CN111187628A

CN111187628A - Liquid crystal compound, composition and liquid crystal display element

Info

Publication number: CN111187628A
Application number: CN201911059918.2A
Authority: CN
Inventors: 岩楯展行; 楠本哲生; 小矶彰宏
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2018-11-15
Filing date: 2019-11-01
Publication date: 2020-05-22
Also published as: JP2020083761A

Abstract

The invention provides a liquid crystal compound, a composition and a liquid crystal display element. The invention provides a liquid crystal compound having a large value of refractive index anisotropy (Delta n). The solution is a compound represented by the general formula (I),

(in the formula, Rⁱ¹And Rⁱ²Each independently represents a carbon number of 1 to 15Alkyl of (A) and the likeⁱ¹And Aⁱ²Each independently represents 1, 4-cyclohexylene or the like, Zⁱ¹And Zⁱ²Each independently represents-CH₂O-, etc., nⁱ¹And mⁱ¹Each independently represents 0, 1 or 2, lⁱ¹Represents 0 or 1, Yⁱ¹represents-O-etc., Yⁱ²represents-O-, etc. ).

Description

Liquid crystal compound, composition and liquid crystal display element

Technical Field

The present invention relates to a liquid crystal compound and a liquid crystal composition containing the same.

Background

Liquid crystal display elements have been used in watches and calculators, and have been developed for use in various household appliances, measuring devices, panels for automobiles, word processors, electronic notebooks, printers, computers, televisions, and the like. Representative examples of liquid crystal display systems include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, IPS (in-plane switching) type, OCB (optically compensated birefringence) type, ECB (voltage controlled birefringence) type, VA (vertically aligned) type, CSH (color super vertical) type, and FLC (ferroelectric liquid crystal). As a driving method of the liquid crystal display, a static driving, a multiplex driving, a simple matrix method, and an Active Matrix (AM) method of driving by a TFT (thin film transistor), a TFD (thin film diode), or the like can be cited.

Among these, in display systems such as IPS mode, ECB mode, VA mode, CSH mode, and the like, a liquid crystal composition having a negative dielectric anisotropy (Δ ∈) is used. These liquid crystal compositions are required to have a low voltage driving, a high-speed response, and a wide operating temperature range, i.e., a large absolute value of Δ ∈, low viscosity, and a high nematic phase-isotropic liquid phase transition temperature (T)_ni). In addition, it is necessary to adjust Δ n of the liquid crystal composition to an appropriate range in accordance with the setting of Δ n × d, which is the product of the refractive index anisotropy (Δ n) and the cell gap (d), in conjunction with the cell gap.

The following compounds having a dibenzofuran ring substituted with 2 fluorine atoms have been reported, but no compound having a dibenzofuran ring not substituted with a fluorine atom has been disclosed (patent document 1 and patent document 2).

[ solution 1]

(in the formula, R¹And R²Each independently represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkynyl group having 2 to 15 carbon atoms, and m and n each independently represent 0 or 1. )

Documents of the prior art

Patent document

Patent document 1: german patent application publication No. 102015002298

Patent document 2: japanese patent No. 4379857 Specification

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a liquid crystal compound having a large value of refractive index anisotropy (Δ n), and also providing a liquid crystal composition and a liquid crystal display element each having the compound as a constituent member.

Means for solving the problems

The present inventors have conducted studies on various compounds in order to solve the above problems, and as a result, have found that a compound having the following condensed ring can effectively solve the problems, and have completed the present invention.

Provided is a compound represented by the general formula (I).

[ solution 2]

(in the formula, Rⁱ¹And Rⁱ²Each independently represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -BR¹R²(in the formula, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O- (wherein R is³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴The same or different), an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and 1-CH present in the alkyl group having 1 to 15 carbon atoms or the alkenyl group having 2 to 15 carbon atoms₂-or 2 or more-CH not adjacent₂Each independently may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SOO-O-or-C.ident.C-, and in addition, the number of carbon atoms is from 1 to 15The hydrogen atom present in the alkyl group or the alkenyl group having 2 to 15 carbon atoms of (a) may be substituted with a fluorine atom,

Aⁱ¹and Aⁱ²Each independently represents a group selected from the group consisting of,

(a)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-or-S-. ) A

(b)1, 4-phenylene (1-CH-or nonadjacent 2 or more-CH-present in the group may be substituted by-N-and hydrogen atoms present in the group may be substituted by halogen atoms); and,

(c)1, 4-cyclohexenylene, naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (the hydrogen atoms present in these groups may be substituted by halogen atoms, and further, 1-CH ═ or not adjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by — N ═ and the like), and

(d) dibenzofuran-3, 7-diyl, dibenzothiophene-3, 7-diyl or fluorene-2, 7-diyl,

Zⁱ¹and Zⁱ²Each independently represents-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-COO-、-OCO-、-CH₂CH₂-、-CF₂CF₂-, -CH-, -CF-, -C.ident.C-or a single bond,

nⁱ¹and mⁱ¹Each independently represents 0, 1 or 2, when nⁱ¹Represents 2 or Aⁱ¹And Zⁱ¹When plural, they may be the same or different, and when m isⁱ¹Represents 2 or Aⁱ²And Zⁱ²When a plurality of them exist, they may be the same or different,

lⁱ¹represents 0 or 1, whenⁱ¹R represents 0ⁱ³Represents a hydrogen atom whenⁱ¹R represents 1ⁱ³And Rⁱ⁴Are linked to each other to form a cyclic structure represented by-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH＝、-CH＝CH-、-CH₂-CH＝、-CH＝CHCH₂-、-CH＝CH₂-CH＝、-CH₂CH-or-CH₂CH₂-CH＝，

Yⁱ¹represents-O-, -S-, -SO-, -SOO-, -CF₂-, -CO-or-CH₂-，

Yⁱ²represents-O-, -S-, -SO-, -SOO-, -CF₂-、-CO-、-CH₂-or a single bond.

