Compounds, liquid crystal compositions, and liquid crystal display elements or dimming elements

Abstract

The problem to be solved by the present invention is to provide a compound that exhibits high lightfastness while also having a large dichroic ratio and high solubility in the host liquid crystal, and to provide a liquid crystal composition using the compound as a constituent element, as well as a liquid crystal display element or a dimming element. As a solution, the present invention provides a compound represented by the following general formula (1), and provides a liquid crystal composition containing the compound and a liquid crystal display element or a dimming element using the liquid crystal composition. The compound represented by the general formula (1) provided by the present invention simultaneously possesses a large dichroic ratio and high solubility in the host liquid crystal. In addition, it also possesses excellent chemical stability at a level suitable for use as an element. Therefore, by using the compound represented by the general formula (1) as a component of a GH-type liquid crystal composition, it is possible to provide a liquid crystal display element or a dimming element with high contrast. [Chemical 1]

Description

Technical Field

[0001] This invention relates to novel dichroic pigments useful as organic electronic materials, pharmaceutical pesticides, and especially as materials for liquid crystal display elements, and liquid crystal compositions using the same. Background Technology

[0002] Liquid crystal materials are not only used in various display elements that display text, images, and videos, such as TVs and smartphones, but their application as dimming elements that regulate light transmission is also becoming practical.

[0003] In the case of using a "guest-host (GH) type liquid crystal composition" in which a dichroic pigment is added to the host liquid crystal composition, since a polarizing plate is not required, it is expected that a dimming element with high transmittance can be achieved at low cost.

[0004] Research on GH-type liquid crystal compositions began very early on, and efforts have been made to develop liquid crystal display elements and dimming elements with useful element properties (e.g., large dichroism ratio, high contrast, high solubility in liquid crystal compositions, excellent light resistance, and excellent heat resistance) (see Patent Document 1).

[0005] However, liquid crystal compositions containing dichroic pigments are sometimes unsuitable for use in liquid crystal display elements and dimming elements, depending on their composition, requiring further performance improvements. For example, to obtain a high dichroism ratio, the liquid crystal composition needs to contain a large amount of dichroic pigments, which presents a solubility problem where the dichroic pigments and liquid crystal compounds precipitate out. In particular, for use as a dimming element, it is necessary to present a nematic liquid crystal phase over a wide temperature range, but the molecular weight of the pigment is larger than that of the liquid crystal compound, thus posing a challenge regarding solubility at low temperatures.

[0006] To address the issues described above, it is necessary to improve the liquid crystal composition as the main component, and also to improve the dichroic pigment itself. In particular, to achieve high contrast, the dichroic pigment needs to exhibit a large dichroic ratio and high solubility in the main liquid crystal. Many dichroic pigments have been studied to date, but compounds exhibiting large dichroic ratios generally have large liquid crystal origins and almost all lack solubility in the main liquid crystal, requiring further improvement (Non-Patent Literature 1, 2, 3).

[0007] On the other hand, as pigment compounds, compounds having a benzodipyrrolidone skeleton as described below (Patent Document 2, Non-Patent Document 4) have been reported, but these compounds have not yet achieved the simultaneous possession of high lightfastness, large dichroism ratio and high solubility.

[0008] [Chemistry 1]

[0009]

[0010] [Chemistry 2]

[0011]

[0012] [Existing Technical Documents]

[0013] [Patent Literature]

[0014] [Patent Document 1] Japanese Patent Publication No. 2013-534945

[0015] [Patent Document 2] Japanese Patent Application Publication No. 2015-40231

[0016] [Non-patent literature]

[0017] [Non-Patent Literature 1] "Display Materials and Functional Pigments" by Hiroyuki Nakajima

[0018] [Non-Patent Literature 2] "Technology of Functional Pigments" by Hiroyuki Nakajima

[0019] [Non-Patent Document 3] "Dichroic Dyes for Liquid Crystal Displays" by Aleksandr V. Ivashchenko

[0020] [Non-Patent Literature 4] J. Mater. Chem. C, 2017, 5, 290-300 Summary of the Invention

[0021] The problem that the invention aims to solve

[0022] The problem to be solved by the present invention is to provide a compound that exhibits high lightfastness while having a large dichroism ratio and high solubility in the main liquid crystal, and to provide a liquid crystal composition using the compound as a constituent element, as well as a liquid crystal display element or a dimming element.

[0023] Methods for solving problems

[0024] In order to solve the above-mentioned problems, the inventors of this application have conducted research on various compounds and provided a compound represented by general formula (1), and provided a liquid crystal composition containing the compound and a liquid crystal display element or dimming element using the liquid crystal composition.

[0025] [Chemistry 3]

[0026]

[0027] (In the formula, B is any group selected from the groups represented by general formulas (2), (3) or (4).)

[0028] [Chemistry 4]

[0029]

[0030] In general formulas (2), (3), or (4), the carbon atoms represented by *1 to *4 correspond to the carbon atoms represented by *1 to *4 in general formula (1), and one or more hydrogen atoms in these groups can be substituents L. 1 replace,

[0031] L 1 Each of the following groups 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. Each of these groups can independently be represented by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, - A straight-chain alkyl group with 1 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, substituted with 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-, wherein the oxygen atoms are not directly connected to each other, and any hydrogen atom in the alkyl group can be replaced by a fluorine atom.

[0032] R 1 and R 2 Each group independently represents an alkyl group with 1 to 20 carbon atoms or an alkenyl group with 2 to 30 carbon atoms. One -CH2- or two or more non-adjacent -CH2- groups present in these groups can be represented by -NR. 3 -, -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, or -C≡C- are substituted. The hydrogen atoms in these groups can be replaced by fluorine atoms, where R... 3 This refers to an alkyl group containing 1 to 20 carbon atoms or an alkenyl group containing 2 to 30 carbon atoms, wherein one or more non-adjacent -CH2- atoms may be replaced by -O-, -S-, -COO-, -OCO-, or -CO-, and the hydrogen atoms present in these groups may be replaced by fluorine atoms.

[0033] X 1 and X 2Each can be represented independently as -S- or -NR. 4 -, where R 4 This refers to alkyl groups with 1 to 20 carbon atoms or alkenyl groups with 2 to 30 carbon atoms, wherein one or more non-adjacent -CH2- groups can be substituted with -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-, -C≡C-, or substituted hydrocarbon rings or heterocycles with 3 to 16 carbon atoms, and hydrogen atoms present in these groups can be substituted with fluorine atoms.

[0034] A 1 and A 2 Each can independently represent a hydrocarbon ring or heterocycle with 3 to 16 carbon atoms that can be substituted.

[0035] Z 1 and Z 2 Each can independently represent -CH2O-, -OCH2-, -CF2O-, -OCF2-, -COO-, -OCO-, -CH2CH2-, -CF2CF2-, -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond.

[0036] i and j each independently represent integers from 1 to 4.

[0037] In A 1 and A 2 When there are multiple A's, multiple A's 1 and A 2 They can be the same or different, in Z 1 and Z 2 In the case of multiple Z, multiple Z 1 and Z 2 They can be the same or different, and there are multiple Rs. 3 and R 4 In the case of multiple R 3 and R 4 They can be the same or different.

[0038] Invention Effects

[0039] The compound represented by general formula (1) provided by the present invention possesses both a large dichroism ratio and high solubility in the bulk liquid crystal. In addition, it also possesses excellent chemical stability at a level suitable for use as an element. Therefore, by using the compound represented by general formula (1) as a component of a GH-type liquid crystal composition, it is possible to provide a liquid crystal display element or a dimming element with high contrast. Detailed Implementation

[0040] In general formula (1), for B, in order to increase the dichroism ratio, the structure represented by general formula (3) or general formula (4) is preferred, and when lightfastness and solubility in the bulk liquid crystal are important, the structure represented by general formula (2) is preferred. Furthermore, it is also preferable that one or more hydrogen atoms in these groups are substituents for L. 1 Replace. L 1 Each of the following is preferably an independent hydrogen atom, fluorine atom, chlorine 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. Each of these can be independently replaced 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 having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, each further preferably having hydrogen atoms, fluorine atoms, chlorine atoms, pentafluorothioalkyl groups, nitro groups, cyano groups, isocyano groups, dimethylamino groups, diethylamino groups, diisopropylamino groups, thioisocyano groups, methyl groups, ethyl groups, propyl groups, methoxy groups, ethoxy groups or acetyl groups.

