHF2, —CH2F, —OCF3, —OCHF2, or —OCH2F; Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond, -O-, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, -(CH)-, -(CH)COO-, -(CH)OCO-, -OCO(CH)-, -COO(CH)-, -(CH)CFO-, -(CH)OCF-, -OCF(CH)-, -CFO(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 5 , and L 6 At least one of the following is fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N; In formulas (1-14), (1-16), (1-18), (1-20), (1-22), (1-24), and (1-26), R 1 does not become hydrogen, and in formulas (1-14) to (1-18), (1-21), (1-22), (1-25), and (1-26), R 2 Item 5. The compound according to item 4, wherein is not hydrogen.

[0037] Item 6. The compound according to any one of Items 1 to 3, which is represented by formula (1-1-1), formula (1-3-1) to formula (1-3-6), formula (1-5-1) to formula (1-5-4), or formula (1-9-1) to formula (1-9-3).

[0038] [ka]

[0039] In formula (1-1-1), formula (1-3-1) to formula (1-3-6), formula (1-5-1) to formula (1-5-4), and formula (1-9-1) to formula (1-9-3), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Z 2 and Z 3 are independently a single bond, -O-, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -C≡C-, -(CH)-, -(CH)COO-, -(CHOCO-, -OCO(CH)-, -COO(CH)-, -(CH)CFO-, -(CHOCF-, -OCF(CH)-, -CFO(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -OCF3, -OCHF2, or -OCH2F, and L 1 , L 2 , L 3 , and L 4 at least one of is fluorine, chlorine, —CF3, —CHF2, —OCF3, —OCHF2, or —OCH2F; X 1 and X2 are independently hydrogen, fluorine, or chlorine.

[0040] Item 7. In the above formulas (1-1-1), (1-3-1) to (1-3-6), (1-5-1) to (1-5-4), and (1-9-1) to (1-9-3), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 10 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Z 2 and Z 3 are independently a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF3 or -OCF3, and L 1 , L 2 , L 3 , and L 4 At least one of is fluorine, chlorine, -CF3 or -OCF3, and L 1 , L 2 , L 3 , and L 4 at least two of are hydrogen; X 1 and X 2 Item 7. The compound according to item 6, wherein each of the groups is independently hydrogen, fluorine, or chlorine.

[0041] Item 8. The compound according to any one of items 1, 4, and 5, represented by formula (1-14-1), formula (1-16-1) to formula (1-16-6), formula (1-18-1) to formula (1-18-4), or formula (1-22-1) to formula (1-22-3).

[0042] [ka]

[0043] In equations (1-14-1), (1-16-1) to (1-16-6), (1-18-1) to (1-18-4), and (1-22-1) to (1-22-3), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Z 2 and Z 3 are independently a single bond, -O-, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -C≡C-, -(CH)-, -(CH)COO-, -(CHOCO-, -OCO(CH)-, -COO(CH)-, -(CH)CFO-, -(CHOCF-, -OCF(CH)-, -CFO(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -OCF3, -OCHF2, or -OCH2F, and L 5 and L 6at least one of is fluorine, chlorine, —CF3, —CHF2, —OCF3, —OCHF2, or —OCH2F; X 1 and X 2 are independently hydrogen, fluorine, or chlorine.

[0044] Item 9. In the above formulas (1-14-1), (1-16-1) to (1-16-6), (1-18-1) to (1-18-4), and (1-22-1) to (1-22-3), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched alkyl having 3 to 6 carbon atoms; Z 2 and Z 3 are independently a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF3, -CHF2, -OCF3, -OCHF2, or -OCH2F, and L 5 and L 6 at least one of is fluorine, chlorine, —CF3, —CHF2, —OCF3, —OCHF2, or —OCH2F; X 1 and X 2 Item 9. The compound according to item 8, wherein each of the groups is independently hydrogen, fluorine, or chlorine.

[0045] Item 10. The compound according to any one of Items 1 to 3, 6, and 7, which is represented by formula (1-1-1) or formula (1-3-1) to (1-3-6).

[0046] [ka]

[0047] In formula (1-1-1) and formula (1-3-1) to formula (1-3-6), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms; Z 2 is a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF3, or -OCF3, and L 1 , L 2 , L 3 , and L 4 At least one of is fluorine, chlorine, -CF3, or -OCF3, and L 1 , L 2 , L 3 , and L 4 at least two of are hydrogen; X 1 and X 2 are independently hydrogen, fluorine, or chlorine.

[0048] Item 11. The compound according to any one of items 1, 4, 5, 8, and 9, which is represented by formula (1-14-1) or formula (1-16-1) to formula (1-16-6).

[0049] [ka]

[0050] In equation (1-14-1) and equations (1-16-1) to (1-16-6), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms; Z 2 is a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, or -OCH-CH=CH-; L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF3, or -OCF3, and L 5 and L 6 at least one of is fluorine, chlorine, -CF3, or -OCF3; X 1 and X 2 are independently hydrogen, fluorine, or chlorine.

[0051] Item 12. The compound according to any one of Items 1 to 3, 6, 7, and 10, which is represented by formula (1-1-1), formula (1-3-1-1) to formula (1-3-1-7), formula (1-3-2-1), formula (1-3-2-2), formula (1-3-3-1), formula (1-3-3-2), formula (1-3-4-1), formula (1-3-4-2), formula (1-3-5-1), formula (1-3-5-2), or formula (1-3-6-1) to formula (1-3-6-4).

[0052] [ka]

[0053] In formula (1-1-1), formula (1-3-1-1) to formula (1-3-1-7), formula (1-3-2-1), formula (1-3-2-2), formula (1-3-3-1), formula (1-3-3-2), formula (1-3-4-1), formula (1-3-4-2), formula (1-3-5-1), formula (1-3-5-2), and formula (1-3-6-1) to formula (1-3-6-4), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms; L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, -CF3, or -OCF3, and L 1 , L 2 , L 3 , and L 4 At least two of are fluorine, -CF3, or -OCF3, and L 1 , L 2 , L 3 , and L 4 at least one of is hydrogen; X 1 and X 2are independently hydrogen or fluorine.

[0054] Item 13. The compound according to any one of items 1, 4, 5, 8, 9, and 11, which is represented by formula (1-14-1), formula (1-16-1-1) to formula (1-16-1-7), formula (1-16-2-1), formula (1-16-2-2), formula (1-16-3-1), formula (1-16-3-2), formula (1-16-4-1), formula (1-16-4-2), formula (1-16-5-1), formula (1-16-5-2), or formula (1-16-6-1) to formula (1-16-6-4).

[0055] [ka]

[0056] In formulas (1-14-1-1), (1-16-1-1) to (1-16-1-7), (1-16-2-1), (1-16-2-2), (1-16-3-1), (1-16-3-2), (1-16-4-1), (1-16-4-2), (1-16-5-1), (1-16-5-2), and (1-16-6-1) to (1-16-6-4), R 1 and R 2 are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms; L 5 and L 6 are independently hydrogen, fluorine, -CF3, or -OCF3, and L 5 and L 6 at least one of is fluorine, -CF3, or -OCF3; X 1 and X 2 are independently hydrogen or fluorine.

[0057] Item 14. The compound according to any one of items 1 to 3, 6, 7, 10, and 12, which is represented by formula (1-1-1-1) to formula (1-1-1-7).

[0058] [ka]

[0059] In equations (1-1-1-1) to (1-1-1-7), R 1 and R 2 are independently alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkoxyalkyl having 2 to 6 carbon atoms, alkenyl having 2 to 7 carbon atoms, or alkenyloxy having 2 to 7 carbon atoms. R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms.

[0060] Item 15. The compound according to any one of items 1, 4, 5, 8, 9, 11, and 13, which is represented by formula (1-14-1-1) or formula (1-14-1-2).

[0061] [ka]

[0062] In formula (1-14-1-1) or formula (1-14-1-2), R 1 and R 2 are independently alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkoxyalkyl having 2 to 6 carbon atoms, alkenyl having 2 to 7 carbon atoms, or alkenyloxy having 2 to 7 carbon atoms. R a is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched alkyl having 3 or 4 carbon atoms.

[0063] Item 16. A liquid crystal composition containing at least one compound according to any one of items 1 to 15.

[0064] Item 17. The liquid crystal composition according to item 16, comprising at least one compound selected from the group of compounds represented by formulas (2) to (4):

[0065] [ka]

[0066] In equations (2) to (4), R 11 and R 12 are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and 11 and R 12 wherein at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; Ring B 1 , ring B 2 , ring B 3 , and ring B 4 is independently 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 a single bond, —COO—, —(CH 2 ) 2 —, —CH═CH—, or —C≡C—.

[0067] Item 18. The liquid crystal composition according to item 16 or 17, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (13):

[0068] [ka]

[0069] In equations (5) to (13), R 13 and R 14are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and 13 and R 14 wherein at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; R 15 is hydrogen, fluorine, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and 15 wherein at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; Ring C 1 , ring C 2 , ring C 3 , and ring C 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Ring C 5 and ring C 6 is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z 14 , Z 15 , Z 16 , and Z 17 are independently a single bond, -COO-, -CH2O-, -OCF2-, -(CH2)2-, or -OCF2-(CH2)2-; L 11 and L 12 are independently fluorine or chlorine; S 11 is hydrogen or methyl; X is -CHF- or -CF2-; j, k, m, n, p, q, r, and s are independently 0 or 1; the sum of k, m, n, and p is 1 or 2; the sum of q, r, and s is 0, 1, 2, or 3; and t is 1, 2, or 3.

[0070] Item 19. The liquid crystal composition according to any one of items 16 to 18, further comprising at least one compound selected from the group of compounds represented by formulas (21) to (23):

[0071] [ka]

[0072] In equations (21) to (23), R 16 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and this R 16 wherein at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X 11 is fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCF2CHF2, or -OCF2CHFCF3; Ring D 1 , Ring D 2 , and ring D 3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z 18 , Z 19 , and Z 20 are independently a single bond, -COO-, -CHO-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -C≡C-, or -(CH)-; L 13 and L 14 are independently hydrogen or fluorine.

[0073] Item 20. The liquid crystal composition according to any one of items 16 to 19, further comprising at least one compound selected from the group of compounds represented by formula (24):

[0074] [ka]

[0075] In equation (24), R 17 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and this R 17 wherein at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X 12 is -C≡N or -C≡CC≡N; Ring E 1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z 21 is a single bond, -COO-, -CH2O-, -CF2O-, -OCF2-, -(CH2)2-, or -C≡C-; L 15 and L 16 are independently hydrogen or fluorine; i is 1, 2, 3, or 4.

[0076] Item 21. A liquid crystal display device comprising the liquid crystal composition according to any one of items 16 to 20.

[0077] The present invention also includes the following: (a) the above composition, further comprising at least one optically active compound and / or polymerizable compound, and (b) the above composition, further comprising at least one antioxidant and / or ultraviolet absorber.

[0078] The present invention also includes the following: (c) the above composition, further containing one, two, or at least three additives selected from the group consisting of a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent. (d) the above composition, having a maximum temperature of a nematic phase of 70°C or higher, an optical anisotropy at a wavelength of 589 nm (measured at 25°C) of 0.08 or higher, and a dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) of -2 or lower.

[0079] The present invention also includes the following: (e) an element containing the above composition and having a PC, TN, STN, ECB, OCB, IPS, VA, FFS, FPA, or PSA mode; (f) an AM element containing the above composition; (g) a transmission element containing the above composition; (h) use of the above composition as a composition having a nematic phase; (i) use of the above composition as an optically active composition by adding an optically active compound to the above composition.

[0080] The embodiments of compound (1), the synthesis of compound (1), the liquid crystal composition, and the liquid crystal display device will be explained in this order.

[0081] 1. Aspects of Compound (1) Compound (1) is characterized by having a divalent group represented by the following formula: In the following formula, X is hydrogen or a substituent.

[0082] [ka]

[0083] This compound is extremely stable physically and chemically under conditions in which a device is normally used, and has good compatibility with other liquid crystal compounds. A composition containing this compound is stable under conditions in which a device is normally used. This composition has a large negative dielectric anisotropy. This compound has general physical properties required for a component of a composition, suitable optical anisotropy, and suitable dielectric anisotropy.

[0084] Terminal group R in compound (1) 1 and R 2 , lateral group R a , ring A 1 , and ring A 2 , ring N 1 , and ring N 2 , bonding group Z 1 , Z 2 , Z 3 , and Z 4 , lateral group L 1 , L 2 , L 3 ,L, 4 , L 5 and L 6 Preferred examples of are as follows. This example also applies to the sub-formula of compound (1). In compound (1), by appropriately combining these groups, it is possible to arbitrarily adjust the physical properties. Since there is no significant difference in the physical properties of the compound, compound (1) is 2 H (deuterium), 13 It may contain an isotope such as C in an amount greater than the natural abundance. The symbols for compound (1) are defined as in Section 1.

[0085] [ka]

[0086] In formula (1), R 1 is hydrogen or alkyl having 1 to 15 carbon atoms, and this R 1 In the formula (I), at least one -CH2- may be replaced with -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced with -CH=CH- or -C≡C-, and at least one hydrogen may be replaced with fluorine or chlorine. R 2 is hydrogen, fluorine, chlorine, -C≡N, -C≡CC≡N, or alkyl having 1 to 15 carbon atoms, and this R 2In the formula (I), at least one -CH2- may be replaced with -O-, -S-, or -CO-, at least one -(CH2)2- may be replaced with -CH=CH- or -C≡C-, and at least one hydrogen may be replaced with fluorine or chlorine.

