Compound, composition, liquid crystal composition, and liquid crystal display element or light control element

Abstract

To solve the problems, the present application provides a compound having excellent light resistance, a large dichroic ratio, and high solubility in a host liquid crystal, and a composition, a liquid crystal composition, and a liquid crystal display element or a light control element each using the compound as a component. As a solution, the present application provides a compound represented by General Formula (1) below, and a liquid crystal composition containing the compound and a liquid crystal display element or a light control element using the liquid crystal composition. The compound represented by General Formula (1) provided by the present application has a large dichroic ratio and high solubility in a host liquid crystal. In addition, the compound has excellent chemical stability as a component of an element. Therefore, by using the compound represented by General Formula (1) as a component of a GH-type liquid crystal composition, a liquid crystal display element or a light control element having high contrast can be provided.[Chem. 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 are also being put into practical use as dimming elements that regulate light transmission.

[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, a nematic liquid crystal phase must be present 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 such as those described below (Patent Document 2) have been reported, but these compounds do not simultaneously possess a large dichroism ratio, high solubility, and high lightfastness.

[0008] [Chemistry 1]

[0009]

[0010] [Existing Technical Documents]

[0011] [Patent Literature]

[0012] [Patent Document 1] Japanese Patent Publication No. 2013-534945

[0013] [Patent Document 2] Chinese Patent Application Publication No. 109369684

[0014] [Non-patent literature]

[0015] [Non-Patent Literature 1] "Display Materials and Functional Pigments" by Hiroyuki Nakajima

[0016] [Non-Patent Literature 2] "Technology of Functional Pigments" by Hiroyuki Nakajima

[0017] [Non-Patent Document 3] "Dichroic Dyes for Liquid Crystal Displays" by Aleksandr V. Ivashchenko Summary of the Invention

[0018] The problem that the invention aims to solve

[0019] The problem to be solved by the present invention is to provide a compound with high lightfastness, a large dichroism ratio and high solubility in a bulk 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.

[0020] Methods for solving problems

[0021] 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.

[0022] [Chemistry 2]

[0023]

[0024] (In the formula, U is any group selected from the groups represented by general formula (2) or (3),)

[0025] [Chemistry 3]

[0026]

[0027] R 1 R 2 R 3 R 4 and R 5Each group independently represents a fluorine atom, a cyano group, 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. 6 -, -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO-, -SO2-, -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... 6 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.

[0028] R a R b and R c Each group independently represents a hydrogen atom, 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. 7 -, -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO-, -SO2-, -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... 7 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.

[0029] X a X b and X c Each can be represented independently as -S- or -O-.

[0030] A 1 A 2 A 4 A 5 A a and A b Each can independently represent a hydrocarbon ring or heterocycle with 3 to 16 carbon atoms that can be substituted.

[0031] Z1 Z 2 Z 4 Z 5 Z a Z b and Z c 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.

[0032] i, j, a, b, c, and d each independently represent an integer from 0 to 4.

[0033] In A 1 A 2 A 4 A 5 A a and A b When there are multiple A's, multiple A's 1 A 2 A 4 A 5 A a and A b They can be the same or different, in Z 1 Z 2 Z 4 Z 5 Z a Z b and Z c In the case of multiple Z, multiple Z 1 Z 2 Z 4 Z 5 Z a Z b and Z c They can be the same or different, and there are multiple Rs. 6 In the case of multiple R 6 They can be the same or different.

[0034] Invention Effects

[0035] 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

[0036] In general formula (1), for U, in order to increase the dichroism ratio, the structure represented by general formula (3) is preferred, and in the case of emphasizing light resistance and solubility in the main liquid crystal, the structure represented by general formula (2) is preferred.

[0037] In general formula (1), R 1 R 2 R 3 R 4 and R 5 Each of the following groups is preferably represented independently as a fluorine atom, a cyano group, an alkyl group with 2 to 20 carbon atoms, or an alkenyl group with 2 to 20 carbon atoms. One or more non-adjacent -CH2- groups are also preferably substituted with -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO-, or -SO2-. To improve solubility in the bulk liquid crystal, each of the following groups is preferably an alkyl or alkenyl group with 1 to 20 carbon atoms, more preferably a non-substituted straight-chain or branched alkyl group with 1 to 20 carbon atoms, further preferably a non-substituted straight-chain or branched alkyl group with 4 to 20 carbon atoms, and particularly preferably a non-substituted branched alkyl group with 4 to 20 carbon atoms. To exhibit a high dichroic ratio, R 3 Preferably, it is a straight-chain alkyl or fluorinated alkyl group having 1 to 5 carbon atoms, and particularly preferably methyl or trifluoromethyl. To achieve a longer absorption wavelength, R... 3 Preferably, the atom is a fluorine atom, a cyano group, a thioether group, an alkyl sulfonyl group, an N,N-dialkyl sulfonamide group, or an alkyl acyl group.

[0038] In general formula (1), R a R b and R c Each of the following groups is preferably represented independently: a hydrogen atom, an alkyl group with 2 to 20 carbon atoms, or an alkenyl group with 2 to 20 carbon atoms. One or more non-adjacent -CH2- groups are preferably substituted with -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO-, or -SO2-. To improve solubility in the bulk liquid crystal, each of the following groups is preferably represented independently: an alkyl group with 1 to 20 carbon atoms, or an alkenyl group; more preferably, a non-substituted straight-chain or branched alkyl group with 1 to 20 carbon atoms; even more preferably, a non-substituted straight-chain or branched alkyl group with 4 to 20 carbon atoms; and particularly preferably, a non-substituted branched alkyl group with 4 to 20 carbon atoms. On the other hand, from the viewpoint of high dichroism ratio and ease of manufacture, a hydrogen atom is preferred. To achieve a long absorption wavelength, alkylsulfonyl, N,N-dialkylsulfonamide, or alkylyl groups are preferred.

[0039] In general formula (1), X a Xb and X c Each can be independently represented as -S- or -O-. From the viewpoint of solubility and making the absorption wavelength a long wavelength, -S- is preferred, while from the viewpoint of dichroism ratio, lightfastness and ease of manufacture, -O- is preferred.

[0040] In general formula (1), A 1 A 2 A 4 A 5 A a and A b Each ring is preferably a hydrocarbon ring or heterocycle with 3 to 16 carbon atoms that can be substituted. The hydrocarbon ring can be an aliphatic ring or an aromatic ring, and may have substituents. Similarly, the heterocycle can be an aliphatic ring or an aromatic ring, and the elements constituting the ring structure may include at least one heteroelement, and may have substituents. A 1 A 2 A 4 A 5 A a and A b Each group is independently preferred from the group consisting of the following groups.