[0041] X 1 and X 2 Preferably, the group consists of alkyl groups with 1 to 20 carbon atoms or alkenyl groups with 2 to 20 carbon atoms. One or more non-adjacent -CH2- groups are preferably 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-. To improve solubility in the bulk liquid crystal, -NR is preferred. 4 -, at this time R 4 Preferably, it is a non-substituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a non-substituted straight-chain or branched alkyl group having 4 to 20 carbon atoms, and particularly preferably a non-substituted branched alkyl group having 4 to 20 carbon atoms. Furthermore, where lightfastness is important, -S- is preferred.

[0042] R 1 and R 2Each of the groups is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. One or more non-adjacent -CH2- groups in these groups are preferably substituted with -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -CH=CH-, -CF=CF-, or -C≡C-. To improve solubility in the bulk liquid crystal, each of the groups is preferably a non-substituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a non-substituted straight-chain or branched alkyl group having 4 to 20 carbon atoms, and particularly preferably a non-substituted branched alkyl group having 4 to 20 carbon atoms.

[0043] From the perspectives of increasing the absorption wavelength, improving dichroism, and enhancing solubility in liquid crystal compositions, A 1 and A 2 Each group is preferably a hydrocarbon ring or heterocycle with 3 to 16 carbon atoms that can be substituted. Preferably, each group is selected from the group consisting of the following groups:

[0044] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups in this group may be replaced by -O- or -S-.)

[0045] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups in this group can be replaced by -N=.)

[0046] (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 contain...) The hydrogen atom can be replaced by a fluorine or chlorine atom. Furthermore, one or more -CH= atoms 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 can be replaced by -N=.

[0047] (d) Thiophene-2,5-diyl, thiophene-2,4-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, thiopheno[3,2-b]thiophene-2,5-diyl (one -CH= or two or more non-adjacent -CH= groups may be substituted by -N=.)

[0048] Furthermore, these groups are preferably unsubstituted or substituted with one or more L groups. 2 replace.

[0049] L 2 Each of the following is preferably an independent hydrogen atom, fluorine atom, chlorine 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. Each of these can be independently replaced 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 having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, each further preferably having hydrogen atoms, fluorine atoms, chlorine atoms, pentafluorothioalkyl groups, nitro groups, cyano groups, isocyano groups, dimethylamino groups, diethylamino groups, diisopropylamino groups, thioisocyano groups, methyl groups, ethyl groups, propyl groups, methoxy groups, ethoxy groups or acetyl groups.

[0050] In addition, as A 1 and A 2 The preferred structure is preferably represented by a group selected from the following structures.

[0051] [Chemistry 5]

[0052]

[0053] Here, R ePreferably, each of the following can be independently represented: methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, diethylamino, cyano, nitro, fluorine atom, or chlorine atom. Specifically, to improve solubility in the bulk liquid crystal, trans-1,4-cyclohexylene, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2-alkyl-1,4-phenylene, 3-alkyl-1,4-phenylene, unsubstituted thiophene-2,5-diyl, unsubstituted thiophene-2,4-diyl, 4-alkyl-thiophene-2,5-diyl, or 5-alkyl-thiophene-2,4-diyl. In this case, when A... 1 and A 2 When multiple A's exist, multiple A's are preferred. 1 and A 2 These represent different structures. To increase the dichroism ratio, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, unsubstituted thiophene-2,5-diyl, unsubstituted thiophene-2,4-diyl, unsubstituted naphthyl-2,6-diyl, or unsubstituted naphthyl-1,4-diyl are preferred.

[0054] In addition, in order to improve solubility in the bulk liquid crystal, R e Preferably, it represents a methyl, ethyl, propyl, fluorine atom, or chlorine atom, more preferably a methyl, ethyl, or fluorine atom. To achieve a longer absorption wavelength, R... e The preferred substituent is an electron-donating substituent, more preferably methoxy, ethoxy, dimethylamino, or diethylamino, and particularly preferably methoxy, ethoxy, or dimethylamino.

[0055] To improve solubility in the bulk liquid crystal, Z 1 and Z 2 Each component is preferably -CH2O-, -OCH2-, -CH2CH2-, or a single bond, and more preferably -CH2CH2- or a single bond. To increase the dichroic ratio, the components are preferably -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond, and more preferably -CH=CH-, -N=N-, -C≡C-, or a single bond. To exhibit high lightfastness, a single bond is preferred.

[0056] To improve solubility in the bulk liquid crystal, i and j are each preferably 1 or 2 independently. To increase the dichroism ratio, 2, 3 or 4 are preferred, and 3 or 4 are even more preferred.

[0057] It should be noted that, in general formula (1), from the viewpoint of compound stability, it is preferable that oxygen atoms are not directly connected to each other and / or oxygen atoms are not directly connected to sulfur atoms.

[0058] The compounds represented by general formula (1) are characterized by having a skeleton such as benzodipyrrolidone in their structure, and having R at both ends. 1 and R 2 The alkyl group and A are represented 1 and A 2 The ring structure is represented. Due to these characteristics, the compound as a whole approximates a rod-like structure, thus improving its solubility in liquid crystal compositions and enhancing its dichroism when used as a pigment. In particular, in A... 1 and A 2 In the case of an aromatic ring, the conjugated system of π electrons extends to the entire molecule, thus being effective for increasing the wavelength of light absorption.

[0059] The compound represented by general formula (1) is preferably represented by the following formulas (1-A) to (1-F).

[0060] [Chemistry 6]

[0061]

[0062] (where R is in the formula) 1 R 2 X 1 X 2 A 1 A 2 Z 1 Z 2 i and j each represent R in general formula (1) 1 R 2 X 1 X 2 A 1 A 2 Z 1 Z 2 (i and j have the same meaning).

[0063] In general formula (1), the compounds represented by the following general formulas (1-1) to (1-96) are particularly preferred.

[0064] [Chemistry 7]

[0065]

[0066] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0067] [Chemistry 8]

[0068]

[0069] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0070] [Chemistry 9]

[0071]

[0072] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0073] [Chemistry 10]

[0074]

[0075] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0076] [Chemistry 11]

[0077]

[0078] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0079] [Chemistry 12]

[0080]

[0081] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0082] [Chemistry 13]

[0083]

[0084] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0085] [Chemistry 14]

[0086]

[0087] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0088] [Chemistry 15]

[0089]

[0090] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0091] [Chemistry 16]

[0092]

[0093] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0094] [Chemistry 17]

[0095]

[0096] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0097] [Chemistry 18]

[0098]

[0099] (where R is in the formula) 1 R 2 and R 4 R represents the general formula (1) 1 R 2 and R 4 Same meaning.

[0100] (Manufacturing method)

[0101] In this invention, among the compounds represented by general formula (1), X 1 and X 2 For -NR 4 The compounds can be manufactured as follows. Of course, the spirit and scope of the invention are not limited to these manufacturing examples.

[0102] The compound represented by general formula (1-a) can be manufactured using the methods described in non-patent literature (Dyes and Pigments, 162 (2019) 883-887).