[0087] However, in formula (1), when l is 0, R 1 cannot be hydrogen, and when o is 0, R 2 never becomes hydrogen.

[0088] Preferred R 1 or R 2 is alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl, alkynyl, and alkynyloxy. 1 or R 2 In this R, at least one hydrogen may be replaced by fluorine or chlorine. Examples of this include groups in which at least two hydrogens are replaced by both fluorine and chlorine. Groups in which at least one hydrogen is replaced by only fluorine are more preferred. 1 or R 2 In the case of R, a straight chain is preferred to a branched chain. 1 or R 2 is preferably a branched chain when it is optically active. 1 or R 2 R is alkyl, alkoxy, alkoxyalkyl, alkenyl, monofluoroalkyl, polyfluoroalkyl, monofluoroalkoxy, and polyfluoroalkoxy. 2 In addition to the groups mentioned above, may be fluorine, chlorine, -C≡N, or -C≡CC≡N.

[0089] The preferred configuration of -CH=CH- in alkenyl depends on the position of the double bond. In alkenyls such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, the trans configuration is preferred. In alkenyls such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

[0090] Specific R 1 or R 2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, butoxymethyl, butoxyethyl, pentoxymethyl, pentoxyethyl, vinyl, 1-propenyl Examples of aryl include 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 2-hexenyloxy, and 1-propynyl.

[0091] Specific R 1 or R 2 are 2-fluoroethyl, 3-fluoropropyl, 2,2,2-trifluoroethyl, 2-fluorovinyl, 2,2-difluorovinyl, 2-fluoro-2-vinyl, 3-fluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 4-fluoro-1-propenyl, and 4,4-difluoro-3-butenyl.

[0092] Specific R 2In addition to the groups mentioned above, may be fluorine, chlorine, -C≡N, -CF3, -CHF2, -CH2F, -CF2CF3, -CF2CHF2, -CF2CH2F, -CF2CF2CF3, -CF2CHFCF3, -CHFCF2CF3, -OCF3, -OCHF2, -OCH2F, -OCF2CF3, -OCF2CHF2, -OCF2CH2F, -OCF2CF2CF3, -OCF2CHFCF3, and -OCHFCF2CF3.

[0093] Even more preferable R 1 or R 2 is ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, methoxymethyl, ethoxymethyl, ethoxyethyl, propoxymethyl, propoxyethyl, butoxymethyl, pentoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2-propenyloxy, 2-butenyloxy, and 2-pentenyloxy. 2 are -OCF3, -OCHF2, -OCH2F, -OCF2CF3, -OCF2CHF2, -OCF2CH2F, -OCF2CF2CF3, -OCF2CHFCF3, -OCHFCF2CF3, fluorine, chlorine, and -C≡N. 1 or R 2 is ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, vinyl, 1-propenyl, 3-butenyl, and 3-pentenyl. 2 are -OCF3, -OCHF2, -CF3, -CHF2, -CH2F, -OCF2CHF2, -OCF2CHFCF3, fluorine, and -C≡N.

[0094] R ais hydrogen, a straight chain alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms.

[0095] Preferred R a is methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, sec-butyl, pentan-2-yl, hexan-2-yl, pentan-3-yl, hexan-3-yl, tert-butyl, tert-pentyl, 3-methylpentan-3-yl, and 3-ethylpentan-3-yl. a Particularly preferred R are methyl, ethyl, propyl, butyl, isopropyl, sec-butyl, and tert-butyl. a are methyl, ethyl, propyl, and isopropyl. a are methyl and ethyl.

[0096] In formula (1), ring A 1 and ring A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and the ring A 1 and ring A 2 In the formula, at least one -CH2- may be replaced with -O-, and at least one -(CH2)2- may be replaced with -CH=CH-.

[0097] Preferred Ring A 1 or ring A 2 Examples of the divalent groups are those represented by the following formulae (25-1) to (25-27). More preferred examples are those represented by the formulae (25-1) to (25-17). Particularly preferred examples are those represented by the formulae (25-1) to (25-3) and (25-13) to (25-17). Most preferred examples are those represented by the formulae (25-1) to (25-3).

[0098] [ka]

[0099] In formula (1), ring N1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, and pyridine-2,5-diyl. , pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofuran-2,5-diyl, benzofuran-2,6-diyl, benzo[b]thiophene-2,5-diyl, benzo[b]thiophene-2,6-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 9H-xanthene-2,6-diyl, or 9H-fluorene-2,7-diyl, and the ring N 1 and ring N 2 In the formula (I), at least one hydrogen may be replaced by fluorine, chlorine, —C≡N, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 , or —OCH 2 F.

[0100] "Ring N 1 and ring N 2 Preferred examples of "wherein at least one hydrogen may be replaced by fluorine, chlorine, -C≡N, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, or -OCH2F" are divalent groups represented by the following formulae (26-1) to (26-71). More preferred examples are divalent groups represented by formulae (26-1) to (26-4), (26-6), (26-10) to (26-15), and (26-54) to (26-59).

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] More preferred ring N 1 or ring N 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and naphthalene-2,6-diyl. The trans configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferred over cis.

[0105] Particularly preferred ring N 1 or ring N 2 are 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, and pyrimidine-2,5-diyl. 1 or ring N 2 are 1,4-cyclohexylene and 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene.

[0106] In formula (1), Z 1 , Z 2 , Z 3 , and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and Z1 , Z 2 , Z 3 , and Z 4 In the formula (I), at least one -CH2- may be replaced by -O-, -S-, -CO-, or -SiH2-, at least one -(CH2)2- may be replaced by -CH=CH- or -C≡C-, and at least one hydrogen may be replaced by fluorine or chlorine.

[0107] Z 1 , Z 2 , Z 3 , or Z 4 Specific examples of the alkyl group include a single bond, -COO-, -OCO-, -CHO-, -OCHO-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, -CHCO-, -COCH-, -(CH)-, -(CH)COO-, -(CH)OCO-, -OCO( The stereochemistry of the double bond of a bonding group such as -CH=CH-, -CF=CF-, -CH=CH-CHO-, and -OCH-CH=CH- is preferably trans rather than cis.

[0108] Preferred Z 1 , Z 2 , Z 3 , or Z 4 is a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, -(CH)-CH=CH-, -CH=CH-CHO-, and -OCH-CH=CH-. More preferred Z 1 , Z 2 or Z 3is a single bond, -COO-, -OCO-, -CHO-, -OCH-, -CFO-, -OCF-, -CH=CH-, -(CH)-, -(CH)-, -(CH)O-, -O(CH)-, -CH=CH-(CH)-, and -(CH)-CH=CH-. 1 , Z 2 , Z 3 , or Z 4 is a single bond, -CH2O- or -OCH2-.

[0109] In formula (1), L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are independently hydrogen, fluorine, chlorine, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 , —OCH 2 F, or —C≡N.

[0110] In formula (1), L 5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , and L 4 at least one of is fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 1 , L 2 , L 3 , and L 4 At least one of the groups may be hydrogen. 1 , L 2 , L 3 , and L 4 is fluorine or -CF3. Particularly preferred L 1 , L 2 , L 3 , and L 4 is fluorine.

[0111] In formula (1), L 1 , L 2 , L 3 , and L 4When both are hydrogen, L 5 and L 6 at least one of is fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCH2F, or -C≡N, and L 5 and L 6 At least one of the groups may be hydrogen. 5 and L 6 is fluorine or -CF3. Particularly preferred L 5 and L 6 is fluorine.

[0112] In formula (1), l and o are independently 0 or 1, m and n are independently 0, 1, or 2, and the sum of l, m, n, and o is an integer from 0 to 4. Compound (1) has one to five rings. These rings include not only normal six-membered rings but also fused rings and bridged six-membered rings. When compound (1) has one or two rings, it has good compatibility with other liquid crystal compounds and low viscosity. When compound (1) has three or four rings, it has a high maximum temperature. When compound (1) has four rings, it has a wide temperature range for the liquid crystal phase.

[0113] By appropriately selecting the terminal group, ring, and bonding group of compound (1), it is possible to arbitrarily adjust physical properties such as optical anisotropy and dielectric anisotropy. 1 and R 2 , ring A 1 , and A 2 , bonding group Z 1 , Z 2 , Z 3 , and Z 4 The effect of the type of compound (1) on the physical properties of the compound (1) will be explained below.

[0114] In compound (1), R 1 or R 2 When R is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. 1 or R 2 When R is a branched chain, the compatibility with other liquid crystal compounds is good. 1 or R2 Compounds in which R is an optically active group are useful as chiral dopants. By adding this compound to a composition, it is possible to prevent the occurrence of reverse twisted domains in devices. 1 or R 2 Compounds in which R is not an optically active group are useful as components of compositions. 1 or R 2 When is an alkenyl, the preferred configuration depends on the position of the double bond. Alkenyl compounds with a preferred configuration have a high upper limit temperature or a wide temperature range of the liquid crystal phase. Detailed explanations are given in Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327.

[0115] Ring A 1 , or ring A 2 However, when the ring is 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3,6-diyl in which at least one hydrogen may be replaced by fluorine or chlorine, the optical anisotropy is large. When the ring is 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.

[0116] When at least two rings are 1,4-cyclohexylene, the maximum temperature is high, the optical anisotropy is small, and the viscosity is small.When at least one ring is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is large.When at least two rings are 1,4-phenylene, the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the maximum temperature is high.

[0117] bonding group Z 1 , Z 2 , Z 3 , or Z 4When the bonding group is a single bond, -CHO-, -CFO-, -OCF-, -(CH)-, -CH=CH-, -CF=CF-, or -(CH)-, the viscosity is small. When the bonding group is a single bond, -OCF-, -CFO-, -(CH)-, or -CH=CH-, the viscosity is smaller. When the bonding group is -CH=CH-, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K 33 / K 11 (K 33 : bend elastic constant, K 11 : Splay elastic constant) is large. When the bonding group is -C≡C-, the optical anisotropy is large.

[0118] When compound (1) has one or two rings, the viscosity is low. When compound (1) has four or five rings, the maximum temperature is high. As described above, by appropriately selecting the types of terminal groups, rings, and bonding groups, and the number of rings, a compound with the required physical properties can be obtained. Therefore, compound (1) is useful as a component of a composition used in devices with modes such as PC, TN, STN, ECB, OCB, IPS, and VA.

[0119] In formula (1), L 5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , or L 4 The compound is preferred when L is fluorine, chlorine, -CF3, or -CHF2. 5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , or L 4 The compound is further preferred when L is fluorine or chlorine. 5 and L 6 When both are hydrogen, L 1 , L 2 , L 3 , or L 4 When is fluorine, the compound is most preferred.

[0120] In formula (1), L1 , L 2 , L 3 , and L 4 When both are hydrogen, L 5 or L 6 The compound is preferred when L is fluorine, chlorine, -CF3, or -CHF2. 1 , L 2 , L 3 , and L 4 When both are hydrogen, L 5 or L 6 The compound is further preferred when L is fluorine or chlorine. 1 , L 2 , L 3 , and L 4 When both are hydrogen, L 5 or L 6 When is fluorine, the compound is most preferred.

[0121] Preferred examples of compound (1) are compounds (1-1) to (1-26) described in items 2 and 4. More preferred examples are the compounds shown by sub-formulas in items 6 and 8. Compound (1) is suitable for devices having modes such as VA, IPS, and PSA.

[0122] 2. Synthesis of Compound (1) The synthesis of compound (1) is described below. Compound (1) can be synthesized by appropriately combining methods of organic synthetic chemistry. Methods for introducing the required terminal groups, rings, and bonding groups into starting materials are described in textbooks such as "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" (John Wiley & Sons, Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), and "New Experimental Chemistry Lectures" (Maruzen).

[0123] 2-1. Formation of bonding group Z bonding group Z 1From Z 4 First, a scheme is shown for the method of producing MSG. Next, the reactions shown in the schemes (1) to (11) are explained. In this scheme, 1 (or MSG 2 ) is a monovalent organic group having at least one ring. 1 (or MSG 2 The monovalent organic groups represented by may be the same or different. Compounds (1A) to (1J) correspond to compound (1).

[0124] [ka]

[0125] [ka]

[0126] (1) Formation of a single bond Compound (1A) is synthesized by reacting arylboronic acid (31), synthesized by a known method, with halide (32) in the presence of carbonate and a catalyst such as tetrakis(triphenylphosphine)palladium. Compound (1A) can also be synthesized by reacting halide (33), synthesized by a known method, with n-butyllithium and then zinc chloride, followed by reaction with halide (32) in the presence of a catalyst such as dichlorobis(triphenylphosphine)palladium.

[0127] (2) -COO- formation Halide (33) is reacted with n-butyllithium and then carbon dioxide to give carboxylic acid (34). Compound (1B) is synthesized by dehydrating compound (35), which is synthesized by a known method, and carboxylic acid (34) in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine).

