Compounds, compositions, liquid crystal compositions and their applications

Abstract

This invention provides a compound, a composition, a liquid crystal composition, and applications thereof. This invention provides a compound represented by the following general formula (I), and provides a liquid crystal composition containing said compound and an element using said liquid crystal composition. The compound of this invention has a large refractive index anisotropy Δn, sufficiently high Tni, high compatibility with liquid crystal compositions, and exhibits large dielectric constant anisotropy in the high-frequency region. Therefore, it can be effectively used as a material for elements such as high-frequency phase shifters, phased array antennas, image recognition devices, ranging devices, liquid crystal display elements, liquid crystal lenses, or birefringent lenses for stereoscopic image displays. [Chemical 1]

Description

Technical Field

[0001] This invention relates to a compound, a liquid crystal composition containing the compound, and elements using the liquid crystal composition and their applications. Background Technology

[0002] Liquid crystal compositions are being used in mobile terminals such as smartphones and tablet devices, as well as displays such as televisions and window displays. As a novel application of these liquid crystal compositions, antennas for transmitting and receiving radio waves between mobile vehicles such as vehicles and communication satellites are attracting considerable attention.

[0003] Previously, satellite communication used parabolic antennas. However, when used on mobile devices, these antennas had to be constantly oriented towards the satellite, requiring a large moving part. Antennas using liquid crystal composites, however, can change the transmission and reception direction of radio waves through the movement of the liquid crystals. Therefore, the antenna itself does not need to move, and its shape can be planar.

[0004] The refractive index anisotropy Δn required for the aforementioned application is, for example, around 0.4, which is very large compared to the Δn required for display applications. Therefore, compounds added to liquid crystal compositions need to have a large Δn, thereby exhibiting a high liquid crystal phase-isotropic phase transition temperature (Tni) that allows for outdoor use. Conventionally, compounds with trans structures have been reported as compounds with large Δn. However, when these compounds are added to liquid crystal compositions for antenna applications, there are problems such as insufficient Δn and insufficient Tni (Patent Document 1). In addition, compounds with a tetrahydronaphthalene (1,2,3,4-tetrahydronaphthalene) structure have been reported as compounds exhibiting a liquid crystal phase (Patent Document 2), but these compounds do not necessarily exhibit a sufficiently large Δn, and the dielectric constant anisotropy in the high-frequency region is low, resulting in insufficient phase modulation characteristics. Furthermore, compounds with an azodiphenylacetylene structure have been reported as compounds to solve these problems (Patent Document 3), but there is a problem of low reliability. Therefore, there is a need to develop a compound with large Δn, sufficiently high Tni, high compatibility with liquid crystal compositions, and large dielectric anisotropy in the high-frequency region.

[0005] [Existing Technical Documents]

[0006] [Patent Literature]

[0007] [Patent Document 1] Japanese Patent Publication No. 2014-514325

[0008] [Patent Document 2] Japanese Patent Application Publication No. 2001-34197

[0009] [Patent Document 3] Japanese Patent Application Publication No. 2013-103897 Summary of the Invention

[0010] [The problem the invention aims to solve]

[0011] The problem to be solved by the present invention is to provide a compound having a large refractive index anisotropy (Δn), sufficiently high Tni, high compatibility with liquid crystal compositions, and exhibiting a large dielectric constant anisotropy (Δε) in the high frequency region, a liquid crystal composition containing the compound, and an element using the liquid crystal composition.

[0012] [Technical means to solve the problem]

[0013] The inventors have conducted intensive research to solve the aforementioned problems, resulting in the development of a specific compound. Specifically, the present invention provides a compound represented by the following general formula (I), and provides a liquid crystal composition containing said compound and an element using said liquid crystal composition.

[0014] [Chemistry 1]

[0015]

[0016] (where R is in the formula) 1 The alkyl group represents a linear alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a halogen atom, and one or more -CH2- atoms in the alkyl group may be independently replaced by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-, but the oxygen atoms are not directly bonded to each other.

[0017] R 2This indicates that a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuryl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, or one or more -CH2- groups can be independently converted by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-C The alkyl group is a straight-chain alkyl group with 1 to 20 carbon atoms, substituted with O-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the oxygen atoms are not directly bonded to each other, and any hydrogen atom in the alkyl group may be replaced with a fluorine atom.

[0018] A 1 and A 2 Each can independently represent a hydrocarbon ring or heterocycle with 3 to 16 substituted carbon atoms, but when multiple A atoms are present... 2 At times, they can be the same or different.

[0019] L 1 and L 2 Each of the following can independently represent a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuryl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one or more -CH2- groups, which can each independently be represented by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C- substituted linear alkyl groups with 1 to 20 carbon atoms or branched or cyclic alkyl groups with 3 to 20 carbon atoms, wherein oxygen atoms are not directly bonded to each other, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom.

[0020] Z 1Each of these terms independently represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH2O-, -OCH2-, -CF2O-, -OCF2-, -CH=CHCOO-, -OCOCH=CH-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH2-CH(CH3)COO-, -OCOCH(CH3)-CH2-, -OCH2CH2O-, -CH=NN=CH-, -CH=N-, -N=CH-, or an alkylene group with 2 to 20 carbon atoms. One or more of the -CH2- atoms in the alkylene group may be substituted with -O-, -COO-, or -OCO-, but the oxygen atoms are not directly bonded to each other. When multiple Z- atoms are present... 1 At that time, they can be the same or different, and Z exists here. 1 At least one of them represents a base other than a single bond.

[0021] n1 represents an integer from 1 to 3.

[0022] The present invention provides a composition comprising the aforementioned compound.

[0023] The present invention provides a high-frequency phase shifter, a phased array antenna, an image recognition device, a ranging device, a liquid crystal display element, a liquid crystal lens or a birefringent lens for stereoscopic image display, which uses the liquid crystal composition described above.

[0024] [The effects of the invention]

[0025] The compounds of the present invention have a large refractive index anisotropy Δn, exhibiting a sufficiently high Tni, high compatibility with liquid crystal compositions, and a large dielectric constant anisotropy in the high-frequency region. Therefore, they can be effectively used as materials for components such as high-frequency phase shifters, phased array antennas, image recognition devices, ranging devices, liquid crystal display elements, liquid crystal lenses, or birefringent lenses for stereoscopic image displays. Detailed Implementation

[0026] The present invention provides a compound represented by general formula (I), a liquid crystal composition containing said compound, and an element using said liquid crystal composition.