[0103] [Chemistry 19]

[0104]

[0105] (where Y) a1 and Y a2 Each independently represents a bromine atom, chlorine atom, iodine atom, or trifluoromethanesulfonyloxy group, R 4 R represents the expression in general formula (1) 4 The same meaning is given by B, which means the same as the B represented by general formula (1). By reacting the compound represented by general formula (1-a) with the compound represented by general formula (1-b) in the presence of a transition metal catalyst and a base, it is possible to produce the target compound represented by general formula (1).

[0106] [Chemistry 20]

[0107]

[0108] (where A is in the formula) b This represents A in general formula (1). 1 Or A 2 The same meaning, Z b This represents Z in general formula (1). 1 and Z 2 With the same meaning, b represents i-1 or j-1 in general formula (1), Rb R represents the general formula (1) 1 or R 2 The same meaning, Y b for

[0109] [Chemistry 21]

[0110]

[0111] (where R is in the formula) i1 and R i2 Each independently represents a hydrogen atom or a straight-chain or branched alkyl group with 1 to 5 carbon atoms, E i1 -(CH2) indicates that one or more hydrogen atoms in the group can be independently replaced by a methyl group. pi -, pi represents 2, 3, or 4.

[0112] As for the transition metal catalyst used, any one is acceptable as long as it is suitable for the reaction to proceed. Preferred catalysts include tetra(triphenylphosphine)palladium (0), palladium acetate (II), bis(triphenylphosphine)palladium (II) dichloride, [1,1'-bis(diphenylphosphino)ferrocene]palladium (II) dichloride, or bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium (II). More preferred catalysts are tetra(triphenylphosphine)palladium (0), [1,1'-bis(diphenylphosphino)ferrocene]palladium (II) dichloride, or bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium (II). Furthermore, to ensure the reaction proceeds smoothly, phosphine ligands such as triphenylphosphine can be added as needed.

[0113] The reaction solvent used can be any solvent that allows the reaction to proceed smoothly. Preferred solvents include ether-based solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether; alcohol-based solvents such as methanol, ethanol, and propanol; and aromatic solvents such as benzene, toluene, and xylene. Tetrahydrofuran, ethanol, and toluene are more preferred. Water can also be used as needed to ensure the reaction proceeds smoothly.

[0114] The base used can be any base that allows the reaction to proceed properly, preferably a carbonate such as potassium carbonate, sodium carbonate, or cesium carbonate, or a phosphate such as tripotassium phosphate or potassium dihydrogen phosphate, and more preferably potassium carbonate, cesium carbonate, or tripotassium phosphate.

[0115] As for the reaction temperature, any temperature is acceptable as long as the reaction is suitable. Room temperature to the temperature at which the solvent used refluxes is preferred, more preferably 40°C to the temperature at which the solvent refluxes, and particularly preferably 60°C to the temperature at which the solvent refluxes.

[0116] In the compound represented by general formula (1), X 1 and X 2Compounds of type -S- can be prepared as follows.

[0117] The compound represented by general formula (1-c) can be manufactured using the methods described in non-patent literature (Chemistry Letters, 1983, 905-908).

[0118] [Chemistry 22]

[0119]

[0120] (where Y) c1 and Y c2 Each of the atoms independently represents a bromine atom, a chlorine atom, an iodine atom, or a trifluoromethanesulfonyloxy group, and B represents the same meaning as B in general formula (1). ) By reacting the compound represented by general formula (1-c) with the compound represented by general formula (1-d) in the presence of a transition metal catalyst and a base, it is possible to produce the target compound represented by general formula (1).

[0121] [Chemistry 23]

[0122]

[0123] (where A is in the formula) d This represents A in general formula (1). 1 Or A 2 The same meaning, Z d This represents Z in general formula (1). 1 or Z 2 With the same meaning, d represents i or j in general formula (1), R d R represents the general formula (1) 1 or R 2 The same meaning, Y b This represents Y in the general formula (1-b) b (Same meaning).

[0124] As for the transition metal catalyst used, any one is acceptable as long as it is suitable for the reaction to proceed. Preferred catalysts include tetra(triphenylphosphine)palladium (0), palladium acetate (II), bis(triphenylphosphine)palladium (II) dichloride, [1,1'-bis(diphenylphosphino)ferrocene]palladium (II) dichloride, or bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium (II). More preferred catalysts are tetra(triphenylphosphine)palladium (0), [1,1'-bis(diphenylphosphino)ferrocene]palladium (II) dichloride, or bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium (II). Furthermore, to ensure the reaction proceeds smoothly, phosphine ligands such as triphenylphosphine can be added as needed.

[0125] The reaction solvent used can be any solvent that allows the reaction to proceed smoothly. Preferred solvents include ether-based solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether; alcohol-based solvents such as methanol, ethanol, and propanol; and aromatic solvents such as benzene, toluene, and xylene. Tetrahydrofuran, ethanol, and toluene are more preferred. Water can also be used as needed to ensure the reaction proceeds smoothly.

[0126] The base used can be any base that allows the reaction to proceed properly, preferably a carbonate such as potassium carbonate, sodium carbonate, or cesium carbonate, or a phosphate such as tripotassium phosphate or potassium dihydrogen phosphate, and more preferably potassium carbonate, cesium carbonate, or tripotassium phosphate.

[0127] As for the reaction temperature, any temperature is acceptable as long as the reaction is suitable. It is preferred to be room temperature to the temperature at which the solvent used is refluxed, more preferably 40°C to the temperature at which the solvent is refluxed, and particularly preferably 60°C to the temperature at which the solvent is refluxed.

[0128] In the liquid crystal composition of the present invention, if the content of the compound represented by general formula (1) is low, its effect will not be apparent. Therefore, as a lower limit, the composition preferably contains 1% by mass (in the following composition, % represents mass%) or more, preferably 2% or more, and more preferably 3% or more. Furthermore, if the content is high, it will cause problems such as precipitation. Therefore, as an upper limit, it is preferably 7% or less, and more preferably 6% or less. The compound represented by general formula (1) may be used only once, or two or more compounds may be used simultaneously.

[0129] Thus, as a preferred example of a compound that can be used in combination with the compound represented by general formula (1), it is particularly preferred that the composition provided by the present invention contains, as a first component, at least one compound represented by general formula (1), and as other components, at least one of the following second to fourth components.

[0130] That is, the second component is a so-called p-type liquid crystal compound with positive dielectric anisotropy, and examples can be given by the following general formulas (LC1) and (LC2).

[0131] [Chemistry 24]

[0132]

[0133] (where R is in the formula) LC11 and R LC21Each of these groups independently represents an alkyl group having 1 to 15 carbon atoms, wherein one or more -CH2- atoms in the alkyl group may be substituted with -O-, -CH=CH-, -CO-, -OCO-, -COO-, or -C≡C- in such a manner that oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the alkyl group may be substituted with halogen atoms in any manner. LC11 and A LC21 Each can independently represent any of the following structures.

[0134] [Chemistry 25]

[0135]

[0136] (In this structure, one or more -CH2- atoms in the cyclohexene group can be replaced by oxygen atoms, one or more -CH= atoms in the 1,4-phenylene group can be replaced by -N= atoms, and one or more hydrogen atoms in this structure can be replaced by fluorine atoms, chlorine atoms, -CF3 or -OCF3 atoms.) X LC11 X LC12 X LC21 ~X LC23 Each of the following can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, -CF3, or -OCF3, Y LC11 and Y LC21 Each can independently represent a hydrogen atom, fluorine atom, chlorine atom, cyano group, -CF3, -OCH2F, -OCHF2 or -OCF3, Z LC11 and Z LC21 Each can independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -OCF2-, -CF2O-, -COO-, or -OCO-, m LC11 and m LC21 Each of the integers from 1 to 4 can be represented independently in A. LC11 A LC21 Z LC11 and Z LC21 If multiple instances exist, they can be the same or different.

[0137] R LC11 and R LC21 Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms; more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms; even more preferably a linear chain; and most preferably an alkenyl group with the following structure.