Wherein the following compounds are excluded:

nⁱ¹、mⁱ¹and lⁱ¹Represents 0, Yⁱ¹represents-O-, Yⁱ²Represents a single bond and Rⁱ¹And Rⁱ²At least one of them represents an alkenyl group having 2 to 15 carbon atoms;

nⁱ¹、mⁱ¹and lⁱ¹Represents 0, Yⁱ¹represents-CH₂-、Yⁱ²Represents a single bond and Rⁱ¹And Rⁱ²At least one of them represents a C1-15 alkyl group;

nⁱ¹represents 1, mⁱ¹And lⁱ¹Represents 0, Yⁱ¹represents-O-, Yⁱ²Represents a single bond, Aⁱ¹Represents 2-O-substituted 1, 4-cyclohexylene, or 1, 4-phenylene, Zⁱ¹Represents a single bond and Rⁱ¹A compound which represents an alkyl group having 1 to 15 carbon atoms; and

nⁱ¹represents 1, mⁱ¹And lⁱ¹Represents 0, Yⁱ¹represents-CH₂-、Yⁱ²Represents a single bond, Aⁱ¹Represents 1, 4-cyclohexylene, or 1, 4-phenylene substituted with a fluorine atom, Zⁱ¹represents-CH₂CH₂-, -C.ident.C-or a single bond and Rⁱ¹A compound which represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms. )

Another aspect of the present invention provides a composition containing 1 or 2 or more compounds represented by the general formula (I), and a liquid crystal display element using the composition.

ADVANTAGEOUS EFFECTS OF INVENTION

The compound of the present invention is a liquid crystal compound having a large value of refractive index anisotropy (Δ n). Therefore, the compound of the present invention is useful as a component of a liquid crystal composition for a liquid crystal display element which requires a high-speed response.

Detailed Description

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

To reduce gamma₁，Rⁱ¹And Rⁱ²Each independently preferably represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and more preferably represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. The alkyl group and the alkenyl group are preferably linear. To increase the absolute value of Δ ε, Rⁱ¹And Rⁱ²Each independently is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. In order to improve miscibility with other liquid crystal components, R is preferably selectedⁱ¹And Rⁱ²In contrast, alkoxy is preferably Rⁱ¹Or Rⁱ²Any one of (1) above. Rⁱ¹And Rⁱ²The hydrogen atoms present in (a) may be substituted by fluorine atoms, but are preferably not substituted by fluorine atoms.

When the formula (I) represents an intermediate, R is preferablyⁱ¹And Rⁱ²At least one of them represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group or-BR¹R²(in the formula, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O- (wherein R is³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴May be the same or different). ).

Aⁱ¹And Aⁱ²Each independently preferably represents a group selected from,

[ solution 3]

More preferably represents a group selected from the following.

[ solution 4]

In particular, to reduce γ₁，Aⁱ¹And Aⁱ²Each independently is preferably trans-1, 4-cyclohexylene, unsubstituted 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene, and further preferably trans-1, 4-cyclohexylene. To improve the miscibility with other liquid crystal components, Aⁱ¹And Aⁱ²Each independently of the others is preferably trans-1, 4-cyclohexylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene. To increase T_ni，Aⁱ¹And Aⁱ²Each independently of the others is preferably unsubstituted 1, 4-phenylene, unsubstituted 1, 4-cyclohexenylene, 1, 4-cyclohexenylene or unsubstituted naphthalene-2, 6-diyl. Note that A isⁱ¹And Aⁱ²When each independently represents a1, 4-cyclohexylene group, 1-CH present in the 1, 4-cyclohexylene group₂-or 2 or more-CH not adjacent₂-is preferably unsubstituted by-O-or-S-. In addition, Aⁱ¹And Aⁱ²When each independently represents a1, 4-phenylene group, the hydrogen atom present in the 1, 4-phenylene group is preferably not substituted with a halogen atom (i.e., the 1, 4-phenylene group is an unsubstituted 1, 4-phenylene group). A. theⁱ¹And/or Aⁱ²When substituted with a halogen atom, the halogen atom is preferably a fluorine atom or a chlorine atom.

To reduce gamma₁，Zⁱ¹And Zⁱ²Each independently is preferably a single bond, -CH₂CH₂-、-CH₂O-or-OCH₂-, more preferably a single bond or-CH₂CH₂-. To increase T_ni，Zⁱ¹And Zⁱ²Each independently is preferably a single bond, -COO-, -OCO-, -CH ≡ CH-or-C ≡ C-, and is more preferably a single bond, -CH ═ CH-or-C ≡ C-. To improve the miscibility with other liquid crystal components，Zⁱ¹And Zⁱ²Each independently is preferably a single bond, -CH₂CH₂-、-CH₂O-or-OCH₂-. In order to improve long-term reliability in the production of a liquid crystal display element, a single bond is preferable.

nⁱ¹And mⁱ¹Preferably each independently represents 0 or 1, more preferably nⁱ¹And mⁱ¹Both represent 0.

lⁱ¹Preferably represents 0.

Yⁱ¹Preferably represents-O-, -S-or-CH₂-more preferably-O-or-S-, and still more preferably-O-.

Yⁱ²Preferably represents-O-, -S-, -CH₂-or a single bond, more preferably-O-, -S-or a single bond, and still more preferably a single bond.

In the general formula (I), when Yⁱ¹represents-O-, Yⁱ²When represents a single bond, R is preferablyⁱ¹Or Rⁱ²Is a group other than an alkenyl group having 2 to 15 carbon atoms, i.e. Rⁱ¹And Rⁱ²Each independently is a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -BR¹R²(in the formula, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O- (wherein R is³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴The same or different)) or an alkyl group having 1 to 15 carbon atoms (1-CH present in the alkyl group)₂-or 2 or more-CH not adjacent₂Each independently of the other may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SOO-O-or-C.ident.C-, and more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

In the general formula (I), when Yⁱ¹represents-CH₂-、Yⁱ²When represents a single bond, R is preferablyⁱ¹Or Rⁱ²Is a group other than an alkyl group having 1 to 15 carbon atoms, i.e. Rⁱ¹And Rⁱ²Each independently is a chlorine atom, a bromine atom,Iodine atom, hydroxyl group, -BR¹R²(in the formula, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O- (wherein R is³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴The same or different)) or an alkenyl group having 2 to 15 carbon atoms (1-CH present in the alkenyl group)₂-or 2 or more-CH not adjacent₂Each independently may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SOO-O-or-C.ident.C-, and more preferably an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

In the general formula (I), the compounds represented by the following general formulae (I-1) to (I-48) are preferred.