[0128] (3) Formation of -CF2O- Compound (1B) is treated with a sulfurating agent such as Lawesson's reagent to give thionoester (36). Thionoester (36) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to give compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be prepared by fluorinating thionoester (36) with DAST ((diethylamino)sulfur trifluoride). See W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. This linking group can also be formed by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

[0129] (4) Formation of -CH=CH- Halide (32) is treated with n-butyllithium and then reacted with DMF (N,N-dimethylformamide) to obtain aldehyde (38). Phosphonium salt (37), synthesized by a known method, is treated with a base such as potassium t-butoxide to generate a phosphorus ylide. This phosphorus ylide is then reacted with aldehyde (38) to synthesize compound (1D). Depending on the reaction conditions, a cis isomer may be produced, so the cis isomer can be isomerized to a trans isomer using a known method, if necessary.

[0130] (5)-(CH2)2- Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium on carbon.

[0131] (6)-(CH2)4- Using phosphonium salt (39) instead of phosphonium salt (37), a compound having the formula -(CH2)2-CH=CH- is obtained according to method (4), which is then catalytically hydrogenated to synthesize compound (1F).

[0132] (7) Formation of -CH2CH=CHCH2- Compound (1G) is synthesized according to Method (4) using phosphonium salt (40) instead of phosphonium salt (37) and aldehyde (41) instead of aldehyde (38). Depending on the reaction conditions, a trans isomer may be produced, so the trans isomer is isomerized to a cis isomer by a known method, if necessary.

[0133] (8) Formation of -C≡C- In the presence of dichloropalladium and copper halide catalysts, halide (33) is reacted with 2-methyl-3-butyn-2-ol, followed by deprotection under basic conditions to obtain compound (32). Compound (42) is reacted with halide (32) in the presence of dichloropalladium and copper halide catalysts to synthesize compound (1H).

[0134] (9) -CF=CF- formation Halide (33) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (43). Halide (32) is treated with n-butyllithium and then reacted with compound (43) to synthesize compound (1I).

[0135] (10) Formation of -OCH2- Aldehyde (38) is reduced with a reducing agent such as sodium borohydride to give compound (44). Compound (44) is brominated with hydrobromic acid to give bromide (45). Bromide (45) is reacted with compound (46) in the presence of a base such as potassium carbonate to give compound (1J).

[0136] Formation of (11)-(CF2)2- According to the method described in J. Am. Chem. Soc., 2001, 123, 5414, a diketone (-COCO-) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to obtain a compound having -(CF2)2-.

[0137] 2-2. Ring A 1 From A 3 and ring N 1 Generation of Next, ring A1 From A 3 and ring N 1 For rings such as 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, pyridine-2,5-diyl, and pyrimidine-2,5-diyl, the starting materials are commercially available or their preparation methods are well known. Therefore, the following compounds (64), (67), and (71) are described.

[0138] [ka]

[0139] Decahydronaphthalene-2,6-dione (64) is the starting compound containing decahydronaphthalene-2,6-diyl. This compound (64) can be obtained by catalytic hydrogen reduction of diol (63) in the presence of ruthenium oxide and further oxidation with chromium oxide according to the method described in JP-A-2000-239564. This compound can be converted to compound (1) by a conventional method.

[0140] [ka]

[0141] The 2,3-(bistrifluoromethyl)phenylene structural unit is synthesized by the method described in Org. Lett., 2000, 2 (21), 3345. Aniline (66) is prepared by the Diels-Alder reaction of furan (65) with 1,1,1,4,4,4-hexafluoro-2-butyne at high temperature. This compound is then subjected to a Sandmeyer reaction according to the method described in Org. Synth. Coll., Vol. 2, 1943, 355 to give iodide (67). This compound is then converted to compound (1) by standard methods.

[0142] [ka]

[0143] The 2-difluoromethyl-3-fluorophenylene structural unit is synthesized as follows. The hydroxyl group of compound (68) is protected with a suitable protecting group to give compound (69). P denotes a protecting group. Compound (69) is treated with s-butyllithium and then reacted with N,N-dimethylformamide (DMF) to give aldehyde (70). This compound is fluorinated with diethylaminosulfur trifluoride (DAST) and subsequently deprotected to give phenol (71). This compound is converted to compound (1) by a conventional method.

[0144] 2-3. Formation of the 3,6-dihydro-2H-pyran ring The method for producing this ring will be explained using compounds (1a) and (1b) having a divalent group represented by formula (pr-1). Compounds having a divalent group represented by formula (pr-2) can also be synthesized by this method. The synthesis scheme for compound (1a) is as follows.

[0145] [ka]

[0146] Compound (s-1) is synthesized according to the method described in JP 2011-136924 A. Compound (s-1) is reduced with a reducing agent such as sodium borohydride to obtain compound (s-2). This compound is halogenated with triphenylphosphine and carbon tetrahalide, and then treated with a dehalogenating agent such as diazabicycloundecene (DBU) to obtain the target compound (1a).

[0147] [ka]

[0148] The synthesis scheme for compound (1b) is as described above. Compound (s-3) is reacted with aldehyde (17) in the presence of a Lewis acid such as boron trifluoride diethyl ether complex, followed by hydrogenation to obtain compound (s-4). This compound is reduced with a reducing agent such as lithium aluminum hydride to obtain compound (s-5). This compound is halogenated with triphenylphosphine and carbon tetrahalide, and then treated with a dehalogenating agent such as diazabicycloundecene (DBU) to obtain compound (1b).

[0149] 2-4. Formation of carbazole ring The synthesis scheme of the compounds (1c) to (1f) is as follows.

[0150] [ka]

[0151] Compound (s-6), compound (s-7), Pd(amphos)Cl2, and sodium t-butoxide are reacted to obtain compound (s-8). P represents a protecting group. Compound (s-9) is obtained by deprotecting this compound. Compound (1c) is obtained by reacting this compound with palladium acetate in acetic acid. Compound (1d) is obtained by alkylating this compound. In these compounds, L 1 , L 2 , L 3 and L 4 The definition of RA is the same as that of the symbol described in Section 1. 1 or RA 2 The definition of MSG 1 and R described in Section 1 1 or R 2 is the same as the definition of

[0152] [ka]

[0153] Compound (s-10), compound (s-11), Pd(amphos)Cl2, and sodium t-butoxide are reacted to obtain compound (s-12). P represents a protecting group. Compound (s-13) is obtained by deprotecting this compound. Compound (1e) is obtained by reacting this compound with palladium acetate in acetic acid. Compound (1f) is obtained by alkylating this compound. In these compounds, L 5 and L 6 The definition of RA is the same as that of the symbol described in Section 1. 1 or RA 2 The definition of MSG 1 and R described in Section 1 1 or R 2 is the same as the definition of

[0154] 3. Liquid crystal composition 3-1.Component compounds The liquid crystal composition of the present invention will be described. This composition contains at least one compound (1) as component (a). This composition may contain two or more compounds (1). The composition may contain only compound (1). The composition preferably contains at least one compound (1) in the range of 1 to 99% by weight in order to exhibit good physical properties. In a composition having negative dielectric anisotropy, the content of compound (1) is preferably in the range of 5 to 60% by weight. In a composition having positive dielectric anisotropy, the content of compound (1) is preferably 30% by weight or less.

[0155] [Table 1]

[0156] This composition contains compound (1) as component (a). This composition preferably further contains a liquid crystal compound selected from components (b) to (e) shown in Table 1. When preparing this composition, it is preferable to select components (b) to (e) in consideration of the positive / negative sign and magnitude of the dielectric anisotropy. This composition may contain a liquid crystal compound other than compounds (1) to (13) and (21) to (24). This composition does not necessarily need to contain such a liquid crystal compound.

[0157] Component (b) is a compound in which the two terminal groups are alkyl or the like. 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). In these compounds, R 11 and R 12 are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and 11 and R 12 In the formula (I), at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine.

[0158] [ka]

[0159] Component (b) has a small dielectric anisotropy. Component (b) is nearly neutral. Compound (2) has the effect of reducing viscosity or adjusting optical anisotropy. Compounds (3) and (4) have the effect of increasing the maximum temperature, thereby expanding the temperature range of the nematic phase, or adjusting optical anisotropy.

[0160] As the content of component (b) increases, the viscosity of the composition decreases, but the dielectric anisotropy also decreases. Therefore, a higher content is preferable as long as the required threshold voltage of the device is satisfied. When preparing a composition for an IPS or VA mode, the content of 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.

[0161] Component (c) is compounds (5) to (13). These compounds have phenylene substituted with two halogens at the lateral positions, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component (c) include compounds (5-1) to (5-9), compounds (6-1) to (6-19), compounds (7-1) and (7-2), compounds (8-1) to (8-3), compounds (9-1) to (9-3), compounds (10-1) to (10-11), compounds (11-1) to (11-3), compounds (12-1) to (12-3), and compound (13-1). In these compounds, R 13 and R 14 are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and 13 and R 14 In the formula (I), at least one -CH2- may be replaced by -O-, at least one hydrogen may be replaced by fluorine, and R 15 is hydrogen, fluorine, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, and 15 In the formula, at least one -CH2- may be replaced by -O-, and this R 15 In the formula (I), at least one hydrogen may be replaced by fluorine.

[0162] [ka]

[0163] [ka]

[0164] Component (c) has a large negative dielectric anisotropy. Component (c) is used when preparing compositions for modes such as IPS, VA, and PSA. As the content of component (c) increases, the negative dielectric anisotropy of the composition increases, but the viscosity also increases. Therefore, as long as the required threshold voltage of the device is met, a small content is preferable. Considering that the dielectric anisotropy is approximately -5, a content of 40% by weight or more is preferable to ensure sufficient voltage driving.

[0165] Among the components (c), compound (5) is a bicyclic compound, which has the effects of decreasing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Compounds (6) and (7) are tricyclic compounds, and compound (8) is a tetracyclic compound, which have the effects of increasing the maximum temperature, increasing optical anisotropy, or increasing dielectric anisotropy. Compounds (9) to (13) have the effect of increasing dielectric anisotropy.

[0166] When preparing a composition for an IPS, VA, PSA, or other mode, the content of component (c) is preferably 40% by weight or more, more preferably 50 to 95% by weight, based on the weight of the liquid crystal composition. When component (c) is added to a composition with positive dielectric anisotropy, the content of component (c) is preferably 30% by weight or less. Adding component (c) adjusts the elastic constant of the composition and makes it possible to adjust the voltage-transmittance curve of the device.

[0167] Component (d) is a compound having a halogen- or fluorine-containing group at the right end. Preferred examples of component (d) include compounds (21-1) to (21-16), compounds (22-1) to (22-116), and compounds (23-1) to (23-59). In these compounds, R 16 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and R 16 In the formula, at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine. X 11is fluorine, chlorine, -OCF3, -OCHF2, -CF3, -CHF2, -CH2F, -OCF2CHF2, or -OCF2CHFCF3.

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] Component (d) has positive dielectric anisotropy and excellent stability against heat and light, and is therefore used when preparing compositions for modes such as IPS, FFS, and OCB. The content of component (d) is suitably in the range of 1 to 99% by weight, preferably 10 to 97% by weight, and more preferably 40 to 95% by weight, based on the weight of the liquid crystal composition. When component (d) is added to a composition with negative dielectric anisotropy, the content of component (d) is preferably 30% by weight or less. Adding component (d) adjusts the elastic constant of the composition and enables the voltage-transmittance curve of the device to be adjusted.

[0176] Component (e) is compound (24) in which the right terminal group is -C≡N or -C≡CC≡N. Preferred examples of component (e) include compounds (24-1) to (24-64). In these compounds, R 17 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and R 17 In the formula (I), at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine. 12 is -C≡N or -C≡CC≡N.

[0177] [ka]

[0178] [ka]

[0179] Component (e) has a positive and large dielectric anisotropy, and is therefore used when preparing compositions for modes such as TN. Adding component (e) increases the dielectric anisotropy of the composition. Component (e) has the effects of broadening the temperature range of the liquid crystal phase, adjusting viscosity, and adjusting optical anisotropy. Component (e) is also useful for adjusting the voltage-transmittance curve of the device.

[0180] When preparing a composition for a TN mode or the like, the content of component (e) is suitably in the range of 1 to 99% by weight, preferably 10 to 97% by weight, and more preferably 40 to 95% by weight, based on the weight of the liquid crystal composition. When component (e) is added to a composition with negative dielectric anisotropy, the content of component (e) is preferably 30% by weight or less. Adding component (e) adjusts the elastic constant of the composition and makes it possible to adjust the voltage-transmittance curve of the device.

[0181] By combining a compound appropriately selected from the above components (b) to (e) with compound (1), it is possible to prepare a liquid crystal composition that satisfies at least one of the following physical properties: high stability against heat and light, a high upper limit temperature, a low lower limit temperature, a small viscosity, a suitable optical anisotropy (i.e., large or small optical anisotropy), a large positive or negative dielectric anisotropy, a large resistivity, and a suitable elastic constant (i.e., large or small elastic constant). A device containing such a composition has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifespan.

[0182] When an element is used for a long period of time, flicker may occur on the display screen. The flicker rate (%) can be expressed by (|luminance when a positive voltage is applied - luminance when a negative voltage is applied| / average luminance) × 100. An element with a flicker rate in the range of 0% to 1% is unlikely to cause flicker on the display screen even when used for a long period of time. This flicker is related to image sticking and is presumed to occur due to the potential difference between the positive and negative frames when driven with an alternating current. Compositions containing compound (1) are also useful for reducing the occurrence of flicker.