[0138] [Chemistry 26]

[0139]

[0140] (In the formula, it connects to the ring structure at the right end.)

[0141] A LC11 and A LC21 Each of them is preferably configured as follows.

[0142] [Chemistry 27]

[0143]

[0144] Y LC11 and Y LC21 Each of the components is preferably a fluorine atom, a cyano group, -CF3 or -OCF3, preferably a fluorine atom or -OCF3, and particularly preferably a fluorine atom.

[0145] Z LC11 and Z LC21 Preferably, it is a single bond, -CH2CH2-, -COO-, -OCO-, -OCH2-, -CH2O-, -OCF2- or -CF2O-, more preferably a single bond, -CH2CH2-, -OCH2-, -OCF2- or -CF2O-, and even more preferably a single bond, -OCH2- or -CF2O-.

[0146] m LC11 and m LC21 Preferably, it is 1, 2 or 3. When it is important to maintain the storage stability and response speed at low temperature, it is preferred to be 1 or 2. In order to improve the upper limit of the nematic phase upper limit temperature, it is preferred to be 2 or 3.

[0147] The general formula (LC1) is preferably one or more compounds selected from the group consisting of compounds represented by the following general formulas (LC1-a) to (LC1-c).

[0148] [Chemistry 28]

[0149]

[0150] (where R is in the formula) LC11 Y LC11 X LC11 and X LC12 Each independently represents R in the above general formula (LC1). LC11 Y LC11 X LC11 and X LC12 Same meaning, A LC1a1 A LC1a2 and A LC1b1 This indicates trans-1,4-cyclohexylene, tetrahydropyran-2,5-diyl, and 1,3-diyl-diyl-2,4-cyclohexylene. Alkyl-2,5-diyl, X LC1b1 X LC1b2 X LC1c1 ~X LC1c4 Each can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, -CF3, or -OCF3.

[0151] R LC11 Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms; more preferably, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0152] X LC11 ~X LC1c4 Each atom is preferably a hydrogen atom or a fluorine atom.

[0153] Y LC11 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0154] Furthermore, the general formula (LC1) is preferably one or more compounds selected from the group consisting of compounds represented by the following general formulas (LC1-d) to (LC1-m).

[0155] [Chemistry 29]

[0156]

[0157] (where R is in the formula) LC11 Y LC11 X LC11 and X LC12 Each independently represents R in the above general formula (LC1). LC11 Y LC11 X LC11 and X LC12 Same meaning, A LC1d1 A LC1f1 A LC1g1 A LC1j1 A LC1k1 A LC1k2 A LC1m1 ~A LC1m3 This represents 1,4-phenylene, trans-1,4-cyclohexylene, tetrahydropyran-2,5-diyl, and 1,3-diphenylene. Alkyl-2,5-diyl, X LC1d1 X LC1d2 X LC1f1 X LC1f2 X LC1g1 X LC1g2 X LC1h1 X LC1h2 X LC1i1 XLC1i2 X LC1j1 ~X LC1j4 X LC1k1 X LC1k2 X LC1m1 and X LC1m2 Each can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, -CF3 or -OCF3, Z LC1d1 Z LC1e1 Z LC1j1 Z LC1k1 Z LC1m1 Each of these can independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -OCF2-, -CF2O-, -COO-, or -OCO-.

[0158] R LC11 Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms; more preferably, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0159] X LC11 ~X LC1m2 Each atom is preferably a hydrogen atom or a fluorine atom.

[0160] Y LC11 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0161] Z LC1d1 ~Z LC1m1 Each is preferably -CF2O- or -OCH2-.

[0162] The general formula (LC2) is preferably one or more compounds selected from the group consisting of compounds represented by the following general formulas (LC2-a) to (LC2-g).

[0163] [Chemistry 30]

[0164]

[0165] (where R is in the formula) LC21 Y LC21 X LC21 ~X LC23 Each independently represents R in the above general formula (LC2). LC21 Y LC21 X LC21 ~X LC23 Same meaning, X LC2d1 ~X LC2d4 X LC2e1~X LC2e4 X LC2f1 ~X LC2f4 and X LC2g1 ~X LC2g4 Each can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, -CF3 or -OCF3, Z LC2a1 Z LC2b1 Z LC2c1 Z LC2d1 Z LC2e1 Z LC2f1 and Z LC2g1 Each of these can independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -OCF2-, -CF2O-, -COO-, or -OCO-.

[0166] R LC21 Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms; more preferably, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.

[0167] X LC21 ~X LC2g4 Each atom is preferably a hydrogen atom or a fluorine atom.

[0168] Y LC21 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0169] Z LC2a1 ~Z LC2g4 Each is preferably -CF2O- or -OCH2-.

[0170] The third component is the so-called n-type liquid crystal compound with negative dielectric constant anisotropy, and the compounds represented by the following general formulas (LC3) to (LC5) can be cited as examples.

[0171] [Chemistry 31]

[0172]

[0173] (where R is in the formula) LC31 R LC32 R LC41 R LC42 R LC51 and R LC52Each of these groups independently represents an alkyl group having 1 to 15 carbon atoms, wherein one or more -CH2- atoms in the alkyl group may be substituted with -O-, -CH=CH-, -CO-, -OCO-, -COO-, or -C≡C- in such a manner that oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the alkyl group may be substituted with halogen atoms in any manner. LC31 A LC32 A LC41 A LC42 A LC51 and A LC52 Each can independently represent any of the following structures.

[0174] [Chemistry 32]

[0175]

[0176] (In this structure, one or more -CH2- atoms in the cyclohexene group can be replaced by oxygen atoms, one or more -CH= atoms in the 1,4-phenylene group can be replaced by -N= atoms, and one or more hydrogen atoms in this structure can be replaced by fluorine atoms, chlorine atoms, -CF3 or -OCF3 atoms.) Z LC31 Z LC32 Z LC41 Z LC42 Z LC51 and Z LC51 Each can independently represent a single bond, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -COO-, -OCH2-, -CH2O-, -OCF2-, or -CF2O-, Z 5 X represents -CH2- or oxygen atom. LC41 Indicates a hydrogen atom or a fluorine atom, m LC31 m LC32 m LC41 m LC42 m LC51 and m LC52 Each can be represented independently from 0 to 3, m LC31 +m LC32 m LC41 +m LC42 and m LC51 +m LC52 It is 1, 2 or 3, in A LC31 ~A LC52 Z LC31 ~Z LC52 If multiple instances exist, they can be the same or different.

[0177] R LC31 ~R LC52Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. The alkenyl group is most preferably represented by the following structure:

[0178] [Chemistry 33]

[0179]

[0180] (In the formula, it connects to the ring structure at the right end.)

[0181] A LC31 ~A LC52 Each of them is preferably configured as follows,

[0182] [Chemistry 34]

[0183]

[0184] Z LC31 ~Z LC51 Each is preferably a single bond, -CH2O-, -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, or -OCH2-.

[0185] The general formula (LC3) is preferably one or more compounds selected from the group of compounds represented by the general formulas (LC3-a) and (LC3-b) below.

[0186] [Chemistry 35]

[0187]

[0188] (where R is in the formula) LC31 R LC32 A LC31 and Z LC31 Each independently represents R in the above general formula (LC3). LC31 R LC32 A LC31 and Z LC31 Same meaning, X LC3b1 ~X LC3b6 It represents a hydrogen atom or a fluorine atom, but X LC3b1 and X LC3b2 Or X LC3b3 and X LC3b4 At least one of the combinations in m simultaneously represents a fluorine atom. LC3a1 For 1, 2, or 3, m LC3b1 Representing 0 or 1, in A LC31 and Z LC31 When multiple compounds exist, they can be the same or different. (Note: Compounds selected from the group represented by general formula (LC3-b) are excluded from general formula (LC3-a).)