[0041] (a) 1,4-cyclohexylene (one or more non-adjacent -CH2- groups may be substituted by -O- or -S-, and one or more non-adjacent -CH2- groups may be substituted by -NH-.)

[0042] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups in this group can be replaced by -N=.)

[0043] (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=.

[0044] (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=.)

[0045] These groups are also preferably unsubstituted or substituented with one or more substituents L. 2 replace.

[0046] L 2 Each of the following is preferably an independent hydrogen atom, fluorine atom, chlorine atom, pentafluorosulfuryl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or one or more -CH2- atoms, and each can be independently replaced by -O-, -S-, -CO-, -CS-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, - The alkyl group consisting of NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C- substituted with a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each of which is further preferably composed of hydrogen, fluorine, chlorine, pentafluorothioalkyl, nitro, cyano, isocyano, dimethylamino, diethylamino, diisopropylamino, thioisocyano, methyl, ethyl, propyl, methoxy, ethoxy, or acetyl.

[0047] In addition, as A 1 A 2 A 4 A 5 A a and A b The preferred structure is preferably represented by a group selected from the following structures.

[0048] [Chemistry 4]

[0049]

[0050] Here, R eEach of the following is preferably represented independently: 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. At this time, 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, unsubstituted naphthyl-1,4-diyl, or unsubstituted thieno[3,2-b]thiophene-2,5-diyl are preferred. To achieve a long absorption wavelength, an electron-donating ring is preferred, particularly thiophene-2,5-diyl, thiophene-2,4-diylthieno[3,2-b]thiophene-2,5-diyl, or piperidine-1,4-diyl. Furthermore, 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.

[0051] In general formula (1), Z 1 Z 2 Z 4 Z 5 Z a Z b and Z cEach of the following is preferably represented independently as -CH2CH2-, -CH=CH-, -CF=CF-, -N=N-, -C≡C-, or a single bond. Furthermore, to improve solubility in the bulk liquid crystal, -CH2O-, -OCH2-, -CH2CH2-, or a single bond are preferred, and -CH2CH2-, or a single bond are even more preferred. To increase the dichroism ratio, -CH=CH-, -CF=CF-, -N=CH-, -CH=N-, -N=N-, -C≡C-, or a single bond are preferred, and -CH=CH-, -N=N-, -C≡C-, or a single bond are even more preferred. To exhibit high lightfastness, a single bond is preferred.

[0052] In general formula (1), i, j, a, b, c, and d each preferably represent an integer from 0 to 3, and from the viewpoint of solubility, it is more preferable to represent an integer from 1 to 2. Furthermore, when i, j, c, and d each represent an integer from 1 to 3, it is preferable from the viewpoint of high dichroism ratio and longer absorption wavelength. In order to increase the dichroism ratio, a and b each preferably represent 0 or 1, and particularly preferably 0.

[0053] 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.

[0054] The compound represented by general formula (1) has a skeleton represented by U in its structure and has R in its structure. 1 R 2 R 3 R 4 and R 5 The alkyl groups, etc., represent high solubility in liquid crystal compositions. In particular, those containing A in the structure... 1 A 2 A 4 A 5 A a and A b In the case of the ring structure, 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, when these rings are aromatic rings, the conjugated system of π electrons extends to the entire molecule, which is effective for increasing the wavelength of light absorption.

[0055] The compound represented by general formula (1) is preferably represented by the following formulas (1-A) to (1-D).

[0056] [Chemistry 5]

[0057]

[0058] (where R is in the formula) 1 R2 R 3 R 4 R 5 R a R b R c A 1 A 2 A 4 A 5 A a A b Z 1 Z 2 Z 4 Z 5 Z a Z b Z c i, j, a, b, c, and d each represent R in general formula (1). 1 R 2 R 3 R 4 R 5 R a R b R c A 1 A 2 A 4 A 5 A a A b Z 1 Z 2 Z 4 Z 5 Z a Z b Z c (i, j, a, b, c, and d have the same meaning.)

[0059] Furthermore, among the compounds represented by general formulas (1-A) to (1-D), the structure represented by general formula (1-E) is preferred.

[0060] [Chemistry 6]

[0061]

[0062] (where R is in the formula) 1 R 2 R 3 and R a Each represents R in general formula (1) 1 R 2 R 3 and R a The same meaning, A 11 A 12 and A 13Each can represent the same or different A in general formula (1) 1 The same meaning or single key, A 21 A 22 and A 23 Each can represent the same or different A in general formula (1) 2 Same meaning or single key.

[0063] In general formula (1), the compounds represented by the following general formulas (1-1) to (1-80) are particularly preferred.

[0064] [Chemistry 7]

[0065]

[0066] (where R is in the formula) 1 R 2 and R 3 R represents the general formula (1) 1 R 2 and R 3 Same meaning.

[0067] [Chemistry 8]

[0068]

[0069] (where R is in the formula) 1 R 2 and R 3 R represents the general formula (1) 1 R 2 and R 3 Same meaning.

[0070] [Chemistry 9]

[0071]

[0072] (where R is in the formula) 1 R 2 and R 3 R represents the general formula (1) 1 R 2 and R 3 Same meaning.

[0073] [Chemistry 10]

[0074]

[0075] (where R is in the formula) 1 R 2 and R 3 R represents the general formula (1) 1 R 2 and R3 Same meaning.

[0076] [Chemistry 11]

[0077]

[0078] (where R is in the formula) 1 R 2 and R 3 R represents the general formula (1) 1 R 2 and R 3 Same meaning.

[0079] [Chemistry 12]

[0080]

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

[0082] [Chemistry 13]

[0083]

[0084] (where R is in the formula) 1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0085] [Chemistry 14]

[0086]

[0087] (where R is in the formula) 1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0088] [Chemistry 15]

[0089]

[0090] (where R is in the formula)1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0091] [Chemistry 16]

[0092]

[0093] (where R is in the formula) 1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0094] [Chemistry 17]

[0095]

[0096] (where R is in the formula) 1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0097] [Chemistry 18]

[0098]

[0099] (where R is in the formula) 1 R 2 R 4 and R 5 R represents the general formula (1) 1 R 2 R 4 and R 5 Same meaning.

[0100] [Chemistry 19]

[0101]

[0102] (where R is in the formula) 1 R 2 R 3 and R aR represents the general formula (1) 1 R 2 R 3 and R a Same meaning.