[0183] 3-2. Additives Liquid crystal compositions are prepared by known methods. For example, component compounds are mixed and then heated to dissolve them. Depending on the intended use, additives may be added to the composition. Examples of additives include polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents. Such additives are well known to those skilled in the art and are described in the literature.

[0184] In a liquid crystal display element having a PSA (polymer sustained alignment) mode, the composition contains a polymer. A polymerizable compound is added to the composition for the purpose of generating a polymer. The polymerizable compound is polymerized by irradiating the composition with ultraviolet light while a voltage is applied between the electrodes, thereby generating a polymer in the composition. This method achieves an appropriate pretilt, thereby shortening the response time and producing an element with improved image sticking.

[0185] Preferred examples of the polymerizable compound include acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. More preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. More preferred examples include compounds having both acryloyloxy and methacryloyloxy groups.

[0186] Further preferred examples are compounds (M-1) to (M-18). In these compounds, R 25 From 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, and R 32 , R 33 , and R 34 at least one of is alkyl having 1 to 5 carbon atoms; v, w, and x are independently 0 or 1; and u and y are independently integers from 1 to 10.21 From L 26 are independently hydrogen or fluorine; L 27 and L 28 are independently hydrogen, fluorine, or methyl.

[0187] [ka]

[0188] Polymerizable compounds can be polymerized rapidly by adding a polymerization initiator. Optimizing the reaction conditions can reduce the amount of residual polymerizable compound. Examples of photoradical polymerization initiators include TPO, 1173, and 4265 from BASF's Darocure series, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 from the Irgacure series.

[0189] Additional examples of photoradical polymerization initiators are 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzil dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture.

[0190] After adding a photo-radical polymerization initiator to the liquid crystal composition, polymerization can be carried out by irradiating it with ultraviolet light while an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking in the device. To prevent this, photopolymerization can be carried out without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm. A more preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.

[0191] When storing a 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 include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine, etc.

[0192] The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecules and providing the necessary twist angle. The helical pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added to adjust the temperature dependence of the helical 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. The * symbol indicates an asymmetric carbon atom.

[0193] [ka]

[0194] The antioxidant is effective in maintaining a high voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2): Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade names; BASF). The ultraviolet absorber is effective in preventing a decrease in the maximum temperature. Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. Specific examples include the following compounds (AO-3) and (AO-4): Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin 328, and Tinuvin 99-2 (trade names; BASF); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0195] Light stabilizers such as sterically hindered amines are preferred for maintaining a high voltage holding ratio. Preferred examples of light stabilizers include the following compounds (AO-5), (AO-6), (AO-7), (AO-8), and (AO-9): Tinuvin 144, Tinuvin 765, Tinuvin 770DF, and Tinuvin 780 (trade names: BASF); and LA-52, LA-57, LA-77Y, and LA-77G (trade names: ADEKA). Thermal stabilizers are also effective for maintaining a high voltage holding ratio, and a preferred example is Irgafos 168 (trade name: BASF). To accommodate GH (guest-host) mode devices, dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition. Antifoaming agents are effective in preventing foaming. Preferred examples of antifoaming agents include dimethyl silicone oil and methylphenyl silicone oil.

[0196] [ka]

[0197] In compound (AO-1), R 40 -COOR is alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, 41 , or -(CH2)2-COOR 41 where R 41 is alkyl having 1 to 20 carbon atoms. In compounds (AO-2) and (AO-5), R 42 is alkyl having 1 to 20 carbon atoms. In compound (AO-5), R 43 is hydrogen, methyl or O · (oxygen radical); Ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compounds (AO-7) and (AO-8), ring G 2 is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and in compounds (AO-5), (AO-7), and (AO-8), z is 1, 2, or 3.

[0198] 4. Liquid crystal display element The liquid crystal composition can be used in liquid crystal display elements driven by the active matrix method, having operating modes such as PC, TN, STN, OCB, and PSA. This composition can also be used in liquid crystal display elements driven by the passive matrix method, having operating modes such as PC, TN, STN, OCB, VA, and IPS. These elements can be applied to any of the reflective, transmissive, and semi-transmissive types.

[0199] This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, in which the composition is microencapsulated. This composition can also be used for polymer-dispersed liquid crystal displays (PDLCDs) and polymer-network liquid crystal displays (PNLCDs). These compositions contain a large amount of polymerizable compound. 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 PSA mode liquid crystal display device is fabricated. A preferred proportion is in the range of 0.1% to 2% by weight, and a more preferred proportion is in the range of 0.2% to 1.0% by weight. PSA mode devices can be driven by a driving method such as an active matrix method or a passive matrix method. These devices can be applied to any of reflective, transmissive, and semi-transmissive types. [Example]

[0200] 1. Example of Compound (1) The present invention will be explained in more detail by way of examples. The examples are typical examples, and the present invention is not limited by the examples. Compound (1) was synthesized according to the following procedure. The synthesized compound was identified by methods such as NMR analysis. The physical properties of the compound and composition, and the characteristics of the device were measured according to the following methods.

[0201] NMR analysis: For the measurement, a DRX-500 manufactured by Bruker Biospin was used. 1 For H-NMR measurements, samples were dissolved in deuterated solvents such as CDCl3 and measured at room temperature, 500 MHz, and with 16 accumulations. Tetramethylsilane was used as the internal standard. 19 F-NMR measurements were performed using CFCl3 as an internal standard with an accumulation count of 24. In the explanation of nuclear magnetic resonance spectra, 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.

[0202] Gas chromatographic analysis: A Shimadzu GC-2010 gas chromatograph was used for the measurements. The column used was a capillary column DB-1 (60 m long, 0.25 mm inner diameter, 0.25 μm film thickness) manufactured by Agilent Technologies Inc. Helium (1 mL / min) was used as the carrier gas. The temperature of the sample vaporizer was set to 300°C, and the temperature of the detector (FID) was also set to 300°C. The sample was dissolved in acetone to prepare a 1 wt% solution, and 1 μL of the resulting solution was injected into the sample vaporizer. A Shimadzu GCSolution system or similar was used as the recorder.

[0203] Gas chromatograph mass spectrometry: A Shimadzu QP-2010 Ultra gas chromatograph mass spectrometer was used for the measurements. The column used was a capillary column DB-1 (60 m long, 0.25 mm inner diameter, 0.25 μm film thickness) manufactured by Agilent Technologies Inc. Helium (1 mL / min) was used as the carrier gas. The sample vaporizer temperature was set to 300°C, the ion source temperature to 200°C, the ionization voltage to 70 eV, and the emission current to 150 μA. The sample was dissolved in acetone to prepare a 1 wt% solution, and 1 μL of the resulting solution was injected into the sample vaporizer. A Shimadzu GCMSsolution system was used as the recorder.

[0204] HPLC analysis: A Shimadzu Prominence (LC-20AD; SPD-20A) was used for the measurements. The column used was a YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) manufactured by YMC. The eluent was a suitable mixture of acetonitrile and water. Detectors used included a UV detector, RI detector, and CORONA detector. When using a UV detector, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. A Shimadzu C-R7Aplus was used as the recorder.

[0205] UV-visible spectroscopic analysis: Measurements were performed using a Shimadzu PharmaSpec UV-1700. The detection wavelength was 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, which was then placed in a quartz cell (path length 1 cm) for measurement.

[0206] Measurement sample: When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as the sample. When measuring physical properties such as the upper limit temperature of the nematic phase, viscosity, optical anisotropy, and dielectric anisotropy, a mixture of the compound and mother liquid crystal was used as the sample.

[0207] When a sample in which the compound was mixed with mother liquid crystals was used, the measurement was carried out as follows. A sample was prepared by mixing 15% by weight of the compound with 85% by weight of the mother liquid crystals. From the measured value of this sample, an extrapolated value was calculated according to the following equation, and this value was recorded. <Extrapolated value> = (100 x <Measured value of sample> - <weight % of mother liquid crystals> x <Measured value of mother liquid crystals>) / <weight % of compound>

[0208] If crystals (or a smectic phase) precipitate at this ratio at 25° C., the ratio of the compound to the mother liquid crystals was changed in the order of 10 wt%:90 wt%, 5 wt%:95 wt%, and 1 wt%:99 wt%, and the physical properties of the sample were measured at the ratio at which crystals (or a smectic phase) no longer precipitated at 25° C. Unless otherwise specified, the ratio of the compound to the mother liquid crystals was 15 wt%:85 wt%.

[0209] When the compound had a dielectric anisotropy of zero or positive, the following base liquid crystal (A) was used: The proportion of each component is expressed in % by weight.

[0210] [ka]

[0211] When the compound had a dielectric anisotropy of zero or negative, the following base liquid crystal (B) was used: The proportion of each component is expressed in % by weight.

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[0213] Base liquid crystals (C): Base liquid crystals (C) containing the following fluorine-based compounds as components were also used. The proportions of the components in the base liquid crystals (C) are expressed in weight %.

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[0215] The ratio of the compound to the mother liquid crystals (C) was 20% by weight:80% by weight. If crystals (or a smectic phase) precipitated at 25°C at this ratio, the ratio of the compound to the mother liquid crystals (C) was changed in the following order: 15% by weight:85% by weight, 10% by weight:90% by weight, 5% by weight:95% by weight, and 1% by weight:99% by weight. The physical properties of the sample were measured at the ratio at which crystals (or a smectic phase) no longer precipitated at 25°C. Unless otherwise specified, the ratio of the compound to the mother liquid crystals (C) was 20% by weight:80% by weight.

[0216] Measurement methods: Physical properties were measured using the following methods. Many of these are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA). Modified methods were also used. No thin-film transistors (TFTs) were attached to the TN devices used for the measurements.

[0217] (1) Phase structure: A sample was placed on the hot plate of a melting point measuring device (Mettler FP-52 hot stage) equipped with a polarizing microscope. The sample was heated at a rate of 3°C / min, and the phase state and its changes were observed under the polarizing microscope to identify the type of phase.

[0218] (2) Transition temperature (°C): Measurements were performed using a PerkinElmer Diamond DSC system scanning calorimeter or an SII NanoTechnology X-DSC7000 high-sensitivity differential scanning calorimeter. The sample was heated and cooled at a rate of 3°C / min, and the onset of the endothermic or exothermic peak associated with the phase change of the sample was extrapolated to determine the transition temperature. The melting point and polymerization onset 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 or nematic phase is sometimes abbreviated as the "lower limit temperature of the liquid crystal phase." The temperature at which a compound transitions from a liquid crystal phase to a liquid is sometimes abbreviated as the "clearing point."

[0219] Crystals are represented as C. When two types of crystals can be distinguished, they are represented as C1 or C2. Smectic phases are represented as S, and nematic phases as N. When phases such as smectic A, smectic B, smectic C, and smectic F can be distinguished, they are represented as S. A , S B , S C , and S F Liquid (isotropic) is represented as I. The transition temperatures are expressed as, for example, "C 50.0 N 100.0 I." This indicates that the transition temperature from crystal to nematic phase is 50.0°C, and the transition temperature from nematic phase to liquid is 100.0°C.

[0220] (3) Compatibility of compounds: Samples were prepared by mixing mother liquid crystals and compounds so that the compound ratios were 20 wt%, 15 wt%, 10 wt%, 5 wt%, 3 wt%, or 1 wt%. The samples were placed in glass bottles and stored in a freezer at -10°C or -20°C for a certain period of time. Observations were made to see whether the nematic phase of the sample was maintained or whether crystals (or a smectic phase) precipitated. The conditions under which the nematic phase was maintained were used as a measure of compatibility. The compound ratios and freezer temperatures may be changed as necessary.

[0221] (4) The maximum temperature of the nematic phase (T NIor NI; °C): A sample was placed on the hot plate of a melting point measuring apparatus 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 a nematic phase to an isotropic liquid was measured. When the sample was a mixture of compound (1) and mother liquid crystals, T NI When the sample is a mixture of compound (1) and a compound selected from compounds (2) to (15), it is represented by the symbol NI. The maximum temperature of the nematic phase is sometimes abbreviated as "maximum temperature."

[0222] (5) The minimum temperature of the nematic phase (T C ; °C): A sample having a nematic phase was placed in a glass bottle and stored in a freezer at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C for 10 days, after which the liquid crystal phase was observed. For example, when the sample remained in the nematic phase at -20 °C and changed to a crystalline or smectic phase at -30 °C, T C The lowest temperature limit of the nematic phase is sometimes abbreviated as "lower limit temperature."

[0223] (6) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s): For the measurement, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

[0224] (7) Optical anisotropy (refractive index anisotropy; measured at 25°C; Δn): Measurements were made using light with a wavelength of 589 nm and an Abbe refractometer equipped with a polarizing plate attached to an eyepiece. After rubbing the surface of the main prism in one direction, a sample was dropped onto the main prism. The refractive index (n∥) was measured when the direction of polarized light was parallel to the rubbing direction. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the rubbing direction. The value of optical anisotropy (Δn) was calculated from the equation Δn = n∥ - n⊥.

[0225] (8) Resistivity (ρ; measured at 25°C; Ωcm): 1.0 mL of sample was poured into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current was measured after 10 seconds. The resistivity was calculated using the following equation: (resistivity) = {(voltage) × (capacity of container)} / {(DC current) × (dielectric constant of vacuum)}.