[ solution 5]

[ solution 6]

[ solution 7]

(in the formula, Rⁱ¹And Rⁱ²Respectively represent R in the general formula (I)ⁱ¹And Rⁱ²The same meaning is used. )

Among the compounds represented by the above general formulae (I-1) to (I-48), the compounds represented by the following formulae are preferred.

[ solution 8]

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

[ solution 13]

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

[ solution 23]

[ solution 24]

[ solution 25]

[ solution 26]

[ solution 27]

[ solution 28]

[ solution 29]

[ solution 30]

[ solution 31]

[ solution 32]

[ solution 33]

[ chemical 34]

[ solution 35]

[ solution 36]

[ solution 37]

[ solution 38]

[ solution 39]

(production method)

In the present invention, the compound represented by the general formula (I) can be produced as follows. The spirit and scope of the present invention are not limited to these production methods.

(production method 1)

[ solution 40]

(in the formula, Rⁱ¹、Rⁱ²、Aⁱ¹、Aⁱ²、Zⁱ¹、Zⁱ²、nⁱ¹、mⁱ¹、lⁱ¹、Rⁱ³、Rⁱ⁴And Yⁱ²Respectively represent R in the general formula (I)ⁱ¹、Rⁱ²、Aⁱ¹、Aⁱ²、Zⁱ¹、Zⁱ²、nⁱ¹、mⁱ¹、lⁱ¹、Rⁱ³、Rⁱ⁴And Yⁱ²The same meaning is given to the same person,

R^im1and R^im2Each independently represents a hydrogen atom, a methyl, ethyl or propyl group, or R^im1And R^im2Are linked to each other to form a cyclic structure represented by-CH₂-CH₂-、-CH₂-CH₂-CH₂-, or-CH₂-C(CH₃)₂-CH₂-，

X^im1Represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,

X^im2represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group,

Y^im1represents-O-or-S-. )

The compound represented by the general formula (S-3) can be obtained by reacting the compound represented by the general formula (S-1) with the compound represented by the general formula (S-2) in the presence of a transition metal catalyst and a base.

The transition metal catalyst used may be any catalyst as long as the reaction can be carried out appropriately, and is preferably tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium (II) dichloride, [1,1 '-bis (diphenylphosphino) ferrocene ] palladium (II) dichloride or bis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride, and more preferably tetrakis (triphenylphosphine) palladium (0), [1, 1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride or bis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride. In addition, in order to make the reaction proceed properly, a phosphine-based ligand such as triphenylphosphine may be added as necessary.

The reaction solvent to be used may be any solvent as long as the reaction can be carried out appropriately, and ether solvents such as tetrahydrofuran, diethyl ether and tert-butyl methyl ether, alcohol solvents such as methanol, ethanol and propanol, aromatic solvents such as benzene, toluene and xylene are preferable, and tetrahydrofuran, ethanol and toluene are more preferable. In addition, water may be used as necessary in order to appropriately proceed the reaction.

The base to be used may be any base as long as the reaction can be carried out appropriately, and is preferably a carbonate such as potassium carbonate, sodium carbonate or cesium carbonate, a phosphate such as tripotassium phosphate or monopotassium phosphate, and more preferably potassium carbonate, cesium carbonate or tripotassium phosphate.

The reaction temperature may be any temperature as long as the reaction can be carried out appropriately, and is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ℃ to the temperature at which the solvent is refluxed, and particularly preferably from 60 ℃ to the temperature at which the solvent is refluxed.

Y in the compound represented by the general formula (I) can be obtained by subjecting the compound represented by the general formula (S-3) to intramolecular reactionⁱ¹A compound represented by the general formula (S-4) which is-O-or-S-. The intramolecular reaction can be carried out by reacting-Y of the general formula (S-3)^im1-H is deprotonated with a base and an anion is generated.

Examples of the base used in this case include metal hydrides, metal carbonates, metal phosphates, metal hydroxides, metal carboxylates, metal amides, and metals, among which alkali metal hydrides, alkali metal phosphates, alkali metal carbonates, alkali metal hydroxides, alkali metal amides, and alkali metals are preferable, and alkali metal phosphates, alkali metal hydrides, and alkali metal carbonates are more preferable. As the alkali metal hydride, lithium hydride, sodium hydride and potassium hydride can be preferably cited, as the alkali metal phosphate, tripotassium phosphate can be preferably cited, and as the alkali metal carbonate, sodium hydrogen carbonate, cesium carbonate, potassium carbonate and potassium hydrogen carbonate can be preferably cited.

The reaction solvent may be any solvent as long as the reaction can be carried out appropriately, and an ether solvent, a chlorine solvent, a hydrocarbon solvent, an aromatic solvent, a polar solvent, or the like can be preferably used. Preferred examples of the ether solvent include 1, 4-dioxane, 1, 3-dioxane, tetrahydrofuran, diethyl ether, and tert-butyl methyl ether, preferred examples of the chlorine solvent include dichloromethane, 1, 2-dichloroethane, and carbon tetrachloride, preferred examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, heptane, and octane, preferred examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene, preferred examples of the polar solvent include N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. Among them, ether solvents such as tetrahydrofuran and diethyl ether and polar solvents such as N-methylpyrrolidone are more preferable. Each of the solvents mentioned above may be used alone, or 2 or more solvents may be mixed and used.

As for the reaction temperature, it may be carried out in the range from the freezing point to the reflux temperature of the solvent, preferably 0 ℃ to 180 ℃.