[0027] In general formula (I), R 1The alkyl group represents a linear alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a halogen atom, and one or more -CH2- atoms in the alkyl group may be independently replaced by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C-, but the oxygen atoms do not directly bond to each other. From the viewpoints of compatibility with liquid crystal compositions, refractive index anisotropy, voltage retention, ease of synthesis, and availability of raw materials, R... 1 Preferably, it indicates that any hydrogen atom in the radical can be replaced with a halogen atom, and one or more of the -CH2- radicals can be independently replaced with a straight-chain or branched alkyl group having 1 to 20 carbon atoms, such as -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-. 1 More preferably, it indicates that any hydrogen atom in the radical can be replaced with a fluorine atom and one or more of the -CH2- radicals can be independently replaced with a straight-chain or branched alkyl group having 1 to 12 carbon atoms, such as -O-, -CH=CH-, or -C≡C-, R. 1 Furthermore, it is more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, R 1 Particularly preferred are alkyl groups having 2 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 3 to 7 carbon atoms.

[0028] In general formula (I), R 2This indicates that a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuryl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, or one or more -CH2- groups can be independently converted by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-C O-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C- substituted linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, but the oxygen atoms are not directly bonded to each other, and any hydrogen atom in the alkyl group may be replaced with a fluorine atom. From the viewpoints of compatibility with liquid crystal compositions, refractive index anisotropy, dielectric constant anisotropy, voltage retention, ease of synthesis, and availability of raw materials, R 2 Preferably, it is a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, representing a fluorine atom, chlorine atom, nitro group, cyano group, isocyano group, or any hydrogen atom in the group can be replaced by a fluorine atom, and one or more -CH2- atoms in the group can be independently replaced by -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-. 2 More preferably, it is a straight-chain alkyl group with 1 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, wherein the fluorine atom, cyano group, or any hydrogen atom in the group can be replaced by a fluorine atom and the -CH2- in the group can be replaced by -O-. 2 More preferably, it represents a fluorine atom, a cyano group, or a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, R 2 Particularly preferred are straight-chain alkyl groups representing fluorine atoms, cyano groups, or carbon atoms numbering 1 to 8.

[0029] In general formula (I), A 1 and A 2 Each can independently represent a hydrocarbon ring or heterocycle with 3 to 16 substituted carbon atoms, but when multiple A atoms are present... 2 At the same time, they can be the same or different. From the perspectives of compatibility with liquid crystal compositions, refractive index anisotropy, dielectric constant anisotropy, voltage retention, ease of synthesis, and availability of raw materials, A 1 and A 2 Preferably, each L represents an unsubstituted or substituent-free group independently. 3 Replacement, freedom of choice

[0030] (a) 1,4-cyclohexylene (one or more non-adjacent -CH2- groups may be replaced with -O- or -S-).

[0031] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=)

[0032] (c) 1,4-cyclohexenyl, bicyclo[2.2.2]octane-1,4-diyl, naphth-2,6-diyl, naphth-1,4-diyl, 1,2,3,4-tetrahydronaphth-2,6-diyl, 5,6,7,8-tetrahydronaphth-1,4-diyl, decahydronaphth-2,6-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, anthracene-9,10-diyl, phenanthrene-2,7-diyl (these groups are present in...) At least one hydrogen atom may be substituted with a fluorine or chlorine atom. Additionally, one or more of the -CH= groups present in naphthalene-2,6-diyl, naphthalene-1,4-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 5,6,7,8-tetrahydronaphthalene-1,4-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, anthracene-9,10-diyl, or phenanthrene-2,7-diyl may be substituted with -N=.

[0033] (d) Thiophene-2,5-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, thieno[3,2-b]thiophene-2,5-diyl (one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=)

[0034] The basis of the group formed, when there are multiple A 2 At that time, they can be the same or different. Additionally, A 1 and A 2 More preferably, each can be independently represented as unsubstituted or receptive to more than one substituent L. 3 The substituted group is selected from 1,4-phenylene, naphthio-2,6-diyl, naphthio-1,4-diyl, 5,6,7,8-tetrahydronaphthio-1,4-diyl, phenanthrene-2,7-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, benzothiazole-2,5-diyl, benzothiazole-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, or thieno[3,2-b]thiophene-2,5-diyl, when multiple A groups are present. 2 At that time, they can be the same or different. Additionally, A 1 and A 2 Preferably, each of the bases is independently represented by a base selected from equations (A-1) to (A-17) below.

[0035] [Chemistry 2]

[0036]

[0037] (In the formula, the dashed line represents the bond position. When there are multiple L...) 3 (At times, they can be the same or different.)

[0038] When there are multiple A 2 In this case, they may be the same or different, and more preferably, each independently represents a basis selected from formulas (A-1) to (A-7), (A-12), (A-15) and (A-17), and particularly preferably, each independently represents a basis selected from formulas (A-1), (A-3) to (A-7).

[0039] L 3 This indicates that a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuryl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or one or more -CH2- groups can be independently converted by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, or -O- groups. A linear alkyl group having 1 to 20 carbon atoms substituted with CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but indicating that oxygen atoms are not directly bonded to each other and that any hydrogen atom in the alkyl group may be replaced by a fluorine atom. From the viewpoints of compatibility with liquid crystal compositions, refractive index anisotropy, dielectric constant anisotropy, voltage retention, ease of synthesis, and availability of raw materials, L 3 Preferably, it refers to a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where one or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-, indicating that the fluorine atom, chlorine atom, or any hydrogen atom in the alkyl group can be replaced by a fluorine atom and one or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-. 3 More preferably, it is a straight-chain alkyl group with 1 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, wherein the fluorine atom or any hydrogen atom in the group can be replaced by a fluorine atom and the -CH2- in the group can be replaced by -O-. 3 More preferably, it represents a fluorine atom, or a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, L 3Particularly preferred are straight-chain alkyl groups representing fluorine atoms or having 1 to 8 carbon atoms.

[0040] In general formula (I), Z 1 Each of these terms independently represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH2O-, -OCH2-, -CF2O-, -OCF2-, -CH=CHCOO-, -OCOCH=CH-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH2-CH(CH3)COO-, -OCOCH(CH3)-CH2-, -OCH2CH2O-, -CH=NN=CH-, -CH=N-, -N=CH-, or an alkylene group having 2 to 20 carbon atoms. Preferably, one or more of the -CH2- atoms in the alkylene group can be substituted by -O-, -COO-, or -OCO-, but the oxygen atoms are not directly bonded to each other. Here, when multiple Z... 1 At that time, they can be the same or different. Furthermore, from the perspective of increasing Δn, the Z present here is preferred. 1 At least one of them represents a group other than a single bond. From the viewpoints of compatibility with liquid crystal compositions, refractive index anisotropy, dielectric constant anisotropy, voltage retention, ease of synthesis, and availability of raw materials, Z 1 More preferably, each of the following can be independently represented as a single bond: -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH2O-, -OCH2-, -CF2O-, -OCF2-, -CH=CHCOO-, -OCOCH=CH-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH=NN=CH-, -CH=N-, or -N=CH-. Additionally, Z 1 Preferably, each of the following can independently represent a single bond: -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH=CHCOO-, -OCOCH=CH-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH=NN=CH-, -CH=N-, or -N=CH-. More preferably, each of the following can independently represent a single bond: -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH=NN=CH-, -CH=N-, or -N=CH-. Particularly preferred are those that independently represent a single bond: -CH=CH-, -CF=CF-, -C≡C-, -CH=NN=CH-, -CH=N-, or -N=CH-. Most preferably, each of the following can independently represent a single bond or -C≡C-.