[0103] [Chemistry 20]

[0104]

[0105] (where R is in the formula) 1 R 2 R 3 and R a R represents the general formula (1) 1 R 2 R 3 and R a Same meaning.

[0106] [Chemistry 21]

[0107]

[0108] (where R is in the formula) 1 R 2 R 3 and R a R represents the general formula (1) 1 R 2 R 3 and R a Same meaning.

[0109] (Manufacturing method)

[0110] In this invention, the compound represented by general formula (1) can be manufactured as follows. Of course, the spirit and scope of this invention are not limited to these manufacturing examples.

[0111] By reacting the compound represented by general formula (1-a) with fuming nitric acid and an acid, it is possible to obtain the compound represented by general formula (1-b).

[0112] [Chemistry 22]

[0113]

[0114] (where X) 1 This indicates that X is related to the general formula (2) or (3). a X b and X c The same meaning, Y a Y b Each atom can be independently represented by a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethanesulfonyloxy group.

[0115] [Chemistry 23]

[0116]

[0117] (where X) 1 This indicates that X is related to the general formula (2) or (3). a X b and X c The same meaning, Y a Y b Each can independently represent a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethanesulfonyloxy group.

[0118] The acid used can be any acid that allows the reaction to proceed appropriately; examples include inorganic and organic acids. Among these, concentrated hydrochloric acid, concentrated sulfuric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid are preferred, with concentrated sulfuric acid and trifluoromethanesulfonic acid being even more preferred.

[0119] The reaction temperature can be any temperature as long as it is suitable for the reaction to proceed, but is preferably between -20°C and 80°C.

[0120] The reaction can be carried out without a solvent, but chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane can be used as needed.

[0121] Next, by reacting the compound represented by general formula (1-b) with the compound represented by general formula (1-c) in the presence of a base and a transition metal catalyst, the compound represented by general formula (1-d) can be obtained.

[0122] [Chemistry 24]

[0123]

[0124] (where R is in the formula) 1a R represents the general formula (1) or (3). 1 R 2 R 4 and R 5 The same meaning, A 1a This indicates that A is related to the general formula (1) or (3). 1 A 2 A 4 and A 5 The same meaning, Z 1a This indicates that Z is related to the general formula (1) or (3). 1 Z 2 Z 4 and Z 5 With the same meaning, n represents the same meaning as i, j, c, and d in general formula (1) or (3), W 1This represents the general formula (B-1) or (B-2).

[0125] [Chemistry 25]

[0126]

[0127] (where R is in the formula) c and R d Each can independently represent an alkyl group or a hydrogen atom with 1 to 5 carbon atoms, which can be straight or branched. E represents a -(CH2) group in which one or more hydrogen atoms can be independently substituted by a methyl group. s -。 ), in A 1a When there are multiple A's, multiple A's 1a They can be the same or different, in Z 1a In the case of multiple Z, multiple Z 1a They can be the same or different.

[0128] [Chemistry 26]

[0129]

[0130] (where R is in the formula) 1a R represents the general formula (1) or (3). 1 R 2 R 4 and R 5 The same meaning, A 1a This indicates that A is related to the general formula (1) or (3). 1 A 2 A 4 and A 5 The same meaning, Z 1a This indicates that Z is related to the general formula (1) or (3). 1 Z 2 Z 4 and Z 5 With the same meaning, n represents the same meaning as i, j, c, and d in general formula (1) or (3).

[0131] The solvent used can be any solvent that is suitable for the reaction to proceed. Preferred solvents include ether solvents such as THF, diethyl ether, and diisopropyl ether; aromatic solvents such as benzene, toluene, and xylene; and amide solvents such as DMF, N,N-dimethylacetamide, and N-methylpyrrolidone. THF, DMF, or toluene are preferred. These solvents can be used alone or in combination as needed. Furthermore, water can be added to make the reaction proceed smoothly.

[0132] The reaction temperature can be any temperature that allows the reaction to proceed appropriately, preferably room temperature to the temperature at which the solvent refluxes, and more preferably 40°C to the temperature at which the solvent refluxes.

[0133] The base used can be any base suitable for the reaction to proceed, including metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides, and metals. Alkali metal hydrides, alkali metal phosphates, alkali metal carbonates, alkali metal hydroxides, alkali metal amides, and alkali metals are preferred, with alkali metal phosphates, alkali metal hydrides, and alkali metal carbonates being more preferred. Lithium hydride, sodium hydride, and potassium hydride are particularly preferred as alkali metal hydrides. Tripotassium phosphate is particularly preferred as an alkali metal phosphate. Sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate, and potassium bicarbonate are particularly preferred as alkali metal carbonates.

[0134] As the transition metal catalyst used, any catalyst suitable for the reaction can be used, preferably a palladium-based or nickel-based catalyst such as 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 preferably, tetra(triphenylphosphine)palladium(0), palladium acetate(II), bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II) dichloride, or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride. Furthermore, phosphine ligands can be added as needed to promote the reaction.

[0135] Next, by reacting the compound represented by general formula (1-d) with metal powder and acid, it is possible to obtain the compound represented by general formula (1-e).

[0136] [Chemistry 27]

[0137]

[0138] (where R is in the formula) 1a R represents the general formula (1) or (3). 1 R 2 R 4 and R 5 The same meaning, A 1a This indicates that A is related to the general formula (1) or (3). 1 A 2 A 4 and A 5 The same meaning, Z 1a This indicates that Z is related to the general formula (1) or (3).1 Z 2 Z 4 and Z 5 With the same meaning, n represents the same meaning as i, j, c, and d in general formula (1) or (3).

[0139] The acid used can be any acid that is suitable for the reaction to proceed, preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and trifluoroacetic acid, and more preferably hydrochloric acid and acetic acid.

[0140] The reaction temperature can be any temperature that allows the reaction to proceed appropriately, preferably room temperature to the temperature at which the solvent refluxes, and more preferably 40°C to 100°C.

[0141] The metal powder used can be any type that is suitable for the reaction to proceed, preferably zinc powder, iron powder, aluminum powder and nickel powder, and more preferably zinc powder and iron powder.

[0142] The reaction can be carried out without a solvent, or chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane can be used as needed.

[0143] Next, by reacting the compound represented by general formula (1-e) with general formula (1-f) or (1-g) in the presence of a reducing agent, it is possible to produce the target compound represented by general formula (1).