(production method 2) [ 41]

R^im3and R^im4Each independently represents a hydrogen atom, a methyl, ethyl or propyl group, or R^im3And R^im4Are linked to each other to form a cyclic structure represented by-CH₂-CH₂-、-CH₂-CH₂-CH₂-, or-CH₂-C(CH₃)₂-CH₂-，

X^im3Represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,

X^im4represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group,

Y^im2represents-O-or-S-. )

The compound represented by the general formula (S-7) can be obtained by reacting the compound represented by the general formula (S-5) with the compound represented by the general formula (S-6) in the presence of a transition metal catalyst and a base.

The transition metal catalyst, the reaction solvent and the base used are the same as those used in the step of obtaining the compound represented by the general formula (S-3). The reaction temperature is the same as that in the step of obtaining the compound represented by the general formula (S-3).

Y in the compound represented by the general formula (I) can be obtained by subjecting the compound represented by the general formula (S-7) to intramolecular reactionⁱ¹A compound represented by the general formula (S-8) which is-O-or-S-. The intramolecular reaction can be carried out by reacting-Y of the general formula (S-7)^im2-H is deprotonated with a base and an anion is generated.

The base and the reaction solvent used are the same as those used in the step of obtaining the compound represented by the general formula (S-4). The reaction temperature is the same as that in the step of obtaining the compound represented by the general formula (S-4).

(production method 3)

[ solution 42]

R^iaand R^ibEach independently represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group or-BR¹R²(in the formula, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O- (wherein R is³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴May be the same or different). )

R^icAnd R^idEach independently represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group, -BR⁵R⁶(in the formula, R⁵And R⁶Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R⁵And R⁶Are linked to each other to form a cyclic structure, and represent-O- (CR)⁷R⁸)_n1-O- (in the formula，R⁷And R⁸Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n1 represents 2 or 3, and a plurality of CR's are present⁷R⁸May be the same or different). ) or-ZnX^im5(in the formula, X^im5Represents a chlorine atom, a bromine atom or an iodine atom. ). )

For example, when R is^iaAnd R^ibIs a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group, R^icAnd R^idis-BR⁵R⁶or-ZnX^im5In this case, the compound represented by the general formula (I) can be obtained by reacting the compound represented by the general formula (Ia) with the compound represented by the general formula (S-9) in the presence of a transition metal catalyst and/or a base. Further, the compound represented by the general formula (I) can be obtained by reacting the compound represented by the general formula (Ib) with the compound represented by the general formula (S-10) in the presence of a transition metal catalyst and/or a base. The reaction solvent, transition metal catalyst and base used are the same as those used in the step of obtaining the compound represented by the general formula (S-3). The reaction temperature is the same as that in the step of obtaining the compound represented by the general formula (S-3).

In addition, for example, when R^iaAnd R^ibIs hydroxy, R^icAnd R^idIn the case of a chlorine atom, a bromine atom or an iodine atom, the compound represented by the general formula (I) can be obtained by reacting the compound represented by the general formula (Ia) with the compound represented by the formula (S-9) in the presence of a base. Further, the compound represented by the general formula (I) can be obtained by reacting the compound represented by the general formula (Ib) with the compound represented by the formula (S-10) in the presence of a base.

(composition)

In the composition of the present invention, since the effect cannot be exhibited if the content of the compound represented by the general formula (I) is small, the lower limit of the content is preferably 1% by mass or more (hereinafter, the% in the composition means% by mass), preferably 2% or more, preferably 5% or more, and more preferably 10% or more. Further, since a large content causes problems such as precipitation, the upper limit is preferably 70% or less, more preferably 60% or less, still more preferably 50% or less, and particularly preferably 40% or less. The compound represented by the general formula (I) may be used alone in 1 kind, or 2 or more kinds may be used simultaneously. In order to adjust the physical property values of the liquid crystal composition, compounds other than the compound represented by the general formula (I) may be used, and a compound having no liquid crystal phase may be added in addition to the compound having a liquid crystal phase as necessary.

The composition of the present invention contains at least 1 compound represented by the general formula (I) as a first component, and particularly preferably contains at least 1 component selected from the group consisting of the following second component, third component and fourth component as another component.

The second component preferably contains 1 or 2 or more compounds selected from the group of compounds represented by the general formulae (N-1), (N-2) and (N-3). These compounds correspond to compounds with negative dielectricity (Δ ∈ negative in sign and greater than 2 ° absolute).

[ solution 43]

(in the formula, wherein,

R^N11、R^N12、R^N21、R^N22、R^N31and R^N32Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

A^N11、A^N12、A^N21、A^N22、A^N31and A^N32Each independently represents a group selected from the group consisting of,

(a11)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-. )

(b11)1, 4-phenylene (1 CH-or nonadjacent 2 or more-CH-present in the radical may be substituted by-N) -) and

(c11) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or 2 or more-CH ═ which are not adjacent may be substituted by-N ═ can be used.)

The above-mentioned group (a11), group (b11) and group (c11) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^N11、Z^N12、Z^N21、Z^N22、Z^N31and Z^N32Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,

X^N21represents a hydrogen atom or a fluorine atom,

T^N31represents-CH₂-or an oxygen atom,

n^N11、n^N12、n^N21、n^N22、n^N31and n^N32Each independently represents an integer of 0 to 3, n^N11+n^N12、n^N21+n^N22And n^N31+n^N32Each independently is 1,2 or 3, A^N11～A^N32、Z^N11～Z^N32When a plurality of them exist, they may be the same or different. Wherein the compound represented by the general formula (N-1) is excluded from the general formula (N-2) and the general formula (N-3), and the compound represented by the general formula (N-2) is excluded from the general formula (N-3). )

The compounds represented by the general formulae (N-1), (N-2) and (N-3) correspond to compounds having negative dielectric properties (Δ ε has a negative sign and an absolute value of more than 2.), and preferably Δ ε has a negative sign and an absolute value of more than 3.