[0041] In general formula (I), n1 is preferably an integer representing 1 to 3, more preferably an integer representing 1 or 2, and particularly preferably 1.

[0042] Furthermore, in general formula (I), from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0043] As mentioned above, n1 represents an integer from 1 to 3, therefore the compound represented by general formula (I) contains three or more ring structures (monocyclic or condensed rings). Especially when the ring structures are linked together and the compound as a whole forms a rod-like molecular structure, liquid crystallinity is improved and Tni becomes higher. Therefore, when added to a liquid crystal composition, the liquid crystal phase temperature range can be effectively expanded while maintaining high compatibility. Furthermore, when the π electrons in the ring structure are conjugated between the rings directly or via linking groups throughout the compound, it exhibits excellent effects in effectively increasing Δn and demonstrating large dielectric anisotropy in the high-frequency region.

[0044] From the viewpoints of wide temperature range of liquid crystal phase, compatibility with liquid crystal compositions, refractive index anisotropy, dielectric constant anisotropy, voltage retention, ease of synthesis, and availability of raw materials, the compound represented by general formula (I) is more preferably the compound represented by the following general formula (Ii).

[0045] [Chemistry 3]

[0046]

[0047] (where R is in the formula) 11 Each alkyl group independently represents a straight-chain or branched alkyl group having 1 to 20 hydrogen atoms and carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a halogen atom, and one or more -CH2- atoms in the alkyl group may be independently replaced by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-.

[0048] R 21 The alkyl group represents a fluorine atom, a chlorine atom, a nitro group, a cyano group, an isocyano group, or a straight-chain alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and one or more -CH2- atoms in the alkyl group may be independently substituted by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-.

[0049] A 11 and A 21Each of these can be independently represented as 1,4-cyclohexene, tetrahydropyran-2,5-diyl, dioxane-2,5-diyl, 1,4-phenylene, naphthi-2,6-diyl, naphthi-1,4-diyl, 5,6,7,8-tetrahydronaphthi-1,4-diyl, phenanthrene-2,7-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, benzothiazole-2,5-diyl, benzothiazole-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, or thieno[3,2-b]thiophene-2,5-diyl, but when multiple A's are present... 21 At the same time, they may be the same or different, and these groups may be unsubstituted or may be substituted by more than one substituent L. 31 replace,

[0050] L 11 and L 21 Each of the following can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a straight-chain alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and one or more -CH2- atoms in the alkyl group may be independently substituted by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-.

[0051] L 31 Each alkyl group independently represents a fluorine atom, a chlorine atom, a straight-chain alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and one or more -CH2- groups in the alkyl group may be independently substituted by -O-, -S-, -CH=CH-, -CF=CF-, or -C≡C-, when multiple L- groups are present. 31 At times, they can be the same or different.

[0052] Z 11 Each can independently represent -OCH2-, -CH2O-, -CH2CH2-, -CF2O-, -OCF2-, -CH=CH-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a single bond, but when multiple Zs exist... 11 At that time, they can be the same or different, and Z exists here. 11 At least one of them represents a base other than a single bond.

[0053] n11 represents an integer from 1 to 3.

[0054] Preferably, the compounds represented by the following general formula (I-ii) are preferred.

[0055] [Chemistry 4]

[0056]

[0057] (where R is in the formula) 12 The alkyl group refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and one or more -CH2- atoms in the alkyl group may be independently replaced by -O-, -CH=CH-, or -C≡C-.

[0058] R 22 The alkyl group represents a fluorine atom, a cyano group, or a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and at least one -CH2- in the alkyl group may be substituted with -O-.

[0059] A 12 and A 22 Each of these bases independently represents a basis selected from equations (A-ii-1) to (A-ii-17) below, but when there are multiple A bases... 22 At times, they can be the same or different.

[0060] [Chemistry 5]

[0061]

[0062] (In the formula, the dashed line represents the bond position. When there are multiple L...) 32 and L 42 (At times, they can be the same or different.)

[0063] L 12 L 22 L 32 and L 42 Each of the following independently represents a hydrogen atom, a fluorine atom, or a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein any hydrogen atom in the alkyl group may be replaced by a fluorine atom, and the -CH2- in the alkyl group may be substituted with -O-.

[0064] Z 12 Each can be independently represented as -CH=CH-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-, but when multiple Z exist... 12 At times, they can be the same or different.

[0065] n12 represents an integer from 1 to 3.

[0066] As for the compounds represented by general formula (I), specifically, the compounds represented by formulas (I-1) to (I-25) can be listed below.

[0067] [Chemistry 6]

[0068]

[0069] [Chemistry 7]

[0070]

[0071] [Chemistry 8]

[0072]

[0073] [Chemistry 9]

[0074]

[0075] [Chemistry 10]

[0076]

[0077] The compounds of the present invention can be manufactured using the following methods.

[0078] (Preparation Method 1) Preparation of the compound represented by the following formula (s-5)

[0079] [Chemistry 11]

[0080]

[0081] (where R is in the formula) 1s R 2s A 1s L 1s L 2s and L 3s R represents the expression in the general formula (I). 1 R 2 A 1 L 1 L 2 and L 3 Same meaning.

[0082] By reacting the compound represented by general formula (s-1) with the compound represented by general formula (s-2), the compound represented by general formula (s-3) can be obtained. Examples of reaction methods include coupling reactions using palladium catalysts, copper catalysts, and bases. Specific examples of palladium catalysts include: [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) dichloride, palladium(II) acetate, dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphine]palladium(II), dichlorobis(triphenylphosphine)palladium(II), tetra(triphenylphosphine)palladium(0), etc. When using palladium(II) acetate as a metal catalyst, ligands such as triphenylphosphine and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl can be added. Specific examples of copper catalysts include copper iodide(I). Specific examples of bases include triethylamine, etc.

[0083] By reacting the compound represented by general formula (s-3) with the compound represented by general formula (s-4), the compound represented by general formula (s-5) can be obtained. Examples of reaction methods include scallion coupling reactions using palladium catalysts, copper catalysts, and bases. Specific examples of palladium catalysts, copper catalysts, and bases are given above.

[0084] (Preparation Method 2) Preparation of the compound represented by the following formula (s-10)

[0085] [Chemistry 12]

[0086]

[0087] (where R is in the formula) 1s R 2s A 1s L 1s L 2s and L 3s R represents the expression in the general formula (I). 1 R 2 A 1 L 1 L 2 and L 3 Same meaning.

[0088] By reacting the compound represented by general formula (s-6) with the compound represented by general formula (s-7), the compound represented by general formula (s-8) can be obtained. Examples of reaction methods include scallion coupling reactions using palladium catalysts, copper catalysts, and bases. Specific examples of palladium catalysts, copper catalysts, and bases are given above.