[0144] [Chemistry 28]

[0145]

[0146] (where R is in the formula) 3 A a Z a Each of 'a' and 'a' independently represents R in general formula (2). 3 A a Z a A has the same meaning as 'a'. b Z b Z c b and each independently represent A in general formula (3). b Z b Z c It has the same meaning as b.

[0147] As the reducing agent used, any one can be used as long as it allows the reaction to proceed appropriately; examples include metal sulfites, with alkali metal sulfites being preferred. Examples of alkali metal sulfites include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and potassium metabisulfite.

[0148] The reaction temperature can be any temperature that allows the reaction to proceed appropriately, preferably room temperature to the temperature at which the solvent refluxes, and more preferably 50°C to the temperature at which the solvent refluxes.

[0149] The solvent used can be any solvent that is suitable for the reaction to proceed. Preferred solvents include ether solvents such as THF, diethyl ether, and diisopropyl ether; aromatic solvents such as benzene, toluene, and xylene; and amide solvents such as DMF, N,N-dimethylacetamide, and N-methylpyrrolidone. DMF and N,N-dimethylacetamide are more preferred. These solvents can be used alone or in combination as needed.

[0150] 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.

[0151] 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.

[0152] 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).

[0153] [Chemistry 29]

[0154]

[0155] (where R is in the formula) LC11 and R LC21 Each 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 of the following structures can be represented independently.

[0156] [Chemistry 30]

[0157]

[0158] (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 be independently represented: hydrogen atom, fluorine atom, 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.

[0159] 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.

[0160] [Chemistry 31]

[0161]

[0162] (In the formula, it connects to the ring structure at the right end.)

[0163] A LC11 and A LC21 Each of them is preferably configured as follows.

[0164] [Chemistry 32]

[0165]

[0166] 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.

[0167] 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-.

[0168] 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.

[0169] 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).

[0170] [Chemistry 33]

[0171]

[0172] (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 The 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.

[0173] 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.

[0174] X LC11 ~X LC1c4 Each atom is preferably a hydrogen atom or a fluorine atom.

[0175] Y LC11 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0176] 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).

[0177] [Chemistry 34]

[0178]

[0179] (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 The 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 X LC1i2 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 LC1m1Each of these can independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -OCF2-, -CF2O-, -COO-, or -OCO-.

[0180] 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.

[0181] X LC11 ~X LC1m2 Each atom is preferably a hydrogen atom or a fluorine atom.

[0182] Y LC11 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0183] Z LC1d1 ~Z LC1m1 Each is preferably -CF2O- or -OCH2-.

[0184] 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).

[0185] [Chemistry 35]

[0186]

[0187] (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 LC2g1Each of these can independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -OCF2-, -CF2O-, -COO-, or -OCO-.

[0188] 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.

[0189] X LC21 ~X LC2g4 Each atom is preferably a hydrogen atom or a fluorine atom.

[0190] Y LC21 Each atom is preferably a fluorine atom, -CF3, or -OCF3.

[0191] Z LC2a1 ~Z LC2g4 Each is preferably -CF2O- or -OCH2-.

[0192] 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.

[0193] [Chemistry 36]

[0194]

[0195] (where R is in the formula) LC31 R LC32 R LC41 R LC42 R LC51 and R LC52 Each 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 of the following structures can be represented independently.

[0196] [Chemistry 37]

[0197]

[0198] (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.

[0199] R LC31 ~R LC52 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:

[0200] [Chemistry 38]

[0201]

[0202] (In the formula, it connects to the ring structure at the right end.)

[0203] A LC31 ~A LC52 Each of them is preferably configured as follows,

[0204] [Chemistry 39]

[0205]

[0206] ZLC31 ~Z LC51 Each is preferably a single bond, -CH2O-, -COO-, -OCO-, -CH2CH2-, -CF2O-, -OCF2-, or -OCH2-.

[0207] 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.

[0208] [Chemistry 40]

[0209]

[0210] (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).)

[0211] 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.

[0212] A LC31 Preferred forms 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.

[0213] Z LC31 Preferably, it represents a single bond, -CH2O-, -COO-, -OCO-, or -CH2CH2-, and more preferably, it represents a single bond.

[0214] As general formula (LC3-a), it is preferable to represent the following general formulas (LC3-a1) to (LC3-a4).

[0215] [Chemistry 41]

[0216]

[0217] (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.

[0218] 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 R represents an alkyl group having 1 to 7 carbon atoms. LC32 More preferably, an alkoxy group representing 1 to 7 carbon atoms.

[0219] As for the general formula (LC3-b), it is preferred to represent the following general formulas (LC3-b1) to (LC3-b12), more preferably general formulas (LC3-b1), (LC3-b6), (LC3-b8), and (LC3-b11), even more preferably general formulas (LC3-b1) and (LC3-b6), and most preferably general formula (LC3-b1).

[0220] [Chemistry 42]

[0221]

[0222] (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.

[0223] 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.

[0224] 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.

[0225] [Chemistry 43]

[0226]

[0227] (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-.

[0228] 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.

[0229] Z LC4a1 ~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.

[0230] 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.

[0231] [Chemistry 44]

[0232]

[0233] (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.

[0234] [Chemistry 45]

[0235]

[0236] (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).

[0237] 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:

[0238] [Chemistry 46]

[0239]

[0240] (In the formula, it connects to the ring structure at the right end.)

[0241] A LC61 ~A LC63 Each of them is preferably configured as follows,

[0242] [Chemistry 47]

[0243]

[0244] Z LC61 and Z LC62Each is preferably a single bond, -CH2CH2-, -COO-, -OCH2-, -CH2O-, -OCF2-, or -CF2O-.

[0245] 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).

[0246] [Chemistry 48]

[0247]

[0248] (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.

[0249] Liquid crystal compositions containing the compounds of the present invention are used as guest-host (GH) type liquid crystal compositions, and are also preferably used as polymer-dispersed liquid crystal compositions. Furthermore, these liquid crystal compositions are suitable for use in liquid crystal display elements for passive matrix driving or active matrix driving.

[0250] GH-type liquid crystal display elements, polymer-dispersed 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 are suitable for devices used outdoors as well as indoor applications.

[0251] [Example]

[0252] 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).

[0253] The following abbreviations are used in the description of compounds.

[0254] THF: Tetrahydrofuran

[0255] amphos: di-tert-butyl(4-dimethylaminophenyl)phosphine

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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 or not precipitation occurred.