In the general formulae (N-1), (N-2) and (N-3), R^N11、R^N12、R^N21、R^N22、R^N31And R^N32Each independently preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atomsOr an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, still more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and particularly preferably an alkenyl group having 3 carbon atoms (propenyl group). Wherein, by reacting R^N11And R^N12The compound represented by the general formula (I) in combination with at least 1 or more of the compounds representing an alkenyl group can significantly suppress a decrease in the Voltage Holding Ratio (VHR). Similarly, by mixing R^N21And R^N22Wherein at least 1 or more of the compounds having an alkenyl group are used in combination with the compound represented by the general formula (I), the decrease in the Voltage Holding Ratio (VHR) can be remarkably suppressed, and R is used^N31And R^N32The compound represented by the general formula (I) in combination with at least 1 or more of the compounds representing an alkenyl group can significantly suppress a decrease in the Voltage Holding Ratio (VHR).

When the ring structure to which the compound is bonded is a phenyl group (aromatic group), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the compound is bonded is a saturated ring structure such as cyclohexane, pyran, dioxane, or the like, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any one of the formulae (R1) to (R5). (Black dots in each formula represent carbon atoms in the ring structure.)

[ solution 44]

A^N11、A^N12、A^N21、A^N22、A^N31And A^N32Independently of each other atWhen Δ n is required to be increased, it is preferably aromatic, and in order to improve the response speed, it is preferably aliphatic, and preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably represents the following structure,

[ solution 45]

More preferably, it represents trans-1, 4-cyclohexylene or 1, 4-phenylene.

Z^N11、Z^N12、Z^N21、Z^N22、Z^N31And Z^N32Each independently preferably represents-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-or a single bond, further preferably-CH₂O-、-CH₂CH₂-or a single bond, particularly preferably-CH₂O-or a single bond.

X^N21Preferably a fluorine atom.

T^N31Preferably an oxygen atom.

n^N11+n^N12、n^N21+n^N22And n^N31+n^N32Preferably 1 or 2, preferably n^N11Is 1 and n^N12A combination of 0, n^N11Is 2 and n^N12A combination of 0, n^N11Is 1 and n^N12Is a combination of 1, n^N11Is 2 and n^N12Is a combination of 1, n^N21Is 1 and n^N22A combination of 0, n^N21Is 2 and n^N22A combination of 0, n^N31Is 1 and n^N32A combination of 0, n^N31Is 2 and n^N32Is a combination of 0.

The lower limit of the preferable content of the compound represented by the formula (N-1) is 0%, 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the composition of the present invention. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

The lower limit of the preferable content of the compound represented by the formula (N-2) is 0%, 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the composition of the present invention. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

The lower limit of the preferable content of the compound represented by the formula (N-3) is 0%, 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the composition of the present invention. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the lower limit value and the upper limit value are preferably low. Further, when T of the composition of the present invention is used_niWhen a composition having high temperature stability is required while keeping the composition high, the lower limit value and the upper limit value are preferably low. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, the lower limit value is preferably high and the upper limit value is preferably high.

In the composition of the present invention, it is preferable that 1 or 2 or more compounds represented by the general formula (i-1) are contained as the general formula (N-1).

[ solution 46]

(in the formula, A)ⁱ¹¹、Aⁱ¹²And Aⁱ¹³Each independently represents 1, 4-cyclohexylene or 1, 4-phenylene, 1-CH present in 1, 4-cyclohexylene₂-or 2 or more-CH not adjacent₂May be substituted by-O-or-S-, 1 hydrogen atom present in the 1, 4-phenylene group may each independently be substituted by a fluorine atom or a chlorine atom, Zⁱ¹represents-OCH₂-、-CH₂O-、-CF₂O-、-OCF₂-、-CH₂CH₂-or-CF₂CF₂-，mⁱ¹¹And mⁱ¹²Each independently represents 0 or 1, R^N11、R^N12And Z^N12Each independently represents R in the general formula (N-1)^N11、R^N12And Z^N12The same meaning is used. )

The compound represented by the general formula (i-1) is preferably a compound represented by the general formula (i-1A), the general formula (i-1B) or the general formula (i-1C).

[ solution 47]

(in the formula, R^N11、R^N12、Aⁱ¹¹And Zⁱ¹Each independently represents R in the general formula (i-1)^N11、R^N12、Aⁱ¹¹And Zⁱ¹The same meaning is used. )

[ solution 48]

(in the formula, R^N11、R^N12、Aⁱ¹¹、Aⁱ¹²And Zⁱ¹Each independently represents R in the general formula (i-1)^N11、R^N12、Aⁱ¹¹、Aⁱ¹²And Zⁱ¹The same meaning is used. )

[ solution 49]

(in the formula, mⁱ¹³Represents 1, R^N11、R^N12、Aⁱ¹¹、Aⁱ¹²、Aⁱ¹³、Zⁱ¹、Zⁱ²And mⁱ¹¹Each independently represents R in the general formula (i-1)^N11、R^N12、Aⁱ¹¹、Aⁱ¹²、Aⁱ¹³、Zⁱ¹、Zⁱ²And mⁱ¹¹The same meaning is used. )

As the compound represented by the general formula (i-1A), compounds represented by the following general formulae (i-1A-1) to (i-1A-4) are preferable.

[ solution 50]

(in the formula, R^N11And R^N12Each independently represents R in the general formula (i-1)^N11And R^N12The same meaning is used. )

The compound represented by the general formula (i-1B) is preferably a compound represented by the following general formula (i-1B-1) to general formula (i-1B-7).

[ solution 51]

As the compound represented by the general formula (i-1C), compounds represented by the following general formula (i-1C-1) and general formula (i-1C-2) are preferable.

[ solution 52]

The composition of the present invention preferably contains 1 or 2 or more compounds represented by the general formula (i-1), may contain 1 or 2 or more compounds selected from the group of compounds represented by the general formula (i-1A), the general formula (i-1B) or the general formula (i-1C), and may contain 1 or more compounds represented by the general formula (i-1A), the general formula (i-1B) or the general formula (i-1C). It preferably contains 1 or 2 or more compounds represented by the general formula (i-1A) and the general formula (i-1B), and more preferably 2 to 10 compounds.