[0089] By reacting the compound represented by general formula (s-8) with the compound represented by general formula (s-9), the compound represented by general formula (s-10) can be obtained. As a reaction method, the Heck reaction using a palladium catalyst and a base can be cited as an example. Specific examples of the palladium catalyst and base mentioned above can be cited as examples.

[0090] (Preparation Method 3) Preparation of the compound represented by the following formula (s-15)

[0091] [Chemistry 13]

[0092]

[0093] (where R is in the formula) 1s R 2s A 1s L 1s L 2s and L 3s R represents the expression in the general formula (I). 1 R 2 A 1 L 1 L 2 and L 3 Same meaning.

[0094] By reacting the compound represented by general formula (S-11) with the compound represented by general formula (S-12), the compound represented by general formula (S-13) can be obtained. Examples of reaction methods include scallion coupling reactions using palladium catalysts, copper catalysts, and bases. Specific examples of palladium catalysts, copper catalysts, and bases are given above.

[0095] The compound represented by general formula (s-15) can be obtained by reacting the compound represented by general formula (s-14). For example, the Wittig reaction can be cited as a reaction method.

[0096] (Preparation Method 4) Preparation of the compound represented by the following formula (s-21)

[0097] [Chemistry 14]

[0098]

[0099] (where R is in the formula) 1s R 2s A 1s L 1s L 2s and L 3s R represents the expression in the general formula (I). 1 R 2 A1 L 1 L 2 and L 3 Same meaning.

[0100] By reacting the compound represented by general formula (S-16) with the compound represented by general formula (S-17), the compound represented by general formula (S-18) can be obtained. As a reaction method, the Heck reaction using a palladium catalyst and a base can be cited as an example. Specific examples of the palladium catalyst and base mentioned above can be cited as examples.

[0101] By reacting a compound represented by general formula (S-18) with hydrogen, a compound represented by general formula (S-19) can be obtained. Examples of reaction methods include hydrogenation in the presence of a metal catalyst. Specific examples of metal catalysts include 10% palladium on carbon.

[0102] By reacting the compound represented by general formula (S-19) with the compound represented by general formula (S-20), the compound represented by general formula (S-21) can be obtained. Examples of reaction methods include scallion coupling reactions using palladium catalysts, copper catalysts, and bases. Specific examples of palladium catalysts, copper catalysts, and bases are given above.

[0103] Other reaction conditions not specified in the steps described can be listed as follows: those described in publications such as *Lectures on Experimental Chemistry* (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), *Organic Syntheses* (published by John Wiley & Sons, Inc.), *Beilstein Handbook of Organic Chemistry* (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K.), and *Fiesers' Reagents for Organic Synthesis* (John Wiley & Sons, Inc.); or those described in the SciFinder (Chemical Abstracts Service, American Chemical Society) database. The criteria are included in databases such as the Society, the Reaxys database (Elsevier Ltd.), and others.

[0104] In each step, functional groups can be protected as needed. Examples of protecting groups include those described in "GREENE'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS" (Fourth Edition, co-authored by Peter GMWUTS and Theodora W. Greene, published by John Wiley & Sons, Inc.).

[0105] In addition, purification can be carried out as needed at each step. Examples of purification methods include: chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid-liquid extraction. Specific examples of refining agents include: silica gel, alumina, and activated carbon.

[0106] The compound represented by general formula (I) is preferably added to the liquid crystal composition for use. When the liquid crystal composition contains a compound represented by general formula (I), it may contain one compound represented by general formula (I) or multiple compounds represented by general formula (I). When the liquid crystal composition of the present invention contains a compound represented by general formula (I), the total content of the compound represented by general formula (I) in the liquid crystal composition is preferably 5% by mass or more, more preferably 10% by mass or more and 95% by mass or less, further preferably 15% by mass or more and 90% by mass or less, and particularly preferably 20% by mass or more and 85% by mass or less. Here, "the total content of the compound represented by general formula (I)" refers to the content of the compound represented by general formula (I) when the liquid crystal composition contains one compound represented by general formula (I), and refers to the total content of the multiple compounds represented by general formula (I) when the liquid crystal composition contains multiple compounds represented by general formula (I).

[0107] The refractive index anisotropy (Δn) of the liquid crystal composition containing the compound represented by general formula (I) is preferably 0.15 or more and 1.00 or less. From the viewpoint of the liquid crystal phase temperature range, driving voltage, rotational viscosity and elastic modulus of the liquid crystal composition, the refractive index anisotropy (Δn) is preferably 0.20 or more and 0.95 or less, more preferably 0.25 or more and 0.90 or less, further preferably 0.30 or more and 0.85 or less, and particularly preferably 0.35 or more and 0.80 or less.

[0108] When a liquid crystal composition containing a compound represented by general formula (I) is used in a high-frequency phase shifter, a phased array antenna, an image recognition device, a ranging device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for stereoscopic image display, the dielectric anisotropy (Δε(1kHz)) of the liquid crystal composition containing a compound represented by general formula (I) at 1 kHz is preferably 2 or more and 60 or less. From the viewpoint of the liquid crystal phase temperature range, storage stability, weather resistance, driving voltage, rotational viscosity, and elastic modulus of the liquid crystal composition, the dielectric anisotropy (Δε(1kHz)) at 1 kHz is preferably 2.5 or more and 50 or less, more preferably 3 or more and 40 or less, and particularly preferably 3.5 or more and 30 or less.

[0109] Liquid crystal compositions containing compounds represented by general formula (I) are preferably used in high-frequency devices. The frequency range is preferably 1 MHz or more and 1 THz or less, more preferably 1 GHz or more and 500 GHz or less, further preferably 2 GHz or more and 300 GHz or less, and particularly preferably 5 GHz or more and 150 GHz or less. Furthermore, liquid crystal compositions containing compounds represented by general formula (I) are also preferably used in image recognition devices and ranging devices, and particularly preferably in optical radar (Light Detection and Ranging, Laser Imaging Detection and Ranging, hereinafter referred to as LiDAR). The frequency range is preferably 50 THz or more and 1000 THz or less, further preferably 100 THz or more and 500 THz or less, and particularly preferably 150 THz or more and 350 THz or less. That is, the light used for LiDAR is preferably infrared light, with a wavelength preferably between 800 nm and 2000 nm, and particularly preferably infrared lasers with wavelengths of 905 nm or 1550 nm. When considering the cost of the photodetector used or its sensitivity under all weather conditions, a 905nm infrared laser is preferred; when considering safety related to human vision, a 1550nm infrared laser is preferred.

[0110] Liquid crystal compositions containing compounds represented by general formula (I) are preferably those containing compounds represented by general formula (IV).

[0111] [Chemistry 15]

[0112]

[0113] (where R is in the formula) 6 The groups are alkyl (1 to 8 carbon atoms), alkoxy (1 to 7 carbon atoms), alkenyl (2 to 8 carbon atoms), or alkenyloxy (2 to 7 carbon atoms).