[0226] (9) Voltage holding ratio (VHR-1; measured at 25°C; %): The TN element used for the measurement had a polyimide alignment film, and the distance between the two glass substrates (cell gap) was 5 μm. After placing a sample inside the element, it was sealed with an adhesive that hardens under ultraviolet light. A pulse voltage (5 V for 60 microseconds) was applied to the element to charge it. The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit period was calculated. Area B was the area when there was no decay. The voltage holding ratio was expressed as the percentage of area A to area B.

[0227] (10) Voltage holding ratio (VHR-2; measured at 80°C; %): The voltage holding ratio was measured in the same manner as above, except that the temperature was 80°C instead of 25°C. The results were indicated by the symbol VHR-2.

[0228] (11) Flicker rate (measured at 25°C; %): A Yokogawa Electric Corporation Multimedia Display Tester 3298F was used for the measurement. An LED was used as the light source. A sample was placed in a normally black mode FFS element with a cell gap of 3.5 μm between the two glass substrates and an anti-parallel rubbing direction. This element was sealed using an adhesive that hardens with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While this voltage was being applied to the element, the sensor unit was brought close to the element, and the displayed flicker rate was read.

[0229] The measurement methods for physical properties may differ between samples with positive and negative dielectric anisotropy. The measurement methods for samples with positive dielectric anisotropy are described in Measurement (12a) to Measurement (16a). For samples with negative dielectric anisotropy, the measurement methods are described in Measurement (12b) to Measurement (16b).

[0230] (12a) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s; sample with positive dielectric anisotropy): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device with a twist angle of 0° and a cell gap of 5 μm between the two glass substrates. A voltage was applied to this device in steps of 0.5 V from 16 V to 19.5 V. After a 0.2-second period without voltage application, a single square wave (rectangular pulse; 0.2 seconds) followed by no voltage application (2 seconds) was applied repeatedly. The peak current and peak time of the transient current generated by this voltage application were measured. The rotational viscosity was calculated from these measurements and equation (8) on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy required for this calculation was determined by the method described below using the device used to measure the rotational viscosity.

[0231] (12b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s; sample with negative dielectric anisotropy): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a VA cell with a cell gap of 20 μm between two glass substrates. Voltage was applied to this cell in 1-V increments from 39 V to 50 V. After a 0.2-second period without voltage application, voltage application was repeated under the following conditions: a single square wave (rectangular pulse; 0.2 seconds) followed by no voltage application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The rotational viscosity value was obtained from these measurements and equation (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation was measured in the dielectric anisotropy section below.

[0232] (13a) Dielectric anisotropy (Δε; measured at 25°C; sample with positive dielectric anisotropy): A sample was placed in a TN device with a cell gap of 9 μm between two glass substrates and a twist angle of 80°. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The dielectric anisotropy value was calculated from the equation Δε = ε∥ - ε⊥.

[0233] (13b) Dielectric anisotropy (Δε; measured at 25°C; sample with negative dielectric anisotropy): The dielectric anisotropy value was calculated from the equation Δε = ε∥ - ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows: 1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a thoroughly cleaned glass substrate. After rotating the glass substrate with a spinner, it was heated at 150°C for 1 hour. The sample was placed in a VA element with a cell gap of 4 μm between the two glass substrates, and the element was sealed with a UV-curable adhesive. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. 2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a thoroughly cleaned glass substrate. After baking the glass substrate, the resulting alignment film was rubbed. The sample was placed in a TN device with a cell gap of 9 μm between the two glass substrates and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds.

[0234] (14a) Elastic constant (K; measured at 25°C; pN; sample with positive dielectric anisotropy): Measurements were performed using an HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. The sample was placed in a horizontally aligned device with a cell gap of 20 μm between the two glass substrates. A charge of 0 V to 20 V was applied to this device, and the capacitance (C) and applied voltage (V) were measured. These measurements were fitted using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the K was calculated from equation (2.99). 11 and K. 33 Next, we use the value of K 11 and K. 33 Using the value of K 22 The elastic constant K was calculated as follows: 11 , K. 22 , and K. 33 The results are expressed as the average value of

[0235] (14b) Elastic constant (K 11 and K. 33 Measured at 25°C; pN; Sample with negative dielectric anisotropy): Measurements were performed using an EC-1 elastic constant measuring instrument manufactured by Toyo Corporation. The sample was placed in a vertically aligned device with a cell gap of 20 μm between the two glass substrates. A voltage of 20 V to 0 V was applied to the device, and the capacitance (C) and applied voltage (V) were measured. These values ​​were fitted using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the elastic constant was obtained from equation (2.100).

[0236] (15a) Threshold voltage (Vth; measured at 25°C; V; sample with positive dielectric anisotropy): Measurements were performed using an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The sample was placed in a normally white mode TN device with a cell gap of 0.45 / Δn (μm) between the two glass substrates and a twist angle of 80°. The voltage applied to the device (32 Hz, square wave) was increased in steps of 0.02 V from 0 V to 10 V. During this increase, light was irradiated perpendicularly to the device, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created, with the transmittance at the maximum light amount being 100% and the transmittance at the minimum light amount being 0%. The threshold voltage was expressed as the voltage at which the transmittance reached 90%.

[0237] (15b) Threshold voltage (Vth; measured at 25°C; V; sample with negative dielectric anisotropy): Measurements were performed using an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The sample was placed in a normally black mode VA device with a cell gap of 4 μm between two glass substrates and an antiparallel rubbing direction, and the device was sealed with a UV-curable adhesive. The voltage applied to the device (60 Hz, square wave) was increased in steps of 0.02 V from 0 V to 20 V. During this increase, light was irradiated perpendicularly onto the device, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created, with the maximum light amount representing 100% transmittance and the minimum light amount representing 0% transmittance. The threshold voltage was expressed as the voltage at which the transmittance reached 10%.

[0238] (16a) Response time (τ; measured at 25°C; ms; sample with positive dielectric anisotropy): Measurements were performed using an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. 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 device with a cell gap of 5.0 μm between the two glass substrates and a twist angle of 80°. A square wave (60 Hz, 5 V, 0.5 s) was applied to the device. Light was irradiated perpendicularly to the device, and the amount of light transmitted through the device was measured. The maximum light intensity was considered to be 100% transmittance, and the minimum light intensity was considered to be 0% transmittance. The rise time (τr; milliseconds) was the time required for the transmittance to change from 90% to 10%. The fall time (τf; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is expressed as the sum of the rise time and fall time thus calculated.

[0239] (16b) Response time (τ; measured at 25°C; ms; sample with negative dielectric anisotropy): Measurements were performed using an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a PVA device in a normally black mode with a cell gap of 3.2 μm between the two glass substrates and an antiparallel rubbing direction. The device was sealed with a UV-curable adhesive. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, and then a voltage of 5.6 V was applied while maintaining a 23.5 mW / cm² illumination. 2 The device was irradiated with ultraviolet light for 8 minutes. A square wave (60 Hz, 10 V, 0.5 seconds) was applied to the device. Light was irradiated perpendicularly to the device, and the amount of light transmitted through the device was measured. The maximum amount of light was considered to be 100% transmittance, and the minimum amount of light was considered to be 0% transmittance. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

[0240] [Synthesis Example 1] Synthesis of compound (a-71)

[0241] [ka]

[0242] Step 1: Synthesis of compound (t-2) Commercially available compound (t-1) (10.0 g, 68.2 mmol), iodoethane (12.8 g, 81.9 mmol), and potassium carbonate (18.9 g, 136 mmol) were dissolved in N,N-dimethylformamide (100 mL) and stirred at 70–80°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 4:1) to obtain compound (t-2) (9.83 g, 56.3 mmol) as a colorless liquid.

[0243] Step 2: Synthesis of compound (t-4) Compound (t-3) (10.0 g, 63.7 mmol), 1-iodobutane (14.1 g, 76.4 mmol), and potassium carbonate (17.6 g, 127 mmol) were dissolved in DMF (100 mL) and stirred at 70–80°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (t-4) (13.2 g, 61.9 mmol) as a yellow liquid.

[0244] Step 3: Synthesis of compound (t-5) Compound (t-4) (13.2 g, 61.9 mmol) was dissolved in 2-propanol (140 mL), and 5% palladium-carbon (0.660 g) was added, followed by hydrogenation. After filtering off the catalyst, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (t-5) (4.50 g, 24.6 mmol) as a brown solid.

[0245] Step 4: Synthesis of compound (t-6) Compound (t-2) (4.29 g, 24.6 mmol), compound (t-5) (4.50 g, 24.6 mmol), sodium t-butoxide (3.54 g, 36.8 mmol), and Pd(amphos)Cl (0.174 g) were dissolved in xylene (50 mL) and stirred at 110 °C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 4:1) to obtain compound (t-6) (4.67 g, 14.5 mmol) as a pink liquid.

[0246] Step 5: Synthesis of compound (a-71) Compound (t-6) (4.67 g, 14.5 mmol) was dissolved in acetic acid (80 mL), palladium acetate (3.91 g, 17.4 mmol) was added, and the mixture was heated to reflux for 50 minutes. After the reaction was completed, the mixture was cooled to room temperature, filtered through Florisil / Celite, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (a-71) (1.61 g, 5.04 mmol) as a colorless solid.

[0247] 1H-NMR(CDCl3;δppm): 8.13(brs,J=8.13Hz,1H), 7.58(d,J=8.6Hz,2H), 6.89(ddd,J=7.9,7.8,1.1Hz,2H), 4.21(q,J=7.0Hz,2 H), 4.14(t,J=6.6Hz,2H), 1.84(quin,J=6.7Hz,2H), 1.54(sext,J=7.5Hz,2H), 1.48(t,J=7.1Hz,3H), 1.00(t,J=7.4Hz,3H).

[0248] Phase transition temperature: C 92.4 I. Upper limit temperature (NI) = -45.7℃; Dielectric constant anisotropy (Δε) = -1.48; Optical anisotropy (Δn) = 0.147; Viscosity (η) = 127.4 mPa s.

[0249] [Synthesis Example 2] Synthesis of compound (a-74)

[0250] [ka]

[0251] Compound (a-71) (0.710 g, 2.22 mmol) was dissolved in N,N-dimethylformamide (10 mL), cooled with ice, and sodium hydride (0.196 g, 4.49 mmol) was added portionwise and stirred for 30 minutes. Methyl iodide (0.821 g, 2.59 mmol) was added dropwise, and the mixture was stirred for 1 hour while cooling with ice. After the reaction was complete, the mixture was poured into water and extracted three times with toluene. The combined organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (a-74) (0.52 g, 1.56 mmol) as a colorless solid.

[0252] 1H-NMR(CDCl3;δppm):7.56(d,J=8.5Hz,2H), 6.86(dd,J=7.8,7.8,1.4Hz,1H), 4.21(s,3H), 4.20(q,J=7.0Hz,2H), 4.1 2(t,J=6.6Hz,2H), 1.84(quin,J=6.6Hz,2H), 1.55(sext,J=7.4Hz,2H), 1.48(t,J=7.0Hz,3H), 1.00(t,J=7.4Hz,3H).

[0253] Phase transition temperature: C 71.0 I. Upper limit temperature (NI) = 37.0℃; dielectric constant anisotropy (Δε) = -3.14; optical anisotropy (Δn) = 0.194; viscosity (η) = 54.1mPa·s.

[0254] [Synthesis Example 3] Synthesis of compound (a-5)

[0255] [ka]

[0256] Step 1: Synthesis of compound (t-8) Commercially available compound (t-7) (12.5 g, 64.1 mmol) and potassium carbonate (11.6 g, 83.4 mmol) were dissolved in N,N-dimethylformamide (125 mL) and heated to 60 °C. A solution of iodoethane (11.2 g, 70.6 mmol) in N,N-dimethylformamide (20 mL) was added dropwise, and the mixture was stirred at 60 °C for 6.5 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with 1N aqueous NaOH solution and water, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by short-course silica gel chromatography (heptane) to obtain compound (t-8) (12.5 g, 56.9 mmol) as a colorless liquid.

[0257] Step 2: Synthesis of compound (t-9) Commercially available compound (t-7) (12.5 g, 65.5 mmol), 1-bromobutane (9.86 g, 72.0 mmol), and potassium carbonate (11.8 g, 85.1 mmol) were dissolved in N,N-dimethylformamide (125 mL) and stirred at 80 °C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with 2N aqueous NaOH and water, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by short silica gel chromatography (heptane) to obtain compound (t-9) (14.2 g, 57.5 mmol) as a pale brown liquid.

[0258] Step 3: Synthesis of compound (t-10) Compound (t-9) (14.0 g, 56.7 mmol), benzylamine (7.29 g, 68.0 mmol), and sodium t-butoxide (8.17 g, 85.0 mmol) were dissolved in toluene (196 mL) and degassed under reduced pressure. Palladium(0) bis(dibenzylideneacetone) (0.652 g) and 2-(di-t-butylphosphino)biphenyl (0.676 g, 2.27 mmol) were added, and the mixture was heated and stirred at 60 °C. After the heat generation subsided, the mixture was gradually heated to the reflux temperature and refluxed for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:ethyl acetate=9:1) to obtain compound (t-10) (15.0 g, 54.9 mmol) as a brown liquid.

[0259] Step 4: Synthesis of compound (t-11) Compound (t-10) (11.0 g, 40.2 mmol), compound (t-8) (8.82 g, 40.2 mmol), sodium t-butoxide (5.80 g, 60.4 mmol), and Pd(amphos)Cl (0.0285 g) were dissolved in toluene (330 mL) and heated under reflux for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (t-11) (11.6 g, 28.2 mmol) as a colorless liquid.