More specifically, the general formula (i-1A), the general formula (i-1B) and the general formula (i-1C) preferably contain 1 or 2 or more compounds selected from the group consisting of the compounds represented by the general formula (i-1A-1), the general formula (i-1B-1) and the general formula (i-1C-1), and more preferably a combination of the compound represented by the general formula (i-1A-1) and the compound represented by the general formula (i-1B-1).

The composition of the present invention preferably contains 1 or 2 or more compounds represented by the general formula (ii).

[ Hua 53]

(in the formula, A)ⁱⁱ¹、Aⁱⁱ²Each independently represents 1, 4-cyclohexylene or 1, 4-phenylene, 1-CH present in 1, 4-cyclohexylene₂-or 2 or more-CH not adjacent₂May be substituted by-O-or-S-, 1 hydrogen atom present in the 1, 4-phenylene group may each independently be substituted by a fluorine atom or a chlorine atom, mⁱⁱ¹And mⁱⁱ²Each independently represents 1 or 2, R^N11And R^N12Each independently represents R in the general formula (N-1)^N11And R^N12The same meaning is used. )

The general formula (ii) preferably contains 1 or 2 or more compounds represented by the general formula (ii-1).

[ solution 54]

(in the formula, R^N11、R^N12、Aⁱⁱ¹And mⁱⁱ¹Represents R in the general formula (ii)^N11、R^N12、Aⁱⁱ¹And mⁱⁱ¹The same meaning is used. )

The compound represented by the general formula (ii-1) is preferably a compound represented by the general formula (ii-1A) or the general formula (ii-1B).

[ solution 55]

(in the formula, R^N11、R^N12And Aⁱⁱ¹Represents R in the general formula (ii)^N11、R^N12And Aⁱⁱ¹The same meaning is used. )

[ solution 56]

(in the formula, A)ⁱⁱ¹¹And Aⁱⁱ¹²Each independently represents 1, 4-cyclohexylene or 1, 4-phenylene, 1-CH present in 1, 4-cyclohexylene₂-or 2 or more-CH not adjacent₂-may be substituted by-O-or-S-, 1 hydrogen atom present in the 1, 4-phenylene group may each independently be substituted by a fluorine atom or a chlorine atom, R^N11And R^N12Represents R in the general formula (ii)^N11And R^N12The same meaning is used. )

As the compound represented by the general formula (ii-1A), compounds represented by the following general formula (ii-1A-1) and general formula (ii-1A-2) are preferable.

[ solution 57]

(in the formula, R^N11And R^N12Represents R in the general formula (ii)^N11And R^N12The same meaning is used. )

The compound represented by the general formula (ii-1B) is preferably a compound represented by the following general formula (ii-1B-1) to general formula (ii-1B-3).

[ solution 58]

The composition of the present invention preferably contains 1 or 2 or more compounds represented by the general formula (ii), may contain 1 or 2 or more compounds selected from the group consisting of the compounds represented by the general formula (ii-1A) and the general formula (ii-1B), and may contain 1 or more compounds represented by the general formula (ii-1A) and the general formula (ii-1B), respectively. It is preferable to contain 2 to 10 compounds represented by the general formula (ii-1A) and the general formula (ii-1B).

More specifically, the general formula (ii-1A) preferably contains 1 or 2 or more compounds selected from the group of compounds represented by the general formula (ii-1A-1), and the general formula (ii-1B) preferably contains 1 or 2 or more compounds selected from the group of compounds represented by the general formula (ii-1B-1) and the general formula (ii-1B-2), and more preferably a combination of the compounds represented by the general formula (ii-1A-1) and the general formula (ii-1B-1).

Further, the general formula (N-1) preferably contains 1 or 2 or more compounds represented by the following general formula (LC 3-b).

[ chemical 59]

(in the formula, R^N11、R^N12、A^N11、A^N12And Z^N11Each independently represents R in the general formula (N-1)^N11、R^N12、A^N11、A^N12And Z^N11Same meaning as X^LC3b1～X^LC3b4Represents a hydrogen atom or a fluorine atom, X^LC3b1And X^LC3b2Or X^LC3b3And X^LC3b4Each represents a fluorine atom, m^LC3b1Represents 0 or 1. Wherein the compounds represented by the general formula (i-1) and the general formula (ii) are excluded from the general formula (LC 3-b). )

The compound represented by the general formula (LC3-b) is preferably a compound represented by the following general formula (LC3-b1) to general formula (LC3-b 10).

[ solution 60]

(in the formula, R^N11And R^N12Each independently represents R in the general formula (N-1)^N11And R^N12The same meaning is used. )

R^N11And R^N12The combination of (a) is not particularly limited, but a combination of alkyl groups on both sides, a combination of alkenyl groups on both sides, a combination of alkyl groups on either side and alkenyl groups on the other side, a combination of alkyl groups on either side and alkoxy groups on the other side, and a combination of alkyl groups on either side and alkenyloxy groups on the other side are preferable, and a combination of alkyl groups on both sides and alkenyl groups on both sides is more preferable.

The compound represented by the general formula (LC3-b) is preferably a compound represented by the following general formula (LC 3-c).

[ solution 61]

The compound represented by the general formula (N-2) is preferably a compound selected from the group consisting of compounds represented by the general formulae (N-2-1) to (N-2-3).

[ solution 62]

(in the formula, R^N21And R^N22Each independently represents R in the general formula (N-2)^N21And R^N22The same meaning is used. )

The compound represented by the general formula (N-3) is preferably a compound selected from the group of compounds represented by the general formulae (N-3-1) and (N-3-2).

[ solution 63]

(in the formula, R^N31And R^N32Each independently represents R in the general formula (N-3)^N31And R^N32The same meaning is used. )

The third component preferably contains 1 or 2 or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a compound having a substantially neutral dielectric property (Δ ε has a value of-2 to 2).

[ solution 64]

(in the formula, R^L1And R^L2Each independently represents an alkyl group having 1 to 8 carbon atoms, 1 of the alkyl groups being non-adjacent 2 or more-CH₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

n^L1represents 0, 1,2 or 3,

A^L1、A^L2and A^L3Each independently represents a group selected from the group consisting of,

(a12)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-. )

(b12)1, 4-phenylene (1 CH-or nonadjacent 2 or more-CH-present in the radical may be substituted by-N) -) and

(c12) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or 2 or more-CH ═ which are not adjacent may be substituted by-N ═ can be used.)