[0114] A 6 Let A represent a basis selected from equations (A6-1) to (A6-8) below, but when there are multiple A's 6 At times, they can be the same or different.

[0115] [Chemistry 16]

[0116]

[0117] (In the formula, the dashed lines indicate the location of the bonds.)

[0118] Z 4Represents -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO- NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -C H=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bond, but when multiple Z are present 4 At times, they can be the same or different.

[0119] m6 represents an integer from 1 to 4.

[0120] A y Let A represent the basis selected from the following equations (Ay-1) and (Ay-2).

[0121] [Chemistry 17]

[0122]

[0123] (In the formula, the dashed line represents the bond position, Y) 7 Y 9 Y 10 and Y 12 Each can independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, Y 8 and Y 11Each of the following can independently represent a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfuryl group, an alkyl group with 1 to 8 carbon atoms for which any hydrogen atom is replaced by a fluorine atom, an alkoxy group with 1 to 7 carbon atoms for which any hydrogen atom is replaced by a fluorine atom, an alkenyl group with 2 to 8 carbon atoms for which any hydrogen atom is replaced by a fluorine atom, or an alkenoxy group with 2 to 7 carbon atoms for which any hydrogen atom is replaced by a fluorine atom. However, here, one or more -CH2- groups can be independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-. From the viewpoints of liquid crystal phase temperature range, refractive index anisotropy, dielectric constant anisotropy, rotational viscosity, and elastic modulus of the liquid crystal composition, the compound represented by general formula (VI) is preferably the compound represented by the following general formula (VI-i).

[0124] [Chemistry 18]

[0125]

[0126] (where R is in the formula) 61 The groups are alkyl (1 to 5 carbon atoms), alkoxy (1 to 4 carbon atoms), alkenyl (2 to 5 carbon atoms), or alkenyloxy (2 to 4 carbon atoms).

[0127] A 61 The base is selected from equations (A6-1) to (A6-6), but when there are multiple A's... 61 At times, they can be the same or different.

[0128] Z 41 This indicates -OCH2-, -CH2O-, -CH2CH2-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CH=NN=CH-, -CF=CF-, -N=N-, -C≡C-, or a single bond, but when multiple Z are present... 41 At times, they can be the same or different.

[0129] m61 represents an integer from 1 to 3.

[0130] A y1 Let represent the bases selected from the following equations (Ay-1-i) and (Ay-2-i).

[0131] [Chemistry 19]

[0132]

[0133] (In the formula, the dashed line represents the bond position, Y) 71 Y 91 Y 101 and Y 121 Each can independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, Y 81 and Y 111 Each can independently represent a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorothioalkyl group, an alkyl group with 1 to 8 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, an alkoxy group with 1 to 7 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, an alkenyl group with 2 to 8 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, or an alkenyloxy group with 2 to 7 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom.

[0134] The compound represented by general formula (VI) is more preferably the compound represented by the following general formula (VI-ii).

[0135] [Chemistry 20]

[0136]

[0137] (where R is in the formula) 62 The groups are alkyl (1 to 5 carbon atoms), alkoxy (1 to 4 carbon atoms), alkenyl (2 to 5 carbon atoms), or alkenyloxy (2 to 4 carbon atoms).

[0138] A 62 The base is selected from equations (A6-1) to (A6-5), but when there are multiple A bases... 62 At times, they can be the same or different.

[0139] Z 42 This represents -CF₂O-, -OCF₂-, -CH=CH-, -CF=CF-, -N=N-, -C≡C-, or a single bond, but when multiple Z are present... 42 At times, they can be the same or different.

[0140] m62 represents 1, 2, or 3.

[0141] Y 72 and Y 92 Each can independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, Y 82This indicates a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorothioalkyl group, an alkyl group with 1 to 8 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, an alkoxy group with 1 to 7 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, an alkenyl group with 2 to 8 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom, or an alkenyloxy group with 2 to 7 carbon atoms for which any hydrogen atom can be replaced by a fluorine atom.

[0142] The compound represented by general formula (VI) is further preferably the compound represented by the following general formula (VI-iii).

[0143] [Chemistry 21]

[0144]

[0145] (where R is in the formula) 63 The group represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0146] A 63 The base is selected from equations (A6-1) to (A6-5), but when there are multiple A bases... 63 At times, they can be the same or different.

[0147] Z 43 This indicates -CF2O-, -OCF2-, -N=N-, -C≡C-, or a single bond, but when multiple Z are present... 43 At times, they can be the same or different.

[0148] m63 represents 1, 2, or 3.

[0149] Y 73 and Y 93 Each can independently represent a hydrogen atom, a fluorine atom, or a chlorine atom, Y 83 This indicates a fluorine atom, a chlorine atom, a cyano group, or a thioisocyanate group.

[0150] The compounds represented by general formula (VI) are particularly preferred to be those represented by general formulas (VI-iv-1) to (VI-iv-21).

[0151] [Chemistry 22]

[0152]

[0153] [Chemistry 23]

[0154]

[0155] [Chemistry 24]

[0156]

[0157] [Chemistry 25]

[0158]

[0159] [Chemistry 26]

[0160]

[0161] (where R is in the formula) 614 (This refers to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.)

[0162] Liquid crystal compositions containing compounds represented by general formula (I) may also contain compounds represented by general formula (III) below.

[0163] [Chemistry 27]

[0164]

[0165] (where R is in the formula) 31 and R 32 Each of these can be independently represented as an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.

[0166] A 31 and A 32 Each of the bases selected independently from equations (A3-1) to (A3-8) below represents a basis, but when there are multiple A's... 32 At times, they can be the same or different.

[0167] [Chemistry 28]

[0168]

[0169] (In the formula, the dashed lines indicate the location of the bonds.)

[0170] m31 represents an integer from 1 to 4.

[0171] From the viewpoints of liquid crystal phase temperature range, refractive index anisotropy, dielectric constant anisotropy, rotational viscosity, and elastic modulus of the liquid crystal composition, the compound represented by general formula (III) is preferably the compound represented by the following general formula (III-i).

[0172] [Chemistry 29]

[0173]

[0174] (where R is in the formula) 311 and R 321Each of these can be independently represented as an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.

[0175] A 311 and A 321 Each of these bases independently represents a basis selected from equations (A31-1) to (A31-6) below, but when there are multiple A's... 321 At times, they can be the same or different.

[0176] [Chemistry 30]

[0177]

[0178] (In the formula, the dashed lines indicate the location of the bonds.)

[0179] m311 represents an integer from 1 to 3.

[0180] The compound represented by general formula (III) is more preferably the compound represented by the following general formula (III-ii).

[0181] [Chemistry 31]

[0182]

[0183] (where R is in the formula) 312 and R 322 Each of these can be independently represented as an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.

[0184] A 312 and A 322 Each of these bases independently represents a basis selected from equations (A32-1) to (A32-2) below, but when there are multiple A's... 322 At times, they can be the same or different.