[0260] Step 5: Synthesis of compound (t-12) Compound (t-11) (11.6 g, 28.2 mmol) was dissolved in toluene (30 mL) and 2-propanol (60 mL), and palladium hydroxide (0.580 g) was added and hydrogenated. After filtering off the catalyst, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate = 4:1) to obtain compound (t-12) (7.70 g, 24.0 mmol) as a brown liquid.

[0261] Step 6: Synthesis of compound (a-5) Compound (t-12) (6.70 g, 20.9 mmol) was dissolved in acetic acid (110 mL), palladium acetate (5.61 g, 25.0 mmol) was added, and the mixture was heated to reflux for 50 minutes. After the reaction was completed, the mixture was cooled to room temperature, filtered through Florisil / Celite, poured into water, and extracted three times with toluene. The combined organic layer was washed with water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (a-5) (1.34 g, 4.20 mmol) as a colorless solid.

[0262] 1H-NMR(CDCl3;δppm): 7.80(brs,1H), 7.56(dd,J=11.0,2.1Hz,2H), 6.94(d,J=6.9Hz,1H), 4.15(q,J=7.0Hz,2H), 4. 08(t,J=6.6Hz,2H), 1.86(quin,J=6.6,2H), 1.54(sext,J=7.5Hz,2H), 1.50(t,J=7.0Hz,3H), 1.00(t,J=7.4Hz,3H).

[0263] Phase transition temperature: C 217.3 I. Upper limit temperature (NI) = 71.0℃; dielectric constant anisotropy (Δε) = -22.5; optical anisotropy (Δn) = 0.220; viscosity (η) = 202.9mPa·s.

[0264] [Synthesis Example 4] Synthesis of compound (a-11)

[0265] [ka]

[0266] Compound (a-5) (0.26 g, 0.81 mmol) was dissolved in N,N-dimethylformamide (5.0 mL), cooled with ice, and sodium hydride (0.0718 g, 1.64 mmol) was added portionwise and stirred for 30 minutes. Methyl iodide (0.301 g, 2.11 mmol) was added dropwise, and the mixture was stirred for 3 hours while cooling with ice. After the reaction was complete, the mixture was poured into water and extracted three times with toluene. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 1:1) to obtain compound (a-11) (0.20 g, 0.600 mmol) as a colorless solid.

[0267] 1H-NMR(CDCl3;δppm):7.58(dd,J=11.0,2.3Hz,2H), 6.86(d,J=6.8Hz,1H), 4.21(q,J=7.0Hz,2H), 4.13(t,J=6.6Hz, 2H), 3.75(s,3H), 1.88(quin,J=6.6Hz,2H), 1.56(sext,J=7.5Hz,2H), 1.52(t,J=7.0Hz,3H), 1.01(t,J=7.4Hz,3H).

[0268] Phase transition temperature: C 142.5 I.; As only 3% was dissolved, physical properties could not be measured.

[0269] [Synthesis Example 5] Synthesis of compound (a-36)

[0270] [ka]

[0271] Step 1: Synthesis of compound (t-14) Commercially available compound (t-13) (25.0 g, 120 mmol), iodoethane (20.5 g, 132 mmol), and potassium carbonate (21.5 g, 156 mmol) were dissolved in N,N-dimethylformamide (250 mL) and stirred at 80 °C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with 2N aqueous NaOH and water, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by short silica gel chromatography (toluene) to obtain compound (t-14) (25.8 g, 109 mmol) as a brown liquid.

[0272] Step 2: Synthesis of compound (t-16) Compound (t-15) (18.0 g, 72.8 mmol), benzylamine (9.37 g, 87.4 mmol), and sodium t-butoxide (10.5 g, 109 mmol) were dissolved in toluene (252 mL) and degassed under reduced pressure. Palladium(0) bis(dibenzylideneacetone) (0.838 g) and 2-(di-t-butylphosphino)biphenyl (0.870 g, 2.91 mmol) were added, and the mixture was heated and stirred at 60 °C. After the heat generation subsided, the mixture was gradually heated to the reflux temperature and refluxed for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:ethyl acetate=9:1) to obtain compound (t-16) (15.6 g, 57.1 mmol) as a brown liquid.

[0273] Step 3: Synthesis of compound (t-17) Compound (t-14) (13.0 g, 54.9 mmol), compound (t-16) (15.0 g, 54.9 mmol), and sodium t-butoxide (7.91 g, 82.3 mmol) were dissolved in toluene (450 mL), degassed under reduced pressure, and Pd(amphos)Cl (0.0389 g) was added. The mixture was heated and stirred at 60 °C. After the heat generation subsided, the temperature was gradually increased to the reflux temperature and refluxed for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:toluene = 2:1) to obtain compound (t-17) (15.0 g, 34.9 mmol) as a brown liquid.

[0274] Step 4: Synthesis of compound (t-18) Compound (t-17) (15.0 g, 34.9 mmol) was dissolved in toluene (37.5 mL) and 2-propanol (75 mL), and palladium hydroxide (0.75 g) was added and hydrogenated. After filtering off the catalyst, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (t-18) (13.1 g, 38.6 mmol) as a pale brown liquid.

[0275] Step 5: Synthesis of compound (a-36) Compound (t-18) (12.0 g, 35.4 mmol) and potassium carbonate (0.489 g, 3.54 mmol) were dissolved in pivalic acid (120 mL), palladium acetate (0.794 g) was added, and the mixture was heated under reflux in air for 16 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into water, and extracted three times with toluene. The combined organic layer was neutralized with sodium carbonate, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane:ethyl acetate = 3:1) to obtain compound (a-36) (1.50 g, 4.45 mmol) as a colorless solid.

[0276] 1 H-NMR(CDCl3;δppm):7.83(brs,1H), 7.74(d,J=10.5Hz,1H), 6.94(d,J=6.5Hz,1H), 6.72(d,J=5.5Hz,1H), 4.16(q,J=7.0Hz) ,2H), 4.08(t,J=6.5Hz,2H), 1.86(quin,J=7.1,2H), 1.55(sext,J=7.5Hz,2H), 1.50(t,J=7.0Hz,3H), 1.00(t,J=7.5Hz,3H).

[0277] Phase transition temperature: C 187.5 I. Upper limit temperature (NI) = 84.3℃; dielectric anisotropy (Δε) = -21.5; optical anisotropy (Δn) = 0.187; viscosity (η) = 149.4 mPa s.

[0278] [Comparative experiment] The dielectric anisotropy of compound (a-5) was compared with that of comparative compound (Ref-1) as follows. Comparative compound (Ref-1) is compound (1-2-5) described in paragraph

[0143] of WO 2015 / 129412. Synthesis was carried out according to the method described in paragraphs

[0143] to

[0154] of WO 2015 / 129412. The dielectric anisotropy (Δε) of compound (a-5) obtained in the synthesis of compound (3) was compared with that of the comparative compound (Ref-1). It was found that compound (a-5) had a much larger negative dielectric anisotropy. Therefore, it can be concluded that compound (1) is superior to similar compounds.

[0279] [Table 2]

[0280] The compounds shown below can be synthesized by referring to the methods described in the synthesis examples and the section "2. Synthesis of Compound (1)".

[0281] [ka]

[0282] [ka]

[0283] [ka]

[0284] [ka]

[0285] [ka]

[0286]

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[0287]

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[0288]

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[0289]

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[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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[0303]

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[0304]

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[0305]

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[0306]

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[0307]

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[0308]

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[0309]

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[0310]

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[0311]

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[0312]

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[0313]

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[0314]

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[0315]

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[0316]

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[0317]

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[0318]

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[0319]

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[0320]

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[0321]

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[0322]

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[0323]

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[0324]

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[0325]

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[0326]

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[0327]

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[0328]

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[0329] The compounds shown below were synthesized by referring to the methods described in the synthesis examples and the section "2. Synthesis of compound (1)".

[0330] [ka]

[0331] 1 H-NMR(CDCl3;δppm): 7.79(brs,1H), 7.62(d,J=10.9Hz,1H), 7.50(d,J=10.3Hz,1H), 7.15(d,J=6.3Hz,1H), 6.94(d,J=6.9Hz,1H), 4. 17(q,J=6.9Hz,2H), 2.76(t,J=7.5Hz,2H), 1.67(quin,J=7.5Hz,2H), 1.51(t,J=6.9Hz,3H), 1.40-1.32(m,4H), 0.90(t,J=7.5Hz,3H).

[0332] The physical properties of the compound (a-4) were as follows: Transition temperature: C 173.7 I. Upper limit temperature (T NI )=47.3℃; Optical anisotropy (Δn)=0.187; Dielectric anisotropy (Δε)=-15.18; Viscosity (η)=258.2mPa·s.

[0333] [ka]

[0334] 1H-NMR (CDCl3; δppm): 7.64(d,J=11.5Hz,1H), 7.53(d,J=9.7Hz,1H), 7.10(d,J=6.3Hz,1H), 6.87(d,J=6.9Hz,1H), 4.22(q,J=6.9Hz, 2H), 3.77(s,3H), 2.80(t,J=7.5Hz,2H), 1.70(quin,J=7.5Hz,2H), 1.53(t,J=6.9Hz,3H), 1.41-1.35(m,4H), 0.91(t,J=7.5Hz,3H).

[0335] The physical properties of compound (a-9) are as follows: Transition temperature: C 73.4 I. Upper limit temperature (T NI ) = -44.7°C; optical anisotropy (Δn) = 0.127; dielectric anisotropy (Δε) = -7.72; viscosity (η) = 145.7 mPa·s.

[0336]

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[0337] 1 H-NMR (CDCl3; δppm): 7.79 (brs, 1H), 7.57 (d, J = 4.0Hz, 1H), 7.55 (d, J = 3.5Hz, 1H), 6 .95(d,J=6.3Hz,1H), 6.94(d,J=6.3Hz,1H), 4.17(q,J=6.9Hz,2H), 3.88(d,J=6.3Hz ,2H), 1.98-1.94(m,2H), 1.87-1.80(m,3H), 1.51(t,J=6.9Hz,3H), 1.37-1,16(m,5H ), 1.09(dq,J=2.9,12.6Hz,2H), 0.96(dq,J=2.9,12.6Hz,2H), 0.89(t,J=7.5Hz,3H).

[0338] The physical properties of compound (b-7) are as follows: Transition temperature: C 233.1 I. Upper limit temperature (T NI) = 114.3°C; optical anisotropy (Δn) = 0.187; dielectric anisotropy (Δε) = -10.5; viscosity (η) = 99.4 mPa·s.

[0339]

change

[0340] 1 H-NMR (CDCl3; δppm): 7.59(d,J=3.5Hz,1H), 7.57(d,J=4.0Hz,1H), 6.87(d,J=6.9H z,1H), 6.85(d,J=6.9Hz,1H), 4.21(q,J=6.9Hz,2H), 3.91(d,J=6.3Hz,2H), 3.75(s, 3H), 2.00-1.96(m,2H), 1.91-1.81(m,3H), 1.52(t,J=6.9Hz,3H), 1.37-1,17(m,5H) , 1.11(dq,J=3.5,12.6Hz,2H), 0.97(dq,J=3.5,12.6Hz,2H), 0.89(t,J=7.5Hz,3H).

[0341] The physical properties of compound (b-19) are as follows: Transition temperature: C 170.9 I. Upper limit temperature (T NI ) = 84.3°C; optical anisotropy (Δn) = 0.187; dielectric anisotropy (Δε) = -11.5; viscosity (η) = 145.4 mPa·s.

[0342] 2. Examples of compositions The present invention will be explained in more detail with reference to examples. The examples are typical examples, and therefore the present invention is not limited by the examples. For example, the present invention includes the compositions of the Use Examples as well as mixtures of the compositions of Use Example 1 and Use Example 2. The present invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples. The compounds in the Use Examples are represented by symbols based on the definitions in Table 2 below. In Table 2, the configuration of 1,4-cyclohexylene is trans. In the Use Examples, the number in parentheses following the symbol indicates the chemical formula to which the compound belongs. The symbol (-) indicates a liquid crystal compound other than compounds (1) to (15). The proportion (percentage) of the liquid crystal compound is a weight percentage (wt%) based on the weight of the liquid crystal composition without additives. Finally, the physical properties of the compositions are summarized. The physical properties were measured according to the methods described above, and the measured values ​​are reported directly (without extrapolation).

[0343] [Table 3]

[0344] [Usage example 1] 2O-Ca(3F,6F)-O4 (a-5) 3% 1-BB-3 (2-8) 7% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 3-HHB-3 (3-1) 14% 3-HHB-F (22-1) 4% 2-HHB(F)-F (22-2) 7% 3-HHB(F)-F (22-2) 7% 5-HHB(F)-F (22-2) 7% 3-HHB(F,F)-F (22-3) 2% 3-HHEB-F (22-10) 4% 5-HHEB-F (22-10) 4% 2-HB-C (24-1) 5% 3-HB-C (24-1) 12% NI = 95.7 °C; η = 22.1 mPa·s; Δn = 0.112; Δε = 3.8.