The above-mentioned group (a12), group (b12) and group (c12) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^L1and Z^L2Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,

n^L1is 2 or 3 or A^L2When plural, they may be the same or different, and n^L1Is 2 or 3 and thus Z^L2When a plurality of them are present, they may be the same or different, but the compounds represented by the general formula (N-1), the general formula (N-2) and the general formula (N-3) are not included. )

The compounds represented by the general formula (L) may be used alone or in combination. The type of the combinable compound is not particularly limited, and it is suitably used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The kind of the compound used is, for example, 1 as one embodiment of the present invention. Or 2,3,4, 5, 6, 7, 8, 9, 10 or more in other embodiments of the invention.

In the composition of the present invention, the content of the compound represented by the general formula (L) is desirably adjusted depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.

The lower limit of the preferred content of the compound represented by formula (L) is 0%, 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the composition of the present invention. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the lower limit value is preferably high and the upper limit value is preferably high. Further, when T of the composition of the present invention is used_niWhen a composition having high temperature stability is required while keeping the composition high, the lower limit value is preferably high and the upper limit value is preferably high. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to lower the lower limit and lower the upper limit.

When importance is attached to reliability, R is preferably selected^L1And R^L2All of them are alkyl groups, and when importance is attached to reduction in volatility of the compound, alkoxy groups are preferable, and when importance is attached to reduction in viscosity, at least one of them is preferably alkenyl groups.

With respect to R^L1And R^L2When the ring structure to which it is attached is phenyl (aromatic)In the case where the ring structure to which the alkyl group is bonded is a saturated ring structure such as cyclohexane, pyran, dioxane, or the like, the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkenyl group having 2 to 5 carbon atoms are preferably linear. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, and is preferably linear.

[ solution 65]

Wherein, by reacting R^L1And R^L2The compound represented by the general formula (i) in combination with at least 1 or more of the compounds representing an alkenyl group can significantly suppress a decrease in the Voltage Holding Ratio (VHR).

With respect to n^L1When importance is attached to the response speed, 0 is preferable, 2 or 3 is preferable for improving the upper limit temperature of the nematic phase, and 1 is preferable for achieving the balance therebetween. In addition, in order to satisfy the characteristics required as a composition, it is preferable to combine compounds of different values.

With respect to A^L1、A^L2And A^L3When it is desired to increase Δ n, it is preferably aromatic, and it is preferably aliphatic for improving the response speed, and each independently preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] n]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably having the following structure,

[ solution 66]

More preferably, it represents trans-1, 4-cyclohexylene or 1, 4-phenylene.

When importance is attached to the response speed, Z^L1And Z^L2Preferably a single bond.

In the compound represented by the general formula (L), the number of halogen atoms in the molecule is preferably 0 or 1.

The compound represented by the general formula (L) is preferably a compound selected from the compounds represented by the general formula (L-1).

[ solution 67]

(in the formula, R^L1And R^L2Each independently represents R in the general formula (L)^L1And R^L2The same meaning is used. )

R^L1And R^L2Preferably, the alkyl group has a straight chain of 1 to 5 carbon atoms, the alkoxy group has a straight chain of 1 to 4 carbon atoms, and the alkenyl group has a straight chain of 2 to 5 carbon atoms. The compound represented by the general formula (L-1) may be used alone, or 2 or more compounds may be used in combination. The type of the combinable compound is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The types of the compounds used are, for example, 1,2,3,4, 5 or more as one embodiment of the present invention.

The lower limit of the preferred amounts is 1%, 2%, 3%, 5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% relative to the total amount of the composition of the invention. The upper limit of the preferred amounts is 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25% relative to the total amount of the composition of the invention.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the lower limit value is preferably high and the upper limit value is preferably high. Further, when the book is putT of the inventive composition_niWhen a composition having a high holding rate and good temperature stability is required, the lower limit value is preferably medium and the upper limit value is preferably medium. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, the lower limit value and the upper limit value are preferably low.

The compound represented by the general formula (L-1) is preferably a compound represented by the general formula (L-1-1).

[ solution 68]

(in the formula, R^L11Represents a hydrogen atom or a methyl group, R^L2Represents R in the general formula (L)^L2The same meaning is used. )

The compound represented by the general formula (L-1-1) is preferably a compound selected from the group consisting of the compounds represented by the formulae (L-1-1.11) to (L-1-1.13), preferably a compound represented by the formula (L-1-1.12) or (L-1-1.13), and particularly preferably a compound represented by the formula (L-1-1.13).

[ solution 69]

Further, the compound represented by the general formula (L-1-1) is preferably a compound selected from the group consisting of the compounds represented by the formulae (L-1-1.21) to (L-1-1.24), and is preferably a compound represented by the formulae (L-1-1.22) to (L-1-1.24). In particular, the compounds represented by the formula (L-1-1.22) are preferable because they particularly improve the response speed of the composition of the present invention. In addition, a high T is more required than a response speed_niIn this case, it is preferable to use a compound represented by the formula (L-1-1.23) or the formula (L-1-1.24).

[ solution 70]

Further, the compound represented by the general formula (L-1-1) is preferably a compound selected from the group consisting of the compounds represented by the formulae (L-1-1.31) and (L-1-1.41).

[ solution 71]

The compound represented by the general formula (L-1) is preferably a compound represented by the general formula (L-1-2).

[ chemical formula 72]

(in the formula, R^L121And R^L122Each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. )

The compound represented by the general formula (L-1-2) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-1-2.1) to (L-1-2.12), and is preferably a compound represented by the formula (L-1-2.1), the formula (L-1-2.3) or the formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.1) is preferable because it improves the response speed of the composition of the present invention. In addition, a high T is more required than a response speed_niIn this case, it is preferable to use compounds represented by the formula (L-1-2.3), the formula (L-1-2.4), the formula (L-1-2.11) and the formula (L-1-2.12). In order to improve the solubility at low temperatures, the total content of the compounds represented by the formulae (L-1-2.3), (L-1-2.4), (L-1-2.11) and (L-1-2.12) is not preferably 20% or more.