[0185] [Chemistry 32]

[0186]

[0187] (In the formula, the dashed lines indicate the location of the bonds.)

[0188] m312 represents 1 or 2.

[0189] The compound represented by general formula (III) is further preferably the compound represented by the following general formula (III-iii).

[0190] [Chemistry 33]

[0191]

[0192] (where R is in the formula) 313 and R 323 Each can independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0193] A 313 and A 323 Each independently represents a basis selected from equations (A33-1) and (A33-2) below, but when there are multiple A's... 323 At times, they can be the same or different.

[0194] [Chemistry 34]

[0195]

[0196] (In the formula, the dashed lines indicate the location of the bonds.)

[0197] m312 represents 1 or 2.

[0198] Here, the compounds represented by general formula (III) are particularly preferred to be those represented by general formulas (III-iv-1) to (III-iv-10).

[0199] [Chemistry 35]

[0200]

[0201] [Chemistry 36]

[0202]

[0203] (where R is in the formula) 314 and R 324 Each can independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0204] Furthermore, the compound represented by general formula (I) can also be added to liquid crystal compositions with a neutral or negative dielectric anisotropy (Δε). In this case, the dielectric anisotropy (Δε) of the liquid crystal composition containing the compound represented by general formula (I) is preferably -20 or more and 2 or less. From the viewpoints of the liquid crystal phase temperature range, storage stability, weather resistance, driving voltage, rotational viscosity, and elastic modulus of the liquid crystal composition, the dielectric anisotropy (Δε) is preferably -15 or more and 1.5 or less, more preferably -10 or more and 1 or less, and particularly preferably -5 or more and 0.5 or less.

[0205] When the dielectric anisotropy (Δε) of the liquid crystal composition containing the compound represented by general formula (I) is neutral or negative, the liquid crystal composition may contain the compound represented by the following general formula (IV).

[0206] [Chemistry 37]

[0207]

[0208] (where R is in the formula) 41 and R 42 Each of these can be independently represented as an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.

[0209] A 41 and A 42 Each of these bases independently represents a basis selected from equations (A4-1) to (A4-11) below, but when there are multiple A's... 41 At that time, they can be the same or different; when there are multiple A's... 42 At times, they can be the same or different.

[0210] [Chemistry 38]

[0211]

[0212] (In the formula, the dashed lines indicate the location of the bonds.)

[0213] Z 41 and Z 42 Each of these can be independently represented as -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bonds, but when multiple Z are present 41 At that time, they can be the same or different, when there are multiple Z 42 At times, they can be the same or different.

[0214] m41 and m42 each independently represent integers from 0 to 3, but m41 + m42 represents integers from 1 to 3.

[0215] From the viewpoints of liquid crystal phase temperature range, refractive index anisotropy, dielectric constant anisotropy, rotational viscosity, and elastic modulus of the liquid crystal composition, the compound represented by general formula (IV) is preferably the compound represented by the following general formula (IV-i).

[0216] [Chemistry 39]

[0217]

[0218] (where R is in the formula) 411 and R 421 Each of these can be independently represented as an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.

[0219] A 411 and A 421 Each of these represents a basis independently selected from equations (A4-1) to (A4-9), but when multiple A's exist... 411 At that time, they can be the same or different; when there are multiple A's... 421 At times, they can be the same or different.

[0220] Z 411 and Z 421 Each can independently represent -OCH2-, -CH2O-, -CH2CH2-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CH=NN=CH-, -CF=CF-, -C≡C-, or a single bond, but when multiple Zs exist... 411 At that time, they can be the same or different, when there are multiple Z 421 At times, they can be the same or different.

[0221] m411 and m421 each independently represent integers from 0 to 3, but m411 + m421 represents integers from 1 to 3.

[0222] The compound represented by general formula (IV) is more preferably the compound represented by the following general formula (IV-ii).

[0223] [Chemistry 40]

[0224]

[0225] (where R is in the formula) 412 and R 422 Each of these can be independently represented as an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.

[0226] A412 and A 422 Each of these bases independently represents a basis selected from equations (A4-1) to (A4-7), but when multiple A's exist... 412 At that time, they can be the same or different; when there are multiple A's... 422 At times, they can be the same or different.

[0227] Z 412 and Z 422 Each can independently represent -OCH2-, -CH2O-, -CH2CH2-, -COO-, -OCO-, -CF2O-, -OCF2-, or a single bond, but when multiple Zs exist... 412 At that time, they can be the same or different, when there are multiple Z 422 At times, they can be the same or different.

[0228] m412 and m422 each independently represent 0, 1, or 2, but m412 + m422 represents 1 or 2.

[0229] The compound represented by general formula (IV) is further preferably the compound represented by the following general formula (IV-iii).

[0230] [Chemistry 41]

[0231]

[0232] (where R is in the formula) 413 and R 423 Each can independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0233] A 413 and A 423 Each of these bases independently represents a basis selected from equations (A4-1) to (A4-5), but when multiple A's exist... 413 At that time, they can be the same or different; when there are multiple A's... 423 At times, they can be the same or different.

[0234] Z 413 and Z 423 Each can independently represent -OCH2-, -CH2O-, -CH2CH2-, or a single bond, but when multiple Zs exist... 413 At that time, they can be the same or different, when there are multiple Z 423 At times, they can be the same or different.

[0235] m413 and m423 each independently represent 0, 1, or 2, but m413 + m423 represents 1 or 2.

[0236] The compounds represented by general formula (IV) are particularly preferred to be those represented by general formulas (IV-iv-1) to (IV-iv-8).

[0237] [Chemistry 42]

[0238]

[0239] [Chemistry 43]

[0240]

[0241] (where R is in the formula) 414 and R 424 Each can independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0242] To improve the storage stability of liquid crystal compositions containing compounds represented by general formula (I), stabilizers may be added. Examples of usable stabilizers include: hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, etc. When using a stabilizer, the amount of stabilizer added relative to the composition is preferably in the range of 0.005% to 1% by mass, more preferably 0.02% to 0.8% by mass, and even more preferably 0.03% to 0.5% by mass. Furthermore, one stabilizer may be used, or two or more stabilizers may be used in combination. Examples of stabilizers include compounds represented by the following general formula (X1).

[0243] [Chemistry 44]

[0244]

[0245] (where Sp) x1 This indicates that one -CH2- or two or more non-adjacent -CH2- atoms can be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-, with 1 to 20 carbon atoms or a single bond. A x1 Let A represent a basis selected from equations (Ax1-1) to (Ax1-8) below, but when there are multiple A... x1 At times, they can be the same or different.

[0246] [Chemistry 45]

[0247]

[0248] (In the formula, the dashed lines indicate the location of the bonds.)

[0249] Z x1 Represents -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO- NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -C H=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bond, but when multiple Z are present x1 At times, they can be the same or different.

[0250] mx1 represents 0 or 1.

[0251] (mx2 represents an integer from 0 to 4.)