[0345] [Example of Use 2] 4O-Ca(1F,8F)-O2 (a-71) 8% 3-HH-4 (2-1) 12% 7-HB-1 (2-5) 3% 5-HB-O2 (2-5) 2% 5-HBB(F)B-2 (4-5) 7% 5-HBB(F)B-3 (4-5) 6% 3-HB-CL (21-2) 5% 3-HHB(F,F)-F (22-3) 3% 3-HBB(F,F)-F (22-24) 30% 5-HBB(F,F)-F (22-24) 24% NI = 73.6 °C; η = 32.5 mPa·s; Δn = 0.125; Δε = 5.2.

[0346] [Example of Use 3] 2O-Ca(3F,6F,9Me)-O4 (a-11) 3% 1V2-HH-1 (2-1) 3% 1V2-HH-3 (2-1) 4% 7-HB(F,F)-F (21-4) 3% 2-HHB(F)-F (22-2) 10% 3-HHB(F)-F (22-2) 10% 5-HHB(F)-F (22-2) 7% 2-HBB-F (22-22) 4% 3-HBB-F (22-22) 4% 5-HBB-F (22-22) 3% 2-HBB(F)-F (22-23) 9% 3-HBB(F)-F (22-23) 9% 5-HBB(F)-F (22-23) 16% 3-HBB(F,F)-F (22-24) 5% 5-HBB(F,F)-F (22-24) 10%

[0347] [Example of Use 4] 4O-Ca(1F,8F,9Me)-O2 (a-74) 10% 2-HH-3 (2-1) 4% 3-HH-4 (2-1) 12% 1O1-HBBH-5 (4-1) 3% 5-HB-CL (21-2) 16% 3-HHB-F (22-1) 4% 3-HHB-CL (22-1) 3% 4-HHB-CL (22-1) 4% 3-HHB(F)-F (22-2) 5% 4-HHB(F)-F (22-2) 4% 5-HHB(F)-F (22-2) 9% 7-HHB(F)-F (22-2) 8% 5-HBB(F)-F (22-23) 4% 3-HHBB(F,F)-F (23-6) 2% 4-HHBB(F,F)-F (23-6) 3% 5-HHBB(F,F)-F (23-6) 3% 3-HH2BB(F,F)-F (23-15) 3% 4-HH2BB(F,F)-F (23-15) 3% NI = 106.7℃; η = 21.6mPa·s; Δn = 0.101; Δε = 2.7.

[0348] [Example of Use 5] 2O-Ca(3F,4F,6F)-O4 (a-36) 2% V-HBB-2 (3-4) 10% 1O1-HBBH-4 (4-1) 4% 1O1-HBBH-5 (4-1) 2% 3-HHB(F,F)-F (22-3) 9% 3-H2HB(F,F)-F (22-15) 8% 4-H2HB(F,F)-F (22-15) 8% 5-H2HB(F,F)-F (22-15) 8% 3-HBB(F,F)-F (22-24) 11% 5-HBB(F,F)-F (22-24) 20% 3-H2BB(F,F)-F (22-27) 10% 5-HHBB(F,F)-F (23-6) 3% 3-HH2BB(F,F)-F (23-15) 3% 5-HHEBB-F (23-17) 2% NI = 103.0 °C; η = 34.3 mPa·s; Δn = 0.123; Δε = 7.8.

[0349] [Example of Use 6] 2O-Ca(3F,4F,6F)-4 (a-232) 3% 5-HBBH-3 (4-1) 3% 3-HB(F)BH-3 (4-2) 3% 5-HB-F (21-2) 9% 6-HB-F (21-2) 9% 7-HB-F (21-2) 7% 2-HHB-OCF3 (22-1) 7% 3-HHB-OCF3 (22-1) 7% 4-HHB-OCF3 (22-1) 7% 5-HHB-OCF3 (22-1) 5% 3-HHB(F,F)-OCF2H (22-3) 4% 3-HHB(F,F)-OCF3 (22-3) 5% 3-HH2B-OCF3 (22-4) 4% 5-HH2B-OCF3 (22-4) 4% 3-HH2B(F)-F (22-5) 3% 3-HBB(F)-F (22-23) 10% 5-HBB(F)-F (22-23) 10%

[0350] [Usage Example 7] 2O-Ca(3F,6F)-5 (a-4) 3% 2-HH-5 (2-1) 5%<0002​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​3-H4HB(F,F)-CF3 (22-21) 8% 5-H4HB(F,F)-CF3 (22-21) 10% 2-H2BB(F)-F (22-26) 5% 3-H2BB(F)-F (22-26) 10% 3-HBEB(F,F)-F (22-39) 5%

[0352] [Example of Use 9] 2O-Ca(6F)-5 (a-234) 3% 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 5% 3-HB-O2 (2-5) 15% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 5-HB-CL (21-2) 14% 7-HB(F,F)-F (21-4) 3% 2-HHB(F)-F (22-2) 7% 3-HHB(F)-F (22-2) 7% 5-HHB(F)-F (22-2) 7% 3-HHB(F,F)-F (22-3) 6% 3-H2HB(F,F)-F (22-15) 5% 4-H2HB(F,F)-F (22-15) 5% <{}

[0353] <{} [Example of Use 10] 5-HCa(3F,6F)-3 (b-1) 3% 3-HH-4 (2-1) 9% 3-HH-5 (2-1) 10% 3-HHB-3 (3-1) 10% 5-HB-CL (21-2) 3% 7-HB(F)-F (21-3) 7% 2-HHB(F,F)-F (22-3) 4% 3-HHB(F,F)-F (22-3) 5% 3-HHEB-F (22-10) 8% 5-HHEB-F (22-10) 8% 3-HHEB(F,F)-F (22-12) 10% 4-HHEB(F,F)-F (22-12) 5% 3-GHB(F,F)-F (22-109) 5% 4-GHB(F,F)-F (22-109) 6% 5-GHB(F,F)-F (22-109) 7% NI = 82.6℃; η = 21.7mPa·s; Δn = 0.068; Δε = 5.9.

[0354] [Example of Use 11] 3-H1OCa(3F,6F)-3 (b-227) 3% 3-HH-VFF (2-1) 5% 5-HH-VFF (2-1) 25% 2-BTB-1 (2-10) 7% 3-HHB-1 (3-1) 4% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 4% 3-H2BTB-4 (3-17) 4% 3-HB-C (24-1) 18% 1V2-BEB(F,F)-C (24-15) 6%

[0355] [Example of Use 12] [[ID=​​​​​​​​​​​​​3-HHEH-5 (3-13) 3% 1V2-BB―F (21-1) 3% 3-BB(F,F)XB(F,F)-F (22-97) 6% 3-BB(2F,3F)XB(F,F)-F (22-114) 3% 3-HHBB(F,F)-F (23-6) 3% 3-HBBXB(F,F)-F (23-32) 3% 5-HB(F)B(F,F)XB(F,F)-F (23-41) 5% 3-BB(F)B(F,F)XB(F,F)-F (23-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (23-47) 5% 5-BB(F)B(F,F)XB(F,F)-F (23-47) 3% NI = 81.0 °C; η = 18.0 mPa·s; Δn = 0.102; Δε = 3.5.

[0356] [Use Example 13] 4O-Ca(1F,8F)-O2 (a-71) 10% 3-HH-V (2-1) 31% 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 (21-1) 3% 3-BB(F,F)XB(F,F)-F (22-97) 3% 3-HHXB(F,F)-CF3 (22-100) 3% 3-GB(F,F)XB(F,F)-F (22-113) 2% 3-GB(F)B(F,F)-F (22-116) 2% 3-HHBB(F,F)-F (23-6) 3% 3 - BB(F)B(F,F)XB(F,F) - F (23 - 47) 3% 4 - BB(F)B(F,F)XB(F,F) - F (23 - 47) 5% 5 - BB(F)B(F,F)XB(F,F) - F (23 - 47) 3% 3 - GB(F)B(F,F)XB(F,F) - F (23 - 57) 3% NI = 72.3℃; η = 19.9mPa·s; Δn = 0.106; Δε = 3.7.

[0357] [Example of Use 14] 2O - Ca(3F,6F,9Me) - O4 (a - 11) 5% 3 - HH - V (2 - 1) 30% 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) 3% 3 - HHEH - 5 (3 - 13) 3% 1V2 - BB―F (21 - 1) 3% 3 - BB(F,F)XB(F,F) - F (2); 97) 4% 3 - GB(F,F)XB(F,F) - F (22 - 113) 3% 3 - HHBB(F,F) - F (23 - 6) 3% 3 - HBB(F,F)XB(F,F) - F (23 - 38) 3% 3 - BB(F)B(F,F)XB(F) - F (23 - 46) 3% 4 - BB(F)B(F,F)XB(F,F) - F (23 - 47) 3% [[ID=]]5 - BB(F)B(F,F)XB(F,F) - F (23 - 47) 3% 3 - GB(F)B(F,F)XB(F,F) - F (23 - 57) 5% 4 - GB(F)B(F,F)XB(F,F) - F (2); 57) 3% 5-GB(F)B(F,F)XB(F,F)-F (23-57) 2%

[0358] [Example of Use 15] 4O-Ca(1F,8F,9Me)-O2 (a-74) 9% 3-HH-V (2-1) 25% 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 (21-1) 4% 3-BB(F)B(F,F)-F (22-69) 3% 3-BB(F,F)XB(F,F)-F (22-97) 5% ​​​​​​​​​​​​​​​​​​​​​​​​​​​ 3-HH-V1 (2-1) 5% 3-HHB-1 (3-1) 4% V-HHB-1 (3-1) 5% V2-BB(F)B-1 (3-6) 5% 3-HHEH-5 (3-13) 3% 1V2-BB―F (21-1) 3% 3-BB(F)B(F,F)-CF3 (22-69) 3% 3-BB(F,F)XB(F,F)-F (22-97) 5% 3-HHXB(F,F)-F (22-100) 5% 3-GB(F,F)XB(F,F)-F (22-113) 3% 3-GB(F)B(F)-F (22-115) 3% 3-HHBB(F,F)-F (23-6) 3% 5-HB(F)B(F,F)XB(F,F)-F (23-41) 3% 3-GB(F)B(F,F)XB(F,F)-F (23-57) 3% 3-GBB(F,F)XB(F,F)-F (23-58) 3% 4-GBB(F,F)XB(F,F)-F (23-58) 3% 5-GBB(F,F)XB(F,F)-F (23-58) 3% 3-GB(F)B(F)B(F)-F (23-59) 3% NI = 81.9 °C; η = 19.0 mPa·s; Δn = 0.096; Δε = 5.4.

[0360] [Example of Use 17] 2O-Ca(3F,4F,6F)-4 (a-232) 4% 3-HH-4 (2-1) 5% 3-HB-O1 (2-5) 15% 3-HHB-1 (3-1) 6% 3-HB(2F,3F)-O2 (5-1) 12% 5-HB(2F,3F)-O2 (5-1) 12% 2-HHB(2F,3F)-1 (6-1) 8% 3-HHB(2F,3F)-1 (6-1) 12% 3-HHB(2F,3F)-O2 (6-1) 13% 5-HHB(2F,3F)-O2 (6-1) 13%

[0361] [Example of Use 18] 2O-Ca(3F,6F)-5 (a-4) 2% 2-HH-5 (2-1) 3% 3-HH-4 (2-1) 15% 3-HH-5 (2-1) 4% 3-HB-O2 (2-5) 12% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 4% 3-HHB-O1 (3-1) 3% 3-H2B(2F,3F)-O2 (5-4) 15% 5-H2B(2F,3F)-O2 (5-4) 13% 2-HBB(2F,3F)-O2 (6-7) 3% 3-HBB(2F,3F)-O2 (6-7) 9% 5-HBB(2F,3F)-O2 (6-7) 9% 3-HHB(2F,3Cl)-O2 (6-12) 5%<00,02681>

[0362] [Example of Use 19][[ID=4,3]] 2O-Ca(3F,4F)-4 (a-233) 4% 2-HH-3 (2-1) 16% 2-HH-5 (2-1) 5% 3-HH-4 (2-1) 9% 3-HB-O2 (2-5) 2% 1-BB-3 (2-‘8) ‘9% 3-HHB-1 (3-1) 5% 3-HHB-O1 (3-1) 3% 5-B(F)BB-2 (3-8) 2% 3-BB(2F,3F)-O2 (5-3) 9% It should be noted that there seems to be an unclear or incorrect "1-BB-3 (2-8) 9%" and "5-B(F)BB-2 (3-8) 2%" in the original text where the format might be a bit unusual. This might need further clarification in the source context. 5-BB(2F,3F)-O2 (5-3) 6% 2-HH1OB(2F,3F)-O2 (6-5) 13% 3-HH1OB(2F,3F)-O2 (6-5) 17%

[0363] [Example 20] 2O-Ca(6F)-5 (a-234) 3% 2-HH-3 (2-1) 16% 7-HB-1 (2-5) 10% 5-HB-O2 (2-5) 8% 5-HBB(F)B-2 (4-5) 7% 5-HBB(F)B-3 (4-5) 10% 3-HB(2F,3F)-O2 (5-1) 17%[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2-HH-3 (2-1) 6% 3-HH-V1 (2-1) 9% 1V2-HH-1 (2-1) 7% 1V2-HH-3 (2-1) 6% 4-HH-V (2-1) 3% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 2% 3-BB(2F,3F)-O2 (5-3) 8% 5-BB(2F,3F)-O2 (5-3) 4% 3-H1OB(2F,3F)-O2 (5-5) 7% 3-HDhB(2F,3F)-O2 (6-3) 7% 2-HH1OB(2F,3F)-O2 (6-5) 8% 3-HH1OB(2F,3F)-O2 (6-5) 17% 2-BB(2F,3F)B-3 (7-1) 11%

[0366] [Example of Use 23] 2O-Ca(3F,6F)-O4 (a-5) 3% 3-HH-4 (2-1) 5% 3-HH-VFF (2-1) 4% 3-HB-O1 (2-5) 15% 1-BB-5 (2-8) 4% 3-HHB-1 (3-1) 6% 5-HB(2F,3F)-O2 (5-1) 9% V-HB(2F,3F)-O2 (5-1) 4% 2-HHB(2F,3F)-1 (6-1) 12% 3-HHB(2F,3F)-1 (6-1) 12% 3-HHB(2F,3F)-O2 (6-1) 13% 5-HHB(2F,3F)-O2 (6-1) 13% NI = 88.1°C; η = 37.4 mPa·s; Δn = 0.096; Δε = -3.5.