[0189] R LC31 and R LC32 Each of the following is preferred to be an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.

[0190] A LC31 Preferred representations include 1,4-phenylene, trans-1,4-cyclohexylene, tetrahydropyran-2,5-diyl, and 1,3-diylphenylene. Alkyl-2,5-diyl, more preferably 1,4-phenylene or trans-1,4-cyclohexylene.

[0191] Z LC31 Preferably, it represents a single bond, -CH2O-, -COO-, -OCO-, or -CH2CH2-, and more preferably, it represents a single bond.

[0192] As general formula (LC3-a), it is preferable to represent the following general formulas (LC3-a1) to (LC3-a4).

[0193] [Chemistry 36]

[0194]

[0195] (where R is in the formula) LC31 and R LC32 Each independently represents R in the above general formula (LC3). LC31 and R LC32 Same meaning.

[0196] R LC31 and R LC32 Each is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, R LC31 More preferably, it represents an alkyl group having 1 to 7 carbon atoms, R LC32 More preferably, an alkoxy group representing 1 to 7 carbon atoms.

[0197] As for the general formula (LC3-b), it is preferred to represent the following general formulas (LC3-b1) to (LC3-b12), more preferably the general formulas (LC3-b1), (LC3-b6), (LC3-b8), and (LC3-b11), even more preferably the general formulas (LC3-b1) and (LC3-b6), and most preferably the general formula (LC3-b1).

[0198] [Chemistry 37]

[0199]

[0200] (where R is in the formula) LC31and R LC32 Each independently represents R in the above general formula (LC3). LC31 and R LC32 Same meaning.

[0201] R LC31 and R LC32 Each is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, R LC31 More preferably, it represents an alkyl group having 2 or 3 carbon atoms, R LC32 More preferably, an alkyl group having 2 carbon atoms.

[0202] The general formula (LC4) is more preferably one or more compounds selected from the group consisting of compounds represented by the general formulas (LC4-a) to (LC4-c) below, and the general formula (LC5) is more preferably one or more compounds selected from the group consisting of compounds represented by the general formulas (LC5-a) to (LC5-c) below.

[0203] [Chemistry 38]

[0204]

[0205] (where R is in the formula) LC41 R LC42 and X LC41 Each independently represents R in the above general formula (LC4). LC41 R LC42 and X LC41 The same meaning, R LC51 and R LC52 Each independently represents R in the above general formula (LC5). LC51 and R LC52 The same meaning, Z LC4a1 Z LC4b1 Z LC4c1 Z LC5a1 Z LC5b1 and Z LC5c1 Each can independently represent a single bond, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -COO-, -OCH2-, -CH2O-, -OCF2-, or -CF2O-.

[0206] R LC41 R LC42 R LC51 and R LC52 Each of the following is preferred to be an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.

[0207] ZLC4a1 ~Z LC5c1 Each of these terms is preferably represented independently as a single bond, -CH2O-, -COO-, -OCO-, or -CH2CH2-, and more preferably as a single bond.

[0208] The fourth component is the so-called nonpolar liquid crystal compound with a dielectric constant anisotropy of about 0, and the compound represented by the following general formula (LC6) can be cited as an example.

[0209] [Chemistry 39]

[0210]

[0211] (where R is in the formula) LC61 and R LC62 Each of the following independently represents an alkyl group having 1 to 15 carbon atoms, wherein one or more -CH2- atoms in the alkyl group may be replaced by -O-, -CH=CH-, -CO-, -OCO-, -COO-, or -C≡C- in such a way that oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the alkyl group may be arbitrarily replaced by halogens. LC61 ~A LC63 Each can independently represent any of the following structures.

[0212] [Chemistry 40]

[0213]

[0214] (In this structure, one or more -CH2CH2- groups in the cyclohexene group can be substituted by -CH=CH-, -CF2O-, or -OCF2-, and one or more -CH= groups in the 1,4-phenylene group can be substituted by -N=.) Z LC61 and Z LC62 Each can independently represent a single bond, -CH=CH-, -C≡C-, -CH2CH2-, -(CH2)4-, -COO-, -OCH2-, -CH2O-, -OCF2-, or -CF2O-, m Lc6 Representing 0 to 3. This excludes compounds represented by general formulas (LC1) to (LC5) and general formula (i).

[0215] R LC61 and R LC62 Each of the following is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. The alkenyl group is most preferably represented by the following structure:

[0216] [Chemistry 41]

[0217]

[0218] (In the formula, it connects to the ring structure at the right end.)

[0219] A LC61 ~A LC63 Each of the following structures is preferred independently:

[0220] [Chemistry 42]

[0221]

[0222] Z LC61 and Z LC62 Each is preferably a single bond, -CH2CH2-, -COO-, -OCH2-, -CH2O-, -OCF2-, or -CF2O-.

[0223] The general formula (LC6) is more preferably one or more compounds selected from the group consisting of compounds represented by general formulas (LC6-a) to (LC6-m).

[0224] [Chemistry 43]

[0225]

[0226] (where R is in the formula) LC61 and R LC62 Each can independently represent an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an alkenyl group with 2 to 7 carbon atoms, or an alkenyloxy group with 2 to 7 carbon atoms.

[0227] GH-type liquid crystal display elements or dimming elements using liquid crystal compositions containing the compounds of the present invention are useful elements with high contrast that can be used even at low temperatures, and can be used in devices for outdoor applications in addition to indoor applications.

[0228] [Example]

[0229] The present invention will be further described in detail below with reference to examples, but the invention is not limited to these examples. Furthermore, "%" in the compositions of the following examples and comparative examples means "mass %". The phase transition temperature was determined using a polarizing microscope equipped with a temperature stage and a differential scanning calorimeter (DSC).

[0230] The following abbreviations are used in the description of compounds.

[0231] THF: Tetrahydrofuran; DMF: N,N-Dimethylformamide

[0232] Me: Methyl, Et: Ethyl, Pr: n-propyl, Bu: n-Butyl

[0233] The dichroism ratio and lightfastness of the GH-type liquid crystal composition were evaluated by sealing it in a glass test panel. The test panel had a cell thickness of 3.5 μm and used AL1051 as the horizontal alignment film.

[0234] The dichroic ratio (R) is calculated as follows. Using linearly polarized light as the light source for the transmittance meter, the transmittance at the maximum absorption wavelength when the orientation of the test panel is parallel to the linearly polarized light is set as A0, and the transmittance at the maximum absorption wavelength when the test panel is rotated so that its orientation is orthogonal to the linearly polarized light is set as A90. The dichroic ratio (R) is then calculated from the formula R = A0 / A90.

[0235] Regarding lightfastness, a visual comparison was conducted using SUNTEST (manufactured by ATLAS) to expose the aforementioned test panels to light for two weeks at 500W / m². 2 The hue of the test panel after illumination is compared with that of the unilluminated test panel, and the evaluation is based on whether a change in hue is observed.

[0236] Regarding the solubility of the GH-type liquid crystal composition, approximately 1g of the liquid crystal composition was placed in a small vial and visually observed at room temperature for one month. The evaluation was based on whether precipitation occurred.

[0237] (Example 1) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(5-(2-ethylhexyl)-2-thienyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0238] [Chemistry 44]

[0239]

[0240] (1-1) Under dry nitrogen conditions, N,N'-bis(2-ethylhexyl)-3,7-bis(4-bromophenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole (1.1 g, prepared by the method described in J. Mater. Chem. C, 2017, 5, 290-300) was mixed with 2-[5-(2-ethylhexyl)-2-thienyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborane (1.0 g), bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II) (11 mg), 2 mol / L potassium carbonate aqueous solution (3 mL), and THF (10 mL), and heated to 65 °C. After stirring under heating for 4 hours, the mixture was cooled to room temperature, and water (30 mL) and toluene (30 mL) were added for separation. The organic layer was washed twice with saturated saline (30 mL) and then dried with anhydrous sodium sulfate. After removing the sodium sulfate by filtration, the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography and then recrystallized from a mixed solvent of acetone and ethanol to obtain N,N'-bis(2-ethylhexyl)-3,7-bis(4-(5-(2-ethylhexyl)-2-thienyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole (1.0 g).