[0260] (Example 1) Preparation of compound (E-1) (4,8-bis(5-methylthiophene-2-yl)-6-(4-propylphenyl)-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0261] [Chemistry 49]

[0262]

[0263] (1-1) After cooling trifluoromethanesulfonic acid (50.0 g) in an ice bath, fuming nitric acid (5.1 g) was slowly added. 4,7-dibromo-2,1,3-benzothiadiazole (8.0 g) was added at room temperature, and the mixture was stirred at 50 °C for 6 hours. The reaction solution was then poured into ice water and neutralized with a 50% sodium hydroxide aqueous solution. The precipitated solid was filtered, washed with water, and dried under reduced pressure to obtain 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (9.5 g).

[0264] (1-2) Under a dry nitrogen atmosphere, 2.0 g of 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (obtained in step 1-1), 1.6 g of 5-methyl-2-thiopheneboronic acid, 0.071 g of bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II) (dichloride), and 65 mL of THF were mixed and heated to 60 °C. While heating, a solution prepared by dissolving 2.9 g of potassium carbonate in 10 mL of water was slowly added dropwise. After stirring further at 60 °C for 6 hours, the mixture was cooled to room temperature, and 100 mL of water and 200 mL of ethyl acetate were added for separation. The organic layer was washed with 100 mL of saturated brine and dried with anhydrous sodium sulfate. After removing the organic solvent by vacuum distillation, the product was purified by silica gel column chromatography to obtain 4,7-bis(5-methylthiophen-2-yl)-5,6-dinitro-2,1,3-benzothiadiazole (0.24 g).

[0265] (1-3) Under a dry nitrogen atmosphere, 0.23 g of 4,7-bis(5-methylthiophen-2-yl)-5,6-dinitro-2,1,3-benzothiadiazole obtained in step 1-2, 0.37 g of iron powder, and 20 mL of acetic acid were mixed and stirred at 60 °C for 2 hours. After cooling to room temperature, the reaction solution was injected into ice water, and the precipitated solid was filtered. The solid was dissolved in ethyl acetate, and the iron powder was removed by filtration. The organic solvent was removed by vacuum distillation to obtain 0.11 g of 4,7-bis(5-methylthiophen-2-yl)-5,6-diamino-2,1,3-benzothiadiazole.

[0266] (1-4) The 4,7-bis(5-methylthiophen-2-yl)-5,6-diamino-2,1,3-benzothiadiazole (0.11 g), 4-propylbenzaldehyde (0.048 g), sodium metabisulfite (0.070 g), and N,N-dimethylacetamide (15 mL) obtained in steps 1-3 were mixed and stirred at 100 °C for 9 hours. After cooling to room temperature, water (80 mL) and ethyl acetate (50 mL) were added for separation. The organic layer was washed with saturated brine (50 mL) and dried with anhydrous sodium sulfate. After removing the organic solvent by vacuum distillation, the compound was purified by silica gel column chromatography to obtain compound (E-1)(4,8-bis(5-methylthiophen-2-yl)-6-(4-propylphenyl)-5H-imidazo[4',5':4,5]benzo[1,2-c][1,2,5]thiadiazole) (0.019 g).

[0267] MS m / z: 486 [M] + ]

[0268] Phase transition temperature (°C) Cr 237Iso

[0269] UV-Vis(CH2Cl2, λ) max 546nm

[0270] 1 ¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.62 (¹H, s), 8.78 (¹H, d, J = 3.6 Hz), 8.05 (²H, d, 8.4 Hz), 7.74 (¹H, d, 3.6 Hz), 7.32 (²H, d, 8.4 Hz), 6.91–6.89 (²H, m), 2.64 (²H, t, 7.6 Hz), 2.58 (⁶H, s), 1.65 (²H, quin, 7.6 Hz), 0.92 (³H, t, 7.6 Hz)

[0271] (Example 2) Preparation of compound (E-2) (1,4-bis(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-5H-imidazo[5,4-f]-2,1,3-benzothiadiazol-6-yl)benzene)

[0272] [Transformation 50]

[0273]

[0274] (2-1) After cooling trifluoromethanesulfonic acid (50.0 g) in an ice bath, fuming nitric acid (5.1 g) was slowly added. 4,7-dibromo-2,1,3-benzothiadiazole (8.0 g) was added at room temperature, and the mixture was stirred at 50 °C for 6 hours. The reaction solution was then poured into ice water and neutralized with a 50% sodium hydroxide aqueous solution. The precipitated solid was filtered, washed with water, and dried under reduced pressure to obtain 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (9.5 g).

[0275] (2-2) Under a dry nitrogen atmosphere, 2.0 g of 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (2.0 g), 0.074 g of 2-(5-(2-ethylhexyl)-2-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (3.7 g), 0.074 g of bis[di-tert-butyl(4-dimethylaminophenyl)phosphine]palladium(II) dichloride, and 30 mL of THF were mixed and heated to 60 °C. While heating, a solution obtained by dissolving 2.9 g of potassium carbonate in 6 mL of water was slowly added dropwise. After further stirring at 60 °C for 5 hours, the mixture was cooled to room temperature, and water (150 mL) and ethyl acetate (200 mL) were added for separation. The organic layer was washed with 100 mL of saturated brine and dried with anhydrous sodium sulfate. After removing the organic solvent by vacuum distillation, the product was purified by silica gel column chromatography to obtain 4,7-bis(5-(2-ethylhexyl)thiophen-2-yl)-5,6-dinitro-2,1,3-benzothiadiazole (0.36 g).

[0276] (2-3) Under a dry nitrogen atmosphere, 0.36 g of 4,7-bis(5-(2-ethylhexyl)thiophen-2-yl)-5,6-dinitro-2,1,3-benzothiadiazole (obtained in step 2-2), 0.39 g of iron powder, and 20 mL of acetic acid were mixed and stirred at 60 °C for 3 hours. After cooling to room temperature, the reaction solution was injected into ice water, and the precipitated solid was filtered. The solid was dissolved in ethyl acetate, and the iron powder was removed by filtration. The organic solvent was removed by vacuum distillation to obtain 0.32 g of 4,7-bis(5-(2-ethylhexyl)thiophen-2-yl)-5,6-diamino-2,1,3-benzothiadiazole.

[0277] (2-4) 4,7-bis(5-(2-ethylhexyl)thiophen-2-yl)-5,6-diamino-2,1,3-benzothiadiazole (0.28 g), benzene-1,4-dicarboxaldehyde (0.034 g), sodium metabisulfite (0.12 g), and N,N-dimethylacetamide (12 mL) were mixed and stirred at 100 °C for 22 hours. After cooling to room temperature, water (30 mL) and ethyl acetate (40 mL) were added for separation. The organic layer was washed with saturated brine (30 mL) and dried with anhydrous sodium sulfate. After removing the organic solvent by vacuum distillation, the compound was purified by silica gel column chromatography to obtain compound (E-2)(1,4-bis(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole-6-yl)benzene)(0.020 g).