[0367] [Example of Use 24] 4O-Ca(1F,8F)-O2 (a-71) 5% 2-HH-3 (2-1) 16% 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 (5-1) 13% 5-HB(2F,3F)-O2 (5-1) 11% 2-H1OB(2F,3F)-O2 (5-5) 2% 3-H1OB(2F,3F)-O2 (5-5) 2% 2O-B(2F,3F)B(F)-O2 (5-9) 2% 4O-B(2F,3F)B(F)-O2 (5-9) 2% V-HHB(2F,3F)-O2 (6-1) 5% V2-HHB(2F,3F)-O2 (6-1) 4% 5-HHB(2F,3Cl)-O2 (6-12) 2% 3-HH1OCro(7F,8F)-5 (10-6) 2% NI = 74.1℃; η = 24.6mPa·s; Δn = 0.108; Δε = -2.4.[[ID=XX]] [[ID=XX]]

[0368] [[ID=XX]] [Example of Use 25] 2O-Ca(3F,6F,9Me)-O4 (a-11) 3%<X 2-HH-5 (2-1) 3% 3-HH-4 (2-1) 15% 3-HH-5 (2-1) 4% 3-HB-O2 (2-5) 12% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 4% 3-HHB-O1 (3-1) 3% 3-DhB(2F,3F)-O2 (5-2) 3% 2-BB(2F,3F)-O2 (5-3) 9% 5-H2B(2F,3F)-O2 (5-4) 9% 3-HH2B(2F,3F)-O2 (6-4) 3% 3-HBB(2F,3F)-O2 (6-7) 9% 5-HBB(2F,3F)-O2 (6-7) 9% V-HBB(2F,3F)-O2 (6-7) 3% 3-HHB(2F,3Cl)-O2 (6-12) 5% 2O-B(2F,3F)B(F)H-3 (6-19) 3%

[0369] [Example 26] 4O-Ca(1F,8F,9Me)-O2 (a-74) 12% 2-HH-3 (2-1) 6% 3-HH-V1 (2-1) 10% 1V2-HH-1 (2-1) 8% 1V2-HH-3 (2-1) 7% V-HHB-1 (3-1) 3% V2-HHB-1 (3-1) 3% 3-HHB-1 (3-1) 3% [[ID=​​​​​​​​​​​​​​​​​​​​​​​2O-Ca(3F,4F,6F)-O4 (a-36) 2% 2-HH-3 (2-1) 21% 3-HH-4 (2-1) 9% 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) 3% 5-B(F)BB-2 (3-8) 3% 3-BB(2F,3F)-O2 (5-3) 9% 5-BB(2F,3F)-O2 (5-3) 6% 2-HH1OB(2F,3F)-O2 (6-5) 13% 3-HH1OB(2F,3F)-O2 (6-5) 13% 3-HB(2F,3F)B-2 (7-2) 4% V-HH2BB(2F,3F)-O2 (8-3) 4% NI=76.8℃; η=17.2mPa·s; Δn=0.100; Δε=-3.2.

[0371] [Use Example 28] 2O-Ca(3F,4F,6F)-4 (a-232) 4% 3-HH-V (2-1) 28% 1-BB-3 (2-8) 7% 3-HHB-1 (3-1) 8% 5-B(F)BB-2 (3-8) 6% 3-BB(2F,3F)-O2 (5-3) 12% 2-HH1OB(2F,3F)-O2 (6-5) 15% 3-HH1OB(2F,3F)-O2 (6-5) 14% 3-H2BBB(2F,3F)-O2 (8-1) 3% 5-HFLF4-3 (13-1) 3% [Possibility of industrial utilization]

[0372] The liquid crystal compound of the present invention has good physical properties, and liquid crystal compositions containing this compound can be widely used in liquid crystal display devices for personal computers, televisions, etc.

Claims

1. A compound represented by formula (1-1-1), formula (1-3-1) to formula (1-3-6), formula (1-14-1), or formula (1-16-1) to formula (1-16-6). 【Chemical 1】 In formula (1-1-1) and formula (1-3-1) to formula (1-3-6), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; Z ２ is a single bond, -CH ２ O-, -OCH ２ - or -(CH ２ ) ２ - and; L １ , L ２ , L ３ , and L ４ are independently hydrogen, fluorine, or —CF ３ or -OCF ３ and L １ , L ２ , L ３ , and L ４ At least two of the groups are fluorine, —CF ３ , or -OCF ３ and X １ and X ２ are independently hydrogen or fluorine; 【Chemistry 2】 In formula (1-14-1) and formula (1-16-1) to formula (1-16-6), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; Z ２ is a single bond, -CH ２ O-, -OCH ２ - or -(CH ２ ) ２ - and; L ５ and L ６ are independently hydrogen, fluorine, or —CF ３ , or -OCF ３ and L ５ and L ６ At least one of the groups is fluorine, —CF ３ , or -OCF ３ and X １ and X ２ are independently hydrogen or fluorine.

2. The compound according to claim 1, represented by formula (1-1-1), formula (1-3-1) to formula (1-3-6), formula (1-14-1), or formula (1-16-1) to formula (1-16-6). 【Chemistry 3】 In formula (1-1-1) and formula (1-3-1) to formula (1-3-6), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; Z ２ is a single bond, -CH ２ O-, -OCH ２ - or -(CH ２ ) ２ - and; L １ , L ２ , L ３ , and L ４ are independently hydrogen, fluorine, or —CF ３ , or -OCF ３ and L １ , L ２ , L ３ , and L ４ At least two of the groups are fluorine, —CF ３ , or -OCF ３ and L １ , L ２ , L ３ , and L ４ at least two of are hydrogen; X １ and X ２ are independently hydrogen or fluorine, 【Chemistry 4】 In formula (1-14-1) and formula (1-16-1) to formula (1-16-6), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; Z ２ is a single bond, -CH ２ O-, -OCH ２ - or -(CH ２ ) ２ - and; L ５ and L ６ are independently hydrogen, fluorine, or —CF ３ , or -OCF ３ and L ５ and L ６ At least one of the groups is fluorine, —CF ３ , or -OCF ３ and X １ and X ２ are independently hydrogen or fluorine.

3. Formula (1-1-1), Formula (1-3-1-1) to Formula (1-3-1-3), Formula (1-3-2-1), Formula (1-3-2-2), Formula (1-3-3-1), Formula (1-3-3-2), Formula (1-3-4-1), Formula (1-3-4-2), Formula (1-3-5-1), Formula (1-3-5-2), Formula (1-3-6-1) to Formula (1-3-6-3), Formula (1-14-1), Formula (1-16-1) -1) to formula (1-16-1-3), formula (1-16-2-1), formula (1-16-2-2), formula (1-16-3-1), formula (1-16-3-2), formula (1-16-4-1), formula (1-16-4-2), formula (1-16-5-1), formula (1-16-5-2), or formula (1-16-6-1) to formula (1-16-6-3). The compound according to claim 1 or 2, 【Chemistry 5】 In formula (1-1-1), formula (1-3-1-1) to formula (1-3-1-3), formula (1-3-2-1), formula (1-3-2-2), formula (1-3-3-1), formula (1-3-3-2), formula (1-3-4-1), formula (1-3-4-2), formula (1-3-5-1), formula (1-3-5-2), and formula (1-3-6-1) to formula (1-3-6-3), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; L １ , L ２ , L ３ , and L ４ are independently hydrogen, fluorine, or —CF ３ , or -OCF ３ and L １ , L ２ , L ３ , and L ４ At least two of the groups are fluorine, —CF ３ , or -OCF ３ and L １ , L ２ , L ３ , and L ４ at least one of is hydrogen; X １ and X ２ are independently hydrogen or fluorine, 【Chemistry 6】 In formula (1-14-1), formula (1-16-1-1) to formula (1-16-1-3), formula (1-16-2-1), formula (1-16-2-2), formula (1-16-3-1), formula (1-16-3-2), formula (1-16-4-1), formula (1-16-4-2), formula (1-16-5-1), formula (1-16-5-2), and formula (1-16-6-1) to formula (1-16-6-3), R １ and R ２ are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, alkoxyalkyl having 2 to 9 carbon atoms, alkenyl having 2 to 10 carbon atoms, or alkenyloxy having 2 to 9 carbon atoms; R ａ is hydrogen or methyl; L ５ and L ６ are independently hydrogen, fluorine, or —CF ３ , or -OCF ３ and L ５ and L ６ At least one of the groups is fluorine, —CF ３ , or -OCF ３ and X １ and X ２ are independently hydrogen or fluorine.

4. The compound according to any one of claims 1 to 3, represented by formula (1-1-1-2) to formula (1-1-1-7), formula (1-14-1-1), or formula (1-14-1-2). 【Chemistry 7】 In the formulas (1-1-1-2) to (1-1-1-7), R １ and R ２ are independently alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkoxyalkyl having 2 to 6 carbon atoms, alkenyl having 2 to 7 carbon atoms, or alkenyloxy having 2 to 7 carbon atoms; R ａ is hydrogen or methyl, 【Chemistry 8】 In formula (1-14-1-1) or formula (1-14-1-2), R １ and R ２ are independently alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkoxyalkyl having 2 to 6 carbon atoms, alkenyl having 2 to 7 carbon atoms, or alkenyloxy having 2 to 7 carbon atoms; R ａ is hydrogen or methyl.

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

6. 6. The liquid crystal composition according to claim 5, comprising at least one compound selected from the group of compounds represented by formulas (2) to (4): 【Chemistry 9】 In the formulas (2) to (4), R １１ and R １２ are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, １１ and R １２ In the formula, at least one —CH ２ - may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; Ring B １ , ring B ２ , ring B ３ , and ring B ４ is independently 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 a single bond, —COO—, —(CH ２ ) ２ -, -CH=CH-, or -C≡C-.

7. 7. The liquid crystal composition according to claim 5, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (13): 【Chemistry 10】 In equations (5) to (13), R １３ and R １４ are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, １３ and R １４ In the formula, at least one —CH ２ - may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; R １５ is hydrogen, fluorine, alkyl having 1 to 10 carbon atoms, or alkenyl having 2 to 10 carbon atoms, １５ In the formula, at least one —CH ２ - may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; Ring C １ , ring C ２ , ring C ３ , and ring C ４ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Ring C ５ and ring C ６ are independently 1,4-cyclohexylene, 1,4-cyclohexeny ethylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z １４ , Z １５ , Z １６ , and Z １７ are independently a single bond, —COO—, or —CH ２ O-, -OCF ２ -, -(CH ２ ) ２ - or -OCF ２ - (CH ２ ) ２ - and; L １１ and L １２ is independently fluorine or chlorine; S １１ is hydrogen or methyl; X is -CHF- or -CF ２ - and; j, k, m, n, p, q, r, and s are independently 0 or 1; the sum of k, m, n, and p is 1 or 2; the sum of q, r, and s is 0, 1, 2, or 3; and t is 1, 2, or 3.

8. The liquid crystal composition according to claim 5 , further comprising at least one compound selected from the group of compounds represented by formulas (21) to (23): 【Chemistry 11】 In equations (21) to (23), R １６ is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and １６ In the formula, at least one —CH ２ - may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X １１ represents fluorine, chlorine, -CF ３ , -CHF ２ , -CH ２ F, -OCF ３ , -OCHF ２ , -OCF ２ CHF ２ , or -OCF ２ CHFCF ３ and Ring D １ , ring D ２ , and ring D ３ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z １８ , Z １９ , and Z ２０ are independently a single bond, —COO—, or —CH ２ O-, -CF ２ O-, -OCF ２ -, -(CH ２ ) ２ -, -CH=CH-, -C≡C-, or -(CH ２ ) ４ - and; L １３ and L １４ are independently hydrogen or fluorine.

9. The liquid crystal composition according to claim 5 , further comprising at least one compound selected from the group of compounds represented by formula (24): 【Chemistry 12】 In formula (24), R １７ is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, This R １７ In the formula, at least one —CH ２ - may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X １２ is —C≡N or —C≡C—C≡N; Ring E １ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl; Z ２１ represents a single bond, -COO-, or -CH ２ O-, -CF ２ O-, -OCF ２ -, -(CH ２ ) ２ - or -C≡C-; L １５ and L １６ are independently hydrogen or fluorine; i is 1, 2, 3, or 4.

10. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 5 to 9.

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