[0252] From the viewpoints of voltage retention rate and compatibility with liquid crystal compositions, the compound represented by general formula (X1) is preferably the compound represented by the following general formula (X1-i).

[0253] [Chemistry 46]

[0254]

[0255] (where Sp) x11 A represents an alkylene group or single bond with 1 to 20 carbon atoms, where one or more non-adjacent -CH2- atoms can be independently substituted by -O-, -COO-, or -OCO-. x11 Let A represent a basis selected from the following equations (Ax11-1) and (Ax11-2), but when there are multiple A... x11 At times, they can be the same or different.

[0256] [Chemistry 47]

[0257]

[0258] (In the formula, the dashed lines indicate the location of the bonds.)

[0259] Z x11 This indicates -COO-, -OCO-, -OCO-CH2CH2-, -CH2CH2-COO-, or a single bond, but when multiple Z are present... x11 At times, they can be the same or different.

[0260] mx11 represents 0 or 1.

[0261] mx21 represents 0 or 1.

[0262] The compounds represented by general formula (X1) are particularly preferred to be those represented by general formulas (X1-ii-1) to (X1-ii-4).

[0263] [Chemistry 48]

[0264]

[0265] (where Sp) x12 (This refers to alkylene groups or single bonds with 1 to 20 carbon atoms.)

[0266] Other examples of stabilizers include compounds represented by the general formula (X2) below.

[0267] [Chemistry 49]

[0268]

[0269] (where R is in the formula) x21 R x22 R x23 and R x24 Each of these elements independently represents a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0270] Sp x21 Sp x22 Sp x23 and Sp x24 Each can independently represent a spacer base or a single bond.

[0271] mx21 represents 0 or 1.

[0272] mx22 represents 0 or 1.

[0273] mx23 represents 0 or 1.

[0274] From the viewpoints of voltage retention rate and compatibility with liquid crystal compositions, the compound represented by general formula (X2) is more preferably the compound represented by the following general formula (X2-i).

[0275] [Transformation 50]

[0276]

[0277] (where R is in the formula) x211 R x221 R x231 and R x241 Each of the following can be independently represented: a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0278] Sp x211 Sp x221 Sp x231 and Sp x241 Each independently represents any hydrogen atom in the radical that can be replaced by a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- can be independently replaced by a straight-chain or branched alkylene group or a single bond with 1 to 20 carbon atoms of -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-.

[0279] mx211 represents 0 or 1.

[0280] mx221 represents 0 or 1.

[0281] mx231 represents 0 or 1.

[0282] The compound represented by general formula (X2) is more preferably the compound represented by the following general formula (X2-ii).

[0283] [Chemistry 51]

[0284]

[0285] (where R is in the formula) x212 and R x222 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0286] Sp x212 and Sp x222 Each -CH2- or two or more non-adjacent -CH2- can be independently substituted with a straight-chain alkylene group or a single bond having 1 to 10 carbon atoms, representing -O-, -COO-, or -OCO-.

[0287] mx212 represents 0 or 1.

[0288] The compound represented by general formula (X2) is particularly preferred to be the compound represented by the following general formula (X2-iii).

[0289] [Chemistry 52]

[0290]

[0291] (where R is in the formula) x213 and R x223 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0292] Sp x213 A linear alkylene group having 1 to 10 carbon atoms, where one or more non-adjacent -CH2- atoms can be independently substituted with -COO- or -OCO-.

[0293] In this invention, the ring structures contained in 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl, and 1,3-dioxane-2,5-diyl can each be either trans or cis-isoforms. However, from the viewpoint of liquid crystal properties, it is preferable that the content of the trans-isoform is greater than the content of the cis-isoform, more preferably that the content of the trans-isoform in the ring structure is 80% or more, further preferably that the content of the trans-isoform in the ring structure is 90% or more, even more preferably that the content of the trans-isoform in the ring structure is 95% or more, and particularly preferably that the content of the trans-isoform in the ring structure is 98% or more. Furthermore, in this invention, the designation (CY-1) refers to the trans-isoform and / or cis-isoform of 1,4-cyclohexylene.

[0294] [Chemistry 53]

[0295]

[0296] (In the formula, the dashed lines indicate the location of the bonds.)

[0297] In addition, in this invention, each element may be replaced by an isotope of the same element.

[0298] [Example]

[0299] The present invention is further described below with reference to examples, but the invention is not limited to these examples. Additionally, "%" in the compositions of the following examples and comparative examples refers to "mass %". When processing substances unstable to oxygen and / or moisture in each step, it is preferable to operate in an inert gas such as nitrogen or argon. The purity of each compound was determined by ultra-high performance liquid chromatography (UPLC) (Waters ACQUITY UPLC, ethylene bridged hybrid (BEH) C). 18(100×2.1mm×1.7μm), acetonitrile / water or acetonitrile / water containing 0.1% formic acid, photodiode array (PDA), column temperature 40℃), gel permeation chromatography (GPC) (Shimadzu Prominence high performance liquid chromatography, Showa KF-801 (300mm×8mm×6μm) + KF-802 (300mm×8mm×6μm), tetrahydrofuran, refractive index (RI), ultraviolet (UV) (254nm), column temperature 40℃), gas chromatography (GC) (Agilent 6890A, J&W DB-1, 30m×0.25mm×0.25μm, carrier gas He, flame ionization detector). detector (FID), 100℃ (1 minute) → increase temperature by 10℃ / minute → 300℃ (12 minutes) or proton NMR ( 1 H nuclear magnetic resonance, 1 The determination is made using H NMR (JEOL, 400MHz).

[0300] (Example 1) Preparation of the compound represented by formula (I-1)

[0301] [Chemistry 54]

[0302]

[0303] Under a nitrogen atmosphere, 10.0 g of the compound represented by formula (I-1-1), 0.3 g of copper iodide (I), 0.5 g of bis(triphenylphosphine)palladium dichloride (II), 25 mL of triethylamine, and 50 mL of tetrahydrofuran were added to a reaction vessel. While stirring at room temperature, a solution containing 9.9 g of the compound represented by formula (I-1-2) dissolved in 50 mL of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 1 hour. 10% hydrochloric acid was injected into the reaction solution, and extraction was performed using toluene. After washing the organic layer with brine, the mixture was purified by column chromatography (silica gel, toluene) and recrystallization (toluene / hexane) to obtain 9.0 g of the compound represented by formula (I-1-3).

[0304] Under a nitrogen atmosphere, 9.0 g of the compound represented by formula (I-1-3), 0.2 g of copper iodide (I), 0.5 g of tetrakis(triphenylphosphine)palladium (0), 36 mL of triethylamine, and 18 mL of N,N-dimethylformamide were added to a reaction vessel. While heating at 75°C, a solution prepared by dissolving 3.6 g of the compound represented by formula (I-1-4) in 18 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 75°C for 2 hours. The mixture was purified by filtration, recrystallization (toluene / hexane), and recrystallization (acetone / methanol) to obtain 8.1 g of the compound represented by formula (I-1).