[0278] MS m / z: 1203 [M] + ]

[0279] UV-Vis(CH2Cl2, λ) max 542nm

[0280] 1 ¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.52 (2H, s), 8.79 (2H, d, J = 3.6 Hz), 7.96 (4H, s), 7.82 (2H, s, J = 4.0 Hz), 6.90 (4H, d, J = 3.6 Hz), 2.90–2.87 (8H, m), 1.82–1.70 (4H, m), 1.54–1.32 (32H, m), 1.00–0.93 (24H, m)

[0281] (Examples 3-4)

[0282] The compounds of Example 3 (E-3) and Example 4 (E-4) were synthesized using the same methods as in Examples 1 and 2.

[0283] [Chemistry 51]

[0284]

[0285] (Example 5) Preparation of compound (E-5) (4,8-bis(2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0286] [Chemistry 52]

[0287]

[0288] Using the same method as in Example 1, compound (E-5) (4,8-bis(2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0289] MS m / z: 862 [M] + ]

[0290] Phase transition temperature (°C) Cr 256N 265Iso

[0291] UV-Vis(CH2Cl2, λ) max ): 436nm

[0292] 1¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.14 (s, ¹H), 8.24 (s, ¹H), 8.12 (d, J = 19.9 Hz, ¹H), 7.84 (s, ¹H), 7.73 (d, J = 7.8 Hz, ¹H), 7.43 (d, J = 7.8 Hz, ¹H), 7.40 (d, J = 8.2 Hz, ¹H), 7.23–7.26 (m, ²H), 6.99–7.10 (m, ²H). 4H), 2.93 (t, J=7.5Hz, 2H), 2.68 (q, J=7.5Hz, 4H), 2.55-2.55 (m, 2H), 1.90-2.01 (m, 6H), 1.50 (q, J =12.7Hz, 4H), 1.26-1.33 (m, 12H), 1.18 (q, J = 7.6Hz, 6H), 1.05-1.12 (m, 7H), 0.91 (t, J = 6.9Hz, 6H)

[0293] (Example 6) Preparation of compound (E-6) (4,8-bis(5-(4-methylpiperidin-1-yl)thiophen-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0294] [Chemistry 53]

[0295]

[0296] Using the same method as in Example 1, compound (E-6) (4,8-bis(5-(4-methylpiperidin-1-yl)thiophen-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0297] MS m / z: 576 [M] + ]

[0298] Phase transition temperature (°C) Cr 217Iso

[0299] UV-Vis(CH2Cl2, λ) max 608nm

[0300] 1 ¹H NMR (DMSO-d6, TMS internal standard) δ (ppm) = 12.03, 8.67, 7.50, 6.30, 3.65, 2.92-2.94 (m, 6H), 1.90 (td, J = 14.9, 7.3 Hz, 2H), 1.74 (d, J = 12.3 Hz, 4H), 1.55-1.57 (m, 2H), 1.32 (dd, J = 20.8, 11.2 Hz, 4H), 1.06 (t, J = 7.3 Hz, 3H), 0.97 (d, J = 6.4 Hz, 6H)

[0301] The NMR results suggest that the product may also be a free radical species.

[0302] (Example 7) Preparation of compound (E-7) (4,8-bis(5-(4-heptylpiperidin-1-yl)thieno[3,2-b]thieno-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0303] [Chemistry 54]

[0304]

[0305] Using the same method as in Example 1, compound (E-7) (4,8-bis(5-(4-heptylpiperidin-1-yl)thieno[3,2-b]thieno-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0306] MS m / z: 956 [M] + ]

[0307] Phase transition temperature (°C) Cr 119Iso

[0308] UV-Vis(CH2Cl2, λ) max 610nm

[0309] 1 ¹H NMR (acetone-d6, TMS internal standard) δ (ppm) = 11.41, 9.17, 7.98, 6.45 (s, 2H), 3.65 (d, J = 11.4 Hz, 4H), 3.04 (t, J = 6.8 Hz, 2H), 2.77–2.99 (m, 6H), 1.86 (d, J = 10.5 Hz, 4H), 1.29–1.42 (m, 28H), 1.13 (t, J = 7.6 Hz, 3H), 0.86–0.93 (m, 6H)

[0310] The NMR results suggest that the product may also be a free radical species.

[0311] (Example 8) Preparation of compound (E-8) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-(trifluoromethyl)-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0312] [Chemistry 55]

[0313]

[0314] Using the same method as in Example 1, compound (E-8) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-(trifluoromethyl)-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0315] MS m / z: 944 [M] + ]

[0316] Phase transition temperature (°C) Cr 268 N 284 Iso

[0317] UV-Vis(CH2Cl2, λ) max ): 443nm

[0318] 1 ¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.74 (s, ¹H), 8.25 (d, J = 1.8 Hz, ¹H), 8.13 (dd, J = 8.0, 1.6 Hz, ¹H), 7.84 (d, J = 1.8 Hz, ¹H), 7.73 (dd, J = 7.8, 1.4 Hz, ¹H), 7.47 (d, J = 7.8 Hz, ¹H), 7.42 (d, J = 7.8 Hz, ¹H), 7.25 (td, J = 7.6, 2.8 Hz, 2H), 7.00-7.11 (m, 4H), 2.69 (q, J = 7.5Hz, 4H), 2.51-2.58 (m, 2H), 1.99 (d, J = 11.9Hz, 4H), 1.92 (d, J = 12.8Hz, 4H), 1.50 (q, J = 12.4Hz , 4H), 1.24-1.34 (m, 18H), 1.20 (t, J=7.6Hz, 3H), 1.17 (t, J=7.6Hz, 3H), 1.09 (q, J=12.3Hz, 4H), 0.91 (t, J=6.9Hz, 6H)

[0319] (Example 9) Preparation of compound (E-9) (4,8-bis(5-(2-fluoro-4-propylphenyl)thiopheno)[3,2-b]thiopheno-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0320] [Chemistry 56]

[0321]

[0322] Using the same method as in Example 1, compound (E-9) (4,8-bis(5-(2-fluoro-4-propylphenyl)thiopheno)[3,2-b]thiophen-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0323] MS m / z: 766 [M] + ]