[0241] Phase transformation temperature: Cr 209 Iso

[0242] λ max 528nm (dichloromethane)

[0243] MS m / z: 950 [M] + ]

[0244] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.74 (4H, d, J = 8.4Hz), 7.66 (4H, d, J = 8.4Hz), 7.21 (2H, d, J = 3.2Hz), 6.76 (2H, d, J = 3.6Hz), 6.40 (2H, s), 3.60-3.47 (4H, m), 2.77 (4H, d, J = 6.4Hz), 1.78-1.75 (2H, m), 1.64-1.60 (2H, m), 1.47-1.32 (32H, m), 0.97-0.88 (24H, m)

[0245] (Example 2) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(6-(2-ethylhexyloxy)-2-naphthyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0246] [Chemistry 45]

[0247]

[0248] (2-1) 2-Bromo-6-hydroxynaphthalene (15 g), potassium carbonate (18.6 g), and 2-ethylhexyl bromide (19.5 g) were suspended in DMF (75 mL) and stirred at 80 °C for 8 hours. After cooling to room temperature, water (150 mL) and toluene (100 mL) were added for separation. The organic layer was washed twice with saturated brine (50 mL) and dried over anhydrous sodium sulfate. The sodium sulfate was removed by filtration and the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography and recrystallized from a mixture of methanol and acetone to obtain 2-bromo-6-(2-ethylhexyloxy)naphthalene (18 g).

[0249] 1 HNMR (400MHz, CDCl3, TMS internal standard): δ (ppm) = 7.90 (1H, d, J = 1.6Hz), 7.63 (1H, d, J = 9.2Hz), 7.58 (1H, d, J = 8.8Hz), 7.49 (1H, d, J = 2.4Hz), 7.47 (1H, d, J = 2.0Hz), 7.16 (1H, dd, J = 1.6Hz). 9.0Hz, J2=2.4Hz), 7.09 (1H, d, J=2.4Hz), 3.94 (2H, d, J=4.4Hz), 1.78 (1H, sep, J=6.0H z), 1.55-1.41 (4H, m), 1.38-1.31 (4H, m), 0.96 (3H, t, J = 7.6Hz), 0.90 (3H, t, J = 7.2Hz)

[0250] (2-2) Under dry nitrogen conditions, a solution prepared in step 2-1, in which 10 g of 2-bromo-6-(2-ethylhexyloxy)naphthalene is dissolved in 20 mL of dry THF, was added to a solution in which 0.86 g of metallic magnesium was suspended in 2 mL of dry THF at a constant reflux rate. The reaction mixture was stirred under reflux for 5 hours, then cooled in an ice bath, and a solution in which 4.0 g of trimethylboric acid was dissolved in 8 mL of dry THF was slowly added. The mixture was then stirred at room temperature for 1 hour. The mixture was cooled again in an ice bath, and 10% hydrochloric acid (30 mL) was slowly added, followed by ethyl acetate (50 mL) for separation. The organic layer was washed twice with saturated brine (30 mL) and dried with anhydrous sodium sulfate. After drying, the sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure to obtain crude 6-(2-ethylhexyloxy)-2-naphthylboronic acid (A, 8.4 g). This intermediate was used in subsequent processes without further purification.

[0251] (2-3) In subsequent processes, A obtained in process 2-2 is used instead of 2-[5-(2-ethylhexyl)-2-thienyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborane in Example 1. Otherwise, the same method is used to produce N,N'-bis(2-ethylhexyl)-3,7-bis(4-(6-(2-ethylhexyloxy)-2-naphthyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole.

[0252] Phase transformation temperature: Cr 250 Iso

[0253] λ max 510nm (dichloromethane)

[0254] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 8.02 (2H, d, J = 1.2Hz), 7.87-7.82 (7H, m), 7.82-7.72 (7H, m), 7.21-7.16 (4H, m), 6.45 (2H, s), 3.99 (4H, d, J = 6.4Hz), 3.63-3.50 (4H, m), 1.86-1.77 (4H, m), 1.63-1.38 (32H, m), 0.98 (¹²H, t, J = 7.6Hz), 0.94-0.90 (¹²H, m)

[0255] (Example 3) Preparation of N,N'-dipentyl-3,7-bis(4-(5-(2-ethylhexyl)-2-thienyl)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole

[0256] [Chemistry 46]

[0257]

[0258] (3-1) 3,7-bis(4-bromophenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole (1.0 g, prepared according to the method described in Dyes and Pigments 162(2019)883-887), 5-iodopentane (1.5 g), and potassium carbonate (1.3 g) were suspended in DMF (10 mL) and stirred at 50 °C for 5 hours. After cooling to room temperature, the reaction solution was added to water (100 mL), and the precipitate was collected by filtration. The obtained solid was purified by silica gel column chromatography and then recrystallized in a mixed solvent of acetone and methanol to obtain 0.45 g of N,N'-dipentyl-3,7-bis(4-bromophenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole.

[0259] (3-2) In subsequent processes, N,N'-dipentyl-3,7-bis(4-(5-(2-ethylhexyl)-2-thiophene)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole is obtained using the same method as in Example 1.

[0260] Phase transition temperature: Cr 196 Iso

[0261] MS m / z: 916 [M] + ]

[0262] λ max 622nm (dichloromethane)

[0263] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.81 (4H, d, J = 8.0Hz), 7.65 (4H, d, J = 8.0Hz), 7.36 (2H, d, J = 9.6Hz), 7.27 (2H, d, J = 10Hz), 7.27 (2H, d, J = 3.6Hz), 6.75 (2H, d, J = 3.6Hz), 4.16-4.12 (4H, m), 2.77 (4H, d, J = 6.4Hz), 1.83-1.74 (4H, m), 1.66-1.55 (4H, m), 1.42-1.25 (22H, m), 0.95-0.88 (18H, m)

[0264] (Example 4) Preparation of 3,7-bis(6-(2-ethylhexyl)-2-naphthyl)-2H,6H-benzo[1,2-b:4,5-b']dithiophene-2,6-dione

[0265] [Chemistry 47]

[0266]

[0267] (4-1) Using 3,7-dibromo-2H,6H-benzo[1,2-b:4,5-b']dithiophene-2,6-dione (prepared using the method described in Chemistry Letters, 1983, 905-908), except that 3,7-bis(6-(2-ethylhexyl)-2-naphthyl)-2H,6H-benzo[1,2-b:4,5-b']dithiophene-2,6-dione was obtained by the same method as in Example 2.

[0268] MS m / z: 728 [M] + ]

[0269] λ max 643nm (dichloromethane)

[0270] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.93 (2H, d, J = 1.5Hz), 7.83-7.71 (10H, m), 7.18 (2H, s), 3.93 (4H, d, J = 4.6Hz), 1.77 (2H, sep, J = 6.2Hz), 1.55-1.41 (8H, m), 1.38-1.31 (8H, m), 0.94 (6H, t, J = 7.3Hz), 0.88 (6H, t, J = 7.1Hz)

[0271] (Examples 5-8)

[0272] The compounds of Examples 5-8 were synthesized using the same method as in Examples 1-4.

[0273] [Chemistry 48]

[0274] (Example 5)

[0275] (Example 6)

[0276] (Example 7)

[0277] (Example 8) (Example 9) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0278] [Chemistry 49]

[0279]

[0280] Using the same method as in Examples 1-4, N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole was obtained.