[0305] Mass spectrometry (MS) (electron impact (EI)): m / z = 438

[0306] (Example 2) Preparation of the compound represented by formula (I-2)

[0307] [Chemistry 55]

[0308]

[0309] In Example 1, the compound represented by formula (I-1-4) was replaced with the compound represented by formula (I-2-2), and the compound represented by formula (I-2) was otherwise manufactured using the same method.

[0310] MS(EI): m / z = 435

[0311] (Example 3) Preparation of the compound represented by formula (I-3)

[0312] [Chemistry 56]

[0313]

[0314] In Example 1, the compound represented by formula (I-1-4) was replaced with the compound represented by formula (I-3-2), and the compound represented by formula (I-3) was otherwise manufactured using the same method.

[0315] MS(EI): m / z = 456

[0316] (Example 4) Preparation of the compound represented by formula (I-4)

[0317] [Chemistry 57]

[0318]

[0319] In Example 1, the compound represented by formula (I-1-4) was replaced with the compound represented by formula (I-4-2), and the compound represented by formula (I-4) was otherwise manufactured using the same method.

[0320] MS(EI): m / z = 456

[0321] (Example 5) Preparation of the compound represented by formula (I-5)

[0322] [Chem.58]

[0323]

[0324] In Example 1, the compound represented by formula (I-1-1) was replaced with the compound represented by formula (I-5-1), and the compound represented by formula (I-5) was otherwise manufactured using the same method.

[0325] MS(EI): m / z = 452

[0326] (Example 6) Preparation of the compound represented by formula (I-6)

[0327] [Chemistry 59]

[0328]

[0329] In Example 1, the compound represented by formula (I-1-2) was replaced with the compound represented by formula (I-6-1), and the compound represented by formula (I-6) was otherwise manufactured using the same method.

[0330] MS(EI): m / z = 402

[0331] (Preparation and Evaluation of Liquid Crystal Compositions)

[0332] A parent liquid crystal (LC-1) exhibiting the following physical properties was prepared. All values ​​are measured values.

[0333] T ni (Nematic-isotropic liquid phase transition temperature): 74.0℃

[0334] Δε (dielectric constant anisotropy at 25℃): 5.11

[0335] Δn (refractive index anisotropy at 25℃): 0.141

[0336] γ1 (rotational viscosity at 25°C): 107

[0337] Liquid crystal compositions were prepared by adding 0%, 5%, and 10% of compounds (I-1) to (I-6) obtained in Examples 1 to 6, respectively, and any one of the compounds represented by formula (C-1) and formula (C-2) described in Patent Document 1 to the parent liquid crystal (LC-1).

[0338] [Transformation 60]

[0339]

[0340] The extrapolated values ​​obtained using the least squares method are shown below. By comparing Examples 7 to 12 and Comparative Examples 1 to 2, it was determined that since the compounds of this application exhibit high Δn and high Tni, they effectively increase Δn and Tni when added to the liquid crystal composition.

[0341] [Table 1]

[0342] compound Δn Tni Comparative Example 1 (C-1) 0.393 131.0 Comparative Example 2 (C-2) 0.326 108.0 Example 7 (I-1) 0.456 ＞250.0 Example 8 (I-2) 0.478 ＞250.0 Example 9 (I-3) 0.424 ＞250.0 Example 10 (I-4) 0.496 ＞250.0 Example 11 (I-5) 0.426 217.0 Example 12 (I-6) 0.435 ＞250.0

[0343] Next, a liquid crystal composition was prepared by adding 10% of compounds (I-1) to (I-6) obtained in Examples 1 to 6 and the compound represented by formula (C-3) described in Patent Document 3 relative to the parent liquid crystal (LC-1), and its properties were measured as follows.

[0344] [Chemistry 61]

[0345]

[0346] A first substrate (common electrode substrate) comprising an alignment film and a second substrate (pixel electrode substrate) comprising an alignment film having a pixel electrode layer having a transparent pixel electrode driven by an active element are fabricated. A sealing material is coated on the first substrate and clamped onto the second substrate. The sealing material is hardened under normal pressure, 120°C, and for 1 hour to obtain a liquid crystal cell with a cell gap of 3.2 μm. After injecting a liquid crystal composition into the liquid crystal cell, it is sealed. While applying a 10V, 100Hz rectangular AC wave, it is irradiated with a high-pressure mercury lamp at an illuminance of 100mW / cm² at 365nm. 2 The liquid crystal cells were fabricated by exposing them to UV light for 200 seconds. The voltage holding ratio (VHR) of the liquid crystal cells, i.e., the voltage holding rate (%) at 60°C under conditions of 60Hz frequency and 1V applied voltage, was evaluated in three stages.

[0347] A: 95%–100%

[0348] B: 85%–95%

[0349] C: Below 85%

[0350] Lightfastness VHR: The liquid crystal composition was irradiated with a backlight for a liquid crystal display (LCD) through a 0.5 mm thick glass for one week. The voltage retention rate of the liquid crystal after irradiation was measured using the same method as the VHR measurement, and evaluated in the following three stages.

[0351] A: 95%–100%

[0352] B: 85%–95%

[0353] C: Below 85%

[0354] [Table 2]

[0355] compound VHR Lightfast VHR Comparative Example 3 (C-3) B C Example 13 (I-1) A A Example 14 (I-2) A A Example 15 (I-3) A A Example 16 (I-4) B B Example 17 (I-5) A A Example 18 (I-6) A A

[0356] By comparing Examples 13 to 18 and Comparative Example 3, it was determined that the compound of this application has high reliability.

Claims

1. A compound represented by the following general formula (I), In the formula, R 1 Indicates a straight-chain alkyl group having 1 to 8 carbon atoms. R 2 It represents a fluorine atom, a cyano group, or a straight-chain alkyl group having 1 to 8 carbon atoms. A 1 and A 2 Each group independently represents 1,4-phenylene, and these groups are either unsubstituted or can be substituted with more than one L group. 3 replace, L 3 Each independently represents a straight-chain alkyl group having 1 to 8 carbon atoms and fluorine atoms. L 1 and L 2 Each independently represents a straight-chain alkyl group having 1 to 20 hydrogen atoms, fluorine atoms, or carbon atoms. Z 1 This means -C≡C-. n1 represents 1.

2. A composition comprising the compound as claimed in claim 1.

3. A liquid crystal composition comprising the compound as described in claim 1.

4. The liquid crystal composition according to claim 3, wherein, The refractive index anisotropy is greater than 0.

15.

5. The liquid crystal composition according to claim 3, wherein, The dielectric constant anisotropy is greater than 2.

6. The liquid crystal composition according to claim 3, wherein, The dielectric constant anisotropy is less than 2.

7. A high-frequency phase shifter, phased array antenna, image recognition device, ranging device, liquid crystal display element, liquid crystal lens or birefringent lens for stereoscopic image display, using the liquid crystal composition as described in any one of claims 3 to 6.

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