[0324] Phase transition temperature (°C) Cr 270Iso

[0325] UV-Vis(CH2Cl2, λ) max 552nm

[0326] 1 ¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.47 (s, ¹H), 9.29 (s, ¹H), 8.25 (s, ¹H), 7.72 (s, ¹H), 7.71 (s, ¹H), 7.56–7.62 (m, 2H), 6.99–7.04 (m, 4H), 3.07 (t, J = 7.5 Hz, 2H). 2.63 (t, J=7.2Hz, 2H), 2.62 (t, J=7.2Hz, 2H), 2.09 (sext, J=7.6Hz, 2H), 1.66-1 .77 (m, 4H), 1.20 (t, J = 7.3Hz, 3H), 0.97 (t, J = 7.3Hz, 3H), 0.98 (t, J = 7.3Hz, 3H)

[0327] (Example 10) Preparation of compound (E-10) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-methyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0328] [Chemistry 57]

[0329]

[0330] Using the same method as in Example 1, compound (E-10) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-methyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0331] MS m / z: 891 [M] + ]

[0332] Phase transition temperature (°C) Cr 248N 280Iso

[0333] UV-Vis(CH2Cl2, λ) max ): 435nm

[0334] 1¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 9.46 (s, ¹H), 8.14 (s, ¹H), 8.04 (d, J = 8.2 Hz, ¹H), 7.83 (s, ¹H), 7.70 (d, J = 9.6 Hz, ¹H), 7.39 (t, J = 7.3 Hz, 2H), 7.22 (td, J = 7.8, 4.6 Hz, 2H), 6.98–7.09 (m, 4H) , 2.63-2.69(m, 4H), 2.62(s, 3H), 2.50-2.54(m, 2H), 1.98(d, J=12.3Hz, 4H), 1.91(d, J=12.8H z, 4H), 1.49 (q, J=12.5Hz, 4H), 1.24-1.34 (m, 18H), 1.04-1.18 (m, 10H), 0.91 (t, J=6.9Hz, 6H)

[0335] (Example 11) Preparation of compound (E-11) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-5,6-methyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0336] [Chem.58]

[0337]

[0338] (11-1) 4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-6-methyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole (1.0 g), methyl iodoform (0.3 g), potassium carbonate (0.5 g), and DMF (10 mL) were mixed and stirred at room temperature for 3 hours. Water (50 mL) and dichloromethane (50 mL) were added for separation. The organic layer was washed with saturated brine (30 mL) and dried with anhydrous sodium sulfate. After removing the organic solvent by vacuum distillation, the obtained solid was purified by silica gel column chromatography. Recrystallization from a mixed solvent of toluene and hexane yielded 0.75 g of compound (E-11) (4,8-bis(2-ethyl-2'-fluoro-4'-(4-pentylcyclohexyl)-(1,1'-biphenyl)-4-yl)-5,6-methyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole).

[0339] Phase transition temperature (°C) Cr 227N 229Iso

[0340] UV-Vis(CH2Cl2, λ) max ): 434nm

[0341] 1 ¹H NMR (CDCl₃, TMS internal standard) δ (ppm) = 8.15 (d, J = 1.4 Hz, 1H), 8.04 (dd, J = 8.0, 1.6 Hz, 1H), 7.52 (s, 1H), 7.49 (dd, J = 7.8, 1.8 Hz, 1H), 7.40 (t, J = 7.3 Hz, 2H), 7.29 (t, J = 8.0 Hz, 1H), 7.25 (t, J = 8.0 Hz, 1H), 6.99-7.1 0 (m, 4H), 3.37 (s, 3H), 2.62-2.71 (m, 4H), 2.64 (s, 3H), 2.55 (s, 2H), 1.99 (d, J=13.3Hz, 4H), 1.91 (d, J=13.3Hz, 4H), 1.50 (q, J=12.7Hz, 4H), 1.26-1.34 (m, 18H), 1.04-1.20 (m, 10H), 0.91 (t, J=6.9Hz, 6H)

[0342] (Example 12) Preparation of compound (E-12) (4,8-bis(5-(4-(3-ethylheptyl)piperidin-1-yl)thiophen-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole)

[0343] [Chemistry 59]

[0344]

[0345] Using the same method as in Example 1, compound (E-12) (4,8-bis(5-(4-(3-ethylheptyl)piperidin-1-yl)thiophen-2-yl)-6-propyl-5H-imidazo[5,4-f]-2,1,3-benzothiadiazole) was obtained.

[0346] Phase transition temperature (°C) Cr 151Iso

[0347] UV-Vis(CH2Cl2, λ) max 600nm

[0348] 1 ¹H NMR (acetone-d6, TMS internal standard) δ (ppm) = 11.17, 8.18, 6.23, 3.75, 2.78-2.98, 1.87 (d, J = 11.0 Hz, 4H), 1.29-1.42 (m, 42H), 1.11 (t, J = 8.0 Hz, 3H), 0.86-0.92 (m, 15H)

[0349] Other compounds used in this invention can also be obtained using the same method as these synthetic examples. Table 1 shows a summary of the evaluation results. In the table, abbreviations for some structures are used. Additionally, the values ​​of λmax in the table are determinations in dichloromethane.

[0350] [Transformation 60]

[0351] Me:-CH3

[0352] Pr: -CH2CH2CH3

[0353] Pent: -CH2CH2CH2CH2CH3

[0354] Hep: -CH2CH2CH2CH2CH2CH2CH2CH3

[0355] HE:

[0356] CF3: -CF3

[0357] CN:-C≡N

[0358] SMe: -S-CH3

[0359] Ms:

[0360] SFM:

[0361] Cy:

[0362] Pi: Pi′:

[0363] P:

[0364] G: G′:

[0365] PE: PE′:

[0366] T: TT:

[0367] BT: BT′:

[0368] [Chemistry 61]

[0369]

[0370] [Table 1]