[0281] Phase transition temperature: Cr 212 N 340 Iso

[0282] MS m / z: 1262 [M] + ]

[0283] λ max 494nm (dichloromethane)

[0284] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.80 (dd, J₁ = 29.7Hz, J₂ = 8.7Hz, 8H), 7.59 (d, J = 1.8Hz, 2H), 7.51 (dd, J₁ = 7.8Hz, J₂ = 1.8Hz, 2H), 7.29 (d, J = 7.8Hz, 2H), 7.19 (t, J = 7.8Hz, 2H), 6.99-7.07 (m, 4H), 6.4 6 (s, 2H), 3.51-3.64 (m, 4H), 2.62 (q, J=7.5Hz, 4H), 2.53 (tt, J1=12.1Hz, J2=3.1Hz, 2H), 1.94 (dd, J1=2 6.8Hz, J2=11.2Hz, 8H), 1.79-1.85(m, 2H), 1.22-1.50(m, 38H), 1.03-1.18(m, 10H), 0.89-0.99(m, 18H)

[0285] (Example 10) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(2-ethylhexyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0286] [Transformation 50]

[0287]

[0288] Using the same method as in Examples 1-4, N,N'-bis(2-ethylhexyl)-3,7-bis(4-(2-ethylhexyl)-2-thiophenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole was obtained.

[0289] Phase transition temperature: Cr 64 Iso

[0290] MS m / z: 798 [M] + ]

[0291] λ max 583nm (dichloromethane)

[0292] 1 ¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.87 (d, J = 3.7Hz, 2H), 6.83 (d, J = 4.1Hz, 2H), 6.56 (s, 2H), 3.56 (dq, J₁ = 24.5Hz, J₂ = 7.2Hz, 4H), 2.81 (d, J = 6.9Hz, 4H), 1.80 (t, J = 5.7Hz, 2H), 1.64 (t, J = 5.9Hz, 2H), 1.35-1.45 (m, 18H), 1.30 (t, J = 3.9Hz, 14H), 0.97 (t, J = 7.3Hz, 6H), 0.93-0.88 (m, 18H)

[0293] (Example 11) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(4-hexyl-2-thienyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0294] [Chemistry 51]

[0295]

[0296] Using the same method as in Examples 1-4, N,N'-bis(2-ethylhexyl)-3,7-bis(4-(4-hexyl-2-thienyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole was obtained.

[0297] Phase transition temperature: Cr 218 Iso

[0298] MS m / z: 906 [M] + ]

[0299] λ max 688nm (dichloromethane)

[0300] 1¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.94 (d, J = 4.1Hz, 2H), 7.13 (d, J = 3.7Hz, 2H), 7.07 (d, J = 3.2Hz, 2H), 6.70 (d, J = 3.2Hz, 2H), 6.54 (s, 2H), 3.51-3.63 (m, 4H), 2.80 (t, J = 7.5Hz, 4H), 1.79 (t, J = 5.5Hz, 2H), 1.65-1.73 (m, 4H), 1.27-1.50 (m, 28H), 1.00 (t, J = 7.3Hz, 6H), 0.93-0.88 (m, 12H)

[0301] (Example 12) Preparation of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole

[0302] [Chemistry 52]

[0303]

[0304] Using the same method as in Examples 1-4, N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole was obtained.

[0305] Phase transition temperature: Cr 233 N 320 Iso

[0306] MS m / z: 1274 [M] + ]

[0307] λ max 638nm (dichloromethane)

[0308] 1H NMR (400MHz, CDCl3, TMS internal standard): δ (ppm) = 8.04 (d, J = 3.2Hz, 2H), 7.61 (s, 2H), 7.51 (d, J = 8.2Hz, 2H), 7.41-7.42 (m, 2H), 7.21 (d, J = 7.8Hz, 2H), 7.15 (t, J = 7.8Hz, 2H), 7.04 (d, J = 8.2Hz, 2H), 6.99 (d, J = 1 1.4Hz, 2H), 6.64 (s, 2H), 3.58-3.62 (m, 4H), 2.50-2.60 (m, 6H), 1.94 (q, J=12.2Hz, 8H), 1.83 (t, J=5 .7Hz, 2H), 1.23-1.50 (m, 38H), 1.12 (q, J=7.3Hz, 8H), 1.03 (t, J=7.3Hz, 8H), 0.91 (t, J=6.6Hz, 12H)

[0309] (Example 13) Preparation of N,N'-dipentyl-3,7-bis(4-(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole

[0310] [Chemistry 53]

[0311]

[0312] Using the same method as in Examples 1-4, N,N'-dipentyl-3,7-bis(4-(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole was obtained.

[0313] Phase transition temperature: Cr 313 Iso

[0314] MS m / z: 1392 [M] + ]

[0315] λ max 624nm (dichloromethane)

[0316] 1¹H NMR (400MHz, CDCl₃, TMS internal standard): δ (ppm) = 7.82 (dd, J1 = 50.8Hz, J2 = 8.2Hz, 8H), 7.52-7.60 (m, 4H), 7.31-7.43 (m, 8H), 7.15-7.24 (m, 4H), 6.99-7.06 (m, 4H), 4.19 (t, J = 7.3Hz, 4H), 2.50-2.62 (m, 6H), 1.90-1.99 (m, 4H), 1.82 (s, 2H), 1.44-1.59 (m, 8H), 1.27-1.38 (m, 26H), 1.00-1.18 (m, 6H), 0.82-0.97 (m, 18H)

[0317] (Examples 14-18)

[0318] The compounds of Examples 14-18 were synthesized using the same method as in Examples 9-13.

[0319] [Chemistry 54]

[0320] (Example 14)

[0321] (Example 15)

[0322] (Example 16)

[0323] (Example 17)

[0324] (Example 18)

[0325] (Example 19) Modulation of the liquid crystal composition - 1

[0326] The modulation consists of a main liquid crystal (H) composed of the following components.

[0327] [Chemistry 55]

[0328]

[0329] A liquid crystal composition (MA) was prepared by mixing 98% of the above-mentioned parent liquid crystal (H) and 2% of N,N'-bis(2-ethylhexyl)-3,7-bis(4-(5-(2-ethylhexyl)-2-thienyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole obtained in Example 1. The optical properties of this composition (MA) were measured as follows.

[0330] λ max 553nm

[0331] Dichroism ratio: 3.8

[0332] Furthermore, the modulated liquid crystal composition (MA) maintains a uniform nematic liquid crystal state at room temperature for one month.

[0333] Furthermore, a two-week lightfastness test was conducted using a liquid crystal composition (MA), and the results confirmed that the hue remained unchanged.

[0334] (Example 20) Modulation of the liquid crystal composition - 2

[0335] A liquid crystal composition (MB) was prepared, consisting of 99% parent liquid crystal (H) and 1% N,N'-bis(2-ethylhexyl)-3,7-bis(4-(6-(2-ethylhexyloxy)-2-naphthyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole obtained in Example 2. The optical properties of this composition (MB) were measured as follows.

[0336] λ max 527nm

[0337] Dichroism ratio: 4.4

[0338] Furthermore, the modulated liquid crystal composition (MB) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0339] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MB), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0340] (Example 21) Modulation of the liquid crystal composition - 3

[0341] A liquid crystal composition (MC) was prepared, consisting of 99% parent liquid crystal (H) and 1% 3N,N'-dipentyl-3,7-bis(4-(5-(2-ethylhexyl)-2-thienyl)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole obtained in Example 3. The optical properties of this composition (MC) were measured as follows.

[0342] λ max 642nm

[0343] Dichroism ratio: 5.5

[0344] Furthermore, the modulated liquid crystal composition (MC) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0345] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MC), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0346] (Example 22) Modulation of the liquid crystal composition - 4

[0347] A liquid crystal composition (MD) was prepared, consisting of 98% parent liquid crystal (H) and 2% 3,7-bis(6-(2-ethylhexyl)-2-naphthyl)-2H,6H-benzo[1,2-b:4,5-b']dithiophene-2,6-dione obtained in Example 4. The optical properties of this composition (MD) were measured as follows.