[0371] Compound <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R a ]]> <![CDATA[A 11 ]]> <![CDATA[A 12 ]]> <![CDATA[A 13 ]]> <![CDATA[A 21 ]]> <![CDATA[A 22 ]]> <![CDATA[A 23 ]]> λmax E-13 Pent Pent Pr H P P - P P - 431nm E-14 Pent Pent Me H P G - P G’ - 434nm E-15 HE HE Pr H P Pi - P Pi’ - 503nm E-5 Pent Pent Pr H P G Cy P G’ Cy 436nm E-10 Pent Pent Me H PE’ G Cy PE G’ Cy 435nm E-11 Pent Pent Me Me PE’ G Cy PE G’ Cy 434nm E-16 Pent Pent Pr H PE’ G Cy PE G’ Cy 435nm E-9 Pr Pr Pr H TT G - TT G’ - 552nm E-17 Pr Pr Pr H TT G Cy TT G’ Cy 550nm E-7 Hep Hep Pr H TT Pi - TT Pi’ - 610nm E-18 HE HE Pr H TT Pi - TT Pi’ - 608nm E-19 HE HE Pr H TT P Pi TT P Pi 589nm E-8 Pent Pent Pr <![CDATA[CF3]]> PE’ G Cy PE G’ Cy 443nm E-6 Me Me Pr H T Pi - T Pi - 608nm E-12 HE HE Pr H T Pi - T Pi - 600nm E-20 Pent Pent Pr H T G - T G’ - 544nm E-21 Pent Pent Pr H T G P T G’ P 551nm E-22 Pent Pent Pr H T T - T T - 562nm E-23 Pent Pent Pr H T T Pi T T Pi’ 624nm E-24 Pr Pr Pr H BT’ - - BT - - 533nm E-25 Pr Pr Pr H BT’ P - BT P - 546nm E-26 Pr Pr Pr H BT’ G Cy BT G’ Cy 543nm E-27 Hep Hep Pr H BT’ P Pi BT P Pi’ 630nm E-28 Pent Pent Me H P TT - P TT - 477nm E-29 Pent Pent Me H P TT Pi P TT Pi’ E-30 [[ID=I34]]539nm Pent Pr H Pent P TT Cy P TT Cy E-31 555nm Pr H Pent G Pent TT G’ Cy TT E-32 Cy Pr H 551nm G P Pent G’ P Pent E-33 TT TT 558nm HE HE SMe - SFM TT - Pi E-34 TT Pi' 661nm HE HE Ms - SFM TT - Pi E-35 TT Pi' 677nm H T T - T T - [[ID=17,2]]HE E-36 HE CF3 577nm HE HE CN - Me TT - Pi E-37 TT Pi' 592nm HE HE SMe - Ms TT - Pi TT Pi' 672nm

[0372] (Example 38) Modulation of the liquid crystal composition - 1

[0373] The modulation consists of a main liquid crystal (H) composed of the following components.

[0374] [Chemistry 62]

[0375]

[0376] A liquid crystal composition (MA) was prepared by modulating 98% of the parent liquid crystal (H) and 2% of the compound (E-1) obtained in Example 1. The optical properties of this composition (MA) were measured as follows.

[0377] λ max 546nm

[0378] Dichroism ratio: 3.4

[0379] In addition, the modulated liquid crystal composition (MA) maintains a uniform nematic liquid crystal state at room temperature for one month.

[0380] Furthermore, a two-week lightfastness test was conducted using a liquid crystal composition (MA), and the results confirmed that the hue remained unchanged.

[0381] (Example 39) Modulation of the liquid crystal composition - 2

[0382] A liquid crystal composition (MB) consisting of 99% parent liquid crystal (H) and 1% of compound (E-2) obtained in Example 2 was prepared. The optical properties of this composition (MB) were measured as follows.

[0383] λ max 545nm

[0384] Dichroism ratio: 6.4

[0385] Furthermore, the modulated liquid crystal composition (MB) maintains a uniform nematic liquid crystal state at room temperature for more than one month.

[0386] 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.

[0387] (Comparative Example 1) Modulation of Liquid Crystal Composition - 3

[0388] A liquid crystal composition (MC) was prepared, consisting of 99% parent liquid crystal (H) and 1% of a compound (R-1) having a thiadiazole quinoxaline skeleton (4,9-bis-(5-methylthiophene-2-yl)-6,7-dimethyl-2-thia-1,3,5,8-tetraaza-cyclopentane[b]naphthalene). The optical properties of this composition (MC) were measured as follows.

[0389] [Chemistry 63]

[0390]

[0391] λ max 647nm

[0392] Dichroism ratio: 4.6

[0393] Furthermore, pigment precipitation was observed in the modulated liquid crystal composition (MC) after 3 days at room temperature.

[0394] Furthermore, lightfastness tests were conducted using a liquid crystal composition (MC), and a color change was confirmed after 10 days.

[0395] Comparing the dichroic ratio, solubility, and lightfastness of Example 38 with Comparative Example 1, it is evident that the compound of this application possesses a larger dichroic ratio, higher solubility, and higher lightfastness compared to the compound of Comparative Example 1. Furthermore, Example 39 exhibits a larger dichroic ratio while maintaining high solubility. Therefore, it is clear that the compound of this application possesses the characteristic of simultaneously possessing a large dichroic ratio and high solubility.

[0396] Table 2 shows the evaluation results of each compound in liquid crystals.

[0397] [Table 2]

[0398]

[0399] The results above show that the compound of this application exhibits a greater dichroism ratio and high solubility in the bulk liquid crystal compared to the compound shown in Comparative Example 1. Furthermore, the compound of this application clearly possesses high lightfastness, indicating that it is an extremely useful compound for industrial applications.

Claims

1. A compound represented by the general formula (1), In the formula, U is the group represented by general formula (2). R 1 R 2 Each can independently represent an alkyl group having 1 to 20 carbon atoms. R 3 This refers to cyano groups and alkyl groups with 1 to 20 carbon atoms. One or more non-adjacent -CH2- groups in these groups can be replaced by -O-, -S-, or -SO2-. Hydrogen atoms in these groups can be replaced by fluorine atoms. R a This refers to a hydrogen atom, an N,N-dialkylsulfonamide group, or an alkyl group having 1 to 20 carbon atoms, where the hydrogen atom may be replaced by a fluorine atom. X a Indicates -S-, A 1 A 2 and A a Each group independently represents a group selected from the following groups: (a) 1,4-cyclohexylene; (b) 1,4-Phenylidene; (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, and thiopheno[3,2-b]thiophene-2,5-diyl, wherein one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=. These groups can be unsubstituted or substituented by one or more substituents L. 2 replace, L 2 Each of the following independently represents a hydrogen atom, a fluorine atom, and 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. Z 1 Z 2 and Z a Indicates a single key. i and j each independently represent integers from 2 to 4. a represents an integer that is either 0 or 1. Multiple A's 1 A 2 They can be the same or different.

2. The compound according to claim 1, in general formula (1), i and j each independently represent integers from 2 to 3.

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

4. A host-guest type (GH type) liquid crystal composition or a polymer-dispersed liquid crystal composition, comprising one or more of the compounds described in claim 1 or 2.

5. A liquid crystal display element or a dimming element that uses the composition of claim 3 or 4.

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