[0348] λ max 659nm

[0349] Dichroism ratio: 5.1

[0350] Furthermore, the modulated liquid crystal composition (MD) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0351] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MD), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0352] (Example 23) Modulation of the liquid crystal composition - 5

[0353] A liquid crystal composition (ME) was prepared, consisting of 98% parent liquid crystal (H) and 2% N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)phenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole obtained in Example 9. The optical properties of this composition (ME) were measured as follows.

[0354] λ max 518nm

[0355] Dichroism ratio: 4.5

[0356] Furthermore, the modulated liquid crystal composition (ME) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0357] Furthermore, lightfastness tests were conducted using a liquid crystal composition (ME), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0358] (Example 24) Modulation of the liquid crystal composition - 6

[0359] A liquid crystal composition (MF) was prepared, consisting of 98% parent liquid crystal (H) and 2% N,N'-bis(2-ethylhexyl)-3,7-bis(4-(2-ethylhexyl)-2-thiophene)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole obtained in Example 10. The optical properties of this composition (MF) were measured as follows.

[0360] λ max 596nm

[0361] Dichroism ratio: 2.9

[0362] Furthermore, the modulated liquid crystal composition (MF) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0363] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MF), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0364] (Example 25) Modulation of the liquid crystal composition - 7

[0365] A liquid crystal composition (MG) was prepared, consisting of 98% parent liquid crystal (H) and 2% N,N'-bis(2-ethylhexyl)-3,7-bis(4-(4-hexyl-2-thienyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole obtained in Example 11. The optical properties of this composition (MG) were measured as follows.

[0366] λ max 688nm

[0367] Dichroism ratio: 4.2

[0368] Furthermore, the modulated liquid crystal composition (MG) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0369] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MG), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0370] (Example 26) Modulation of the liquid crystal composition - 8

[0371] A liquid crystal composition (MJ) was prepared, consisting of 98% parent liquid crystal (H) and 2% N,N'-bis(2-ethylhexyl)-3,7-bis(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole. The optical properties of this composition (MJ) were measured as follows.

[0372] λ max 652nm

[0373] Dichroism ratio: 3.3

[0374] Furthermore, the modulated liquid crystal composition (MJ) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0375] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MJ), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0376] (Example 27) Modulation of the liquid crystal composition - 9

[0377] A liquid crystal composition (MK) was prepared, consisting of 98% parent liquid crystal (H) and 2% N,N'-dipentyl-3,7-bis(4-(4-(3-ethyl-4-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)phenyl)-2-thienyl)phenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b']dipyrrole. The optical properties of this composition (MK) were measured as follows.

[0378] λ max 646nm

[0379] Dichroism ratio: 4.9

[0380] Furthermore, the modulated liquid crystal composition (MK) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0381] Furthermore, lightfastness testing was conducted using a liquid crystal composition (MK), and the results confirmed that the hue remained unchanged over a period of two weeks.

[0382] (Comparative Example 1) Modulation of the liquid crystal composition -10

[0383] A liquid crystal composition (ML) comprising 99% parent liquid crystal (H) and 1% N,N'-dimethyl-3,7-diphenyl-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole as disclosed in Japanese Patent Application Publication No. 2015-40231.

[0384] [Chemistry 56]

[0385]

[0386] The results of the optical properties determination of the composition (ML) are as follows.

[0387] λ max 465nm

[0388] Dichroism ratio: 1.9

[0389] Furthermore, pigment precipitation was observed in the modulated liquid crystal composition (ML) after 3 days at room temperature.

[0390] Furthermore, lightfastness tests were conducted using a liquid crystal composition (ML), and a color change was confirmed after 7 days.

[0391] (Comparative Example 2) Modulation of the liquid crystal composition - 11

[0392] A liquid crystal composition (MM) was prepared, consisting of 99% parent liquid crystal (H) and 1% N,N'-bis(2-ethylhexyl)-3,7-diphenyl-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b']dipyrrole as described in J. Mater. Chem. C, 2017, 5, 290-300.

[0393] [Chemistry 57]

[0394]

[0395] The optical properties of the composition (MM) were measured as follows.

[0396] λ max 470nm

[0397] Dichroism ratio: 1.8

[0398] Furthermore, pigment precipitation was observed in the modulated liquid crystal composition (MM) after 10 days at room temperature.

[0399] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MM), and a color change was confirmed after 7 days.

[0400] Comparing the dichroic ratio, solubility, and lightfastness of Examples 19-27 with Comparative Examples 1 and 2, it is evident that the compounds of this application simultaneously possess a larger dichroic ratio, higher solubility, and higher lightfastness compared to the compounds of Comparative Examples 1 and 2. In particular, the compounds of this application in Examples 21, 22, and 27 exhibit extremely high dichroic ratios while maintaining high solubility. Therefore, it is clear that the compounds of this application possess the characteristic of simultaneously possessing a large dichroic ratio and high solubility.

Claims

1. A compound represented by any one of the following general formulas (1-1) to (1-14), (1-17) to (1-20), (1-22) to (1-24), and (1-49) to (1-72), In the formula, R 1 and R 2 Each independently represents either an alkyl group with 3 to 20 carbon atoms or an alkoxy group with 3 to 20 carbon atoms, R 4 Alkyl groups having 1 to 20 carbon atoms.

2. A liquid crystal composition comprising one or more of the compounds of claim 1.

3. A liquid crystal composition comprising one or more compounds represented by general formula (1), In the formula, B is the group represented by general formula (2). in, The carbon atoms represented by *1 to *4 in general formula (2) correspond to the carbon atoms represented by *1 to *4 in general formula (1), respectively. R 1 and R 2 Each can independently represent either an alkyl group or an alkoxy group having 3 to 20 carbon atoms. X 1 and X 2 Each can be represented independently as -S- or -NR. 4 -, where R 4 Alkyl groups having 1 to 20 carbon atoms A 1 and A 2 Each of these groups independently represents a group selected from the group consisting of 1,4-cyclohexene, 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-1,4-diyl, thiophene-2,5-diyl, and thiophene-2,4-diyl, which may be unsubstituted or substituted with one or more substituents. 2 Replace, L 2 Each of these can independently represent a hydrogen atom, a fluorine atom, and a straight-chain alkyl group having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms. Z 1 and Z 2 Each represents a single key independently. i and j each independently represent integers from 1 to 4. In A 1 and A 2 When there are multiple A's, multiple A's 1 and A 2 They can be the same or different, and there are multiple Rs. 4 In the case of multiple R 4 They can be the same or different.

4. The liquid crystal composition according to claim 3, in general formula (1), R 1 and R 2 Each can be independently represented as a non-substituted straight-chain or branched alkyl group with 4 to 20 carbon atoms.

5. The liquid crystal composition according to claim 3 or 4, wherein in general formula (1), A 1 and A 2 Each group independently represents a group selected from the following groups: R e Each can independently represent a methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, or fluorine atom.

6. The liquid crystal composition according to claim 3 or 4, wherein in general formula (1), X 1 and X 2 Each is represented independently -S-.

7. The liquid crystal composition according to claim 3 or 4, wherein in general formula (1), X 1 and X 2 Each is represented independently -NR 4 - 8. The liquid crystal composition according to claim 3 or 4, wherein the compound represented by general formula (1) is a compound represented by any one of the following general formulas (1-1) to (1-24), (1-49) to (1-72), In the formula, R 1 and R 2 Each independently represents either an alkyl group with 3 to 20 carbon atoms or an alkoxy group with 3 to 20 carbon atoms, R 4 Alkyl groups having 1 to 20 carbon atoms.

9. A liquid crystal display element or a dimming element, which uses the liquid crystal composition according to any one of claims 2 to 8.

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