[ solution 73]

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formulae (L-1-3) and/or (L-1-4).

[ chemical formula 74]

(in the formula, R^L2Is shown andr in the formula (L)^L2The same meaning is used. )

The compound represented by the general formula (L) is preferably a compound represented by the following general formula (L-2) to general formula (L-11). In the composition of the present invention, the compound represented by the general formula (L) preferably contains 1 or 2 or more compounds represented by the general formulae (L-2) to (L-11).

[ solution 75]

(in the formula, R^L31Represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R^L32Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. )

The compound represented by the general formula (L) is preferably a compound selected from the group consisting of the general formula (L-4), the general formula (L-6), the general formula (L-7) and the general formula (L-8), more preferably a compound selected from the group consisting of the general formula (L-7) and the general formula (L-8), and still more preferably a compound selected from the group consisting of the general formula (L-6) and the general formula (L-8). More specifically, when a large Δ n is required, it is preferably a compound selected from the group consisting of the compounds represented by the general formula (L-6), the general formula (L-8) and the general formula (L-11).

In the compounds represented by the general formulae (L-4), (L-7) and (L-8), R is^L31Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R^L32Preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R^L31More preferably an alkenyl group having 2 to 5 carbon atoms, still more preferably an alkenyl group having 2 or 3 carbon atoms, and R in the compound represented by the general formula (L-6)^L31And R^L32Each independently is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

The compound represented by the general formula (L) preferably contains 1 or 2 or more compounds represented by the general formula (L-12), the general formula (L-13) or the general formula (L-14).

[ 76]

(in the formula, R^L51And R^L52Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, X^L51And X^L52Each independently represents a fluorine atom or a hydrogen atom, X^L51And X^L52One of them is a fluorine atom and the other is a hydrogen atom. )

The compound represented by the general formula (L) may contain 1 or 2 or more compounds represented by the general formulae (L-16.1) to (L-16.3).

[ solution 77]

The compound represented by the general formula (L) may contain 1 or 2 or more compounds represented by the general formula (N-001).

[ solution 78]

(in the formula, R^N1And R^N2Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, L¹And L²Each independently represents a hydrogen atom, a fluorine atom, CH₃Or CF₃. Wherein L is not included¹And L²Both represent the case of fluorine atoms. )

R^N1And R^N2Preferably represents an alkyl group having 1 to 5 carbon atoms.

The fourth component preferably contains 1 or 2 or more compounds represented by the general formula (J). These compounds correspond to compounds with positive dielectricity (Δ ∈ is positive in sign and its absolute value is greater than 2.).

[ solution 79]

(in the formula, R^J1Represents an alkyl group having 1 to 8 carbon atoms, 1 or non-adjacent 2 or more-CH groups in the alkyl group₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

n^J1represents 0, 1,2,3 or 4,

A^J1、A^J2and A^J3Each independently represents a group selected from the group consisting of,

(a13)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-. )

(b13)1, 4-phenylene (1 CH-or nonadjacent 2 or more-CH-present in the radical may be substituted by-N) -) and

(c13) naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl (1-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or 2 or more-CH ═ which are not adjacent may be substituted by-N ═ can be used.)

The above-mentioned group (a13), group (b13) and group (c13) may each independently be substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,

Z^J1and Z^J2Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-, -COO-, -OCO-or-C ≡ C-,

n^J1is 2,3 or 4 and A^J2When plural, they may be the same or different, and n^J1Is 2,3 or 4 and thus Z^J1When a plurality of them exist, they may be the same or different,

X^J1represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2, 2-trifluoroethyl group. )

In the general formula (J), R^J1The alkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms or the alkenyloxy group having 2 to 8 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms or the alkenyloxy group having 2 to 5 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is more preferable, the alkyl group having 2 to 5 carbon atoms or the alkenyl group having 2 to 3 carbon atoms is further preferable, and the alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

When reliability is important, R^J1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.

The alkenyl group is preferably selected from groups represented by any one of the formulae (R1) to (R5). (Black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

[ solution 80]

A^J1、A^J2And A^J3Each independently is preferably aromatic when an increase in Δ n is required, is preferably aliphatic for improving the response speed, and preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, which may be substituted with a fluorine atom, more preferably represents the following structure,

[ solution 81]

More preferably, the following structure is shown.

[ solution 82]

Z^J1And Z^J2Each independently preferably represents-CH₂O-、-OCH₂-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-or a single bond, further preferably-OCH₂-、-CF₂O-、-CH₂CH₂-or a single bond, particularly preferably-OCH₂-、-CF₂O-or a single bond.

X^J1Preferably a fluorine atom or a trifluoromethoxy group, preferably a fluorine atom.

n^J1Preferably 0, 1,2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasis is placed on improvement of Δ ∈ and preferably 1 or 2 when Tni is emphasized.

The kind of the combinable compound is not particularly limited, and it is used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. The types of the compounds used are, for example, 1,2, and 3 as one embodiment of the present invention. In other embodiments of the present invention, the number of the cells is 4, 5, 6, 7 or more.

In the composition of the present invention, the content of the compound represented by the general formula (J) is desirably adjusted depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.

The lower limit of the preferable content of the compound represented by the general formula (J) is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the composition of the present invention. The upper limit of the preferred content relative to the total amount of the composition of the present invention is, for example, 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25% in one embodiment of the present invention.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when the Tni of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. In addition, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the lower limit value and increase the upper limit value.

The compound represented by the general formula (J) is preferably a compound represented by the general formula (M) or a compound represented by the general formula (K).

The composition of the present invention preferably contains 1 or 2 or more compounds represented by the general formula (M). These compounds correspond to compounds with positive dielectricity (Δ ∈ is positive in sign and its absolute value is greater than 2.).

[ solution 83]

(in the formula, R^M1Represents an alkyl group having 1 to 8 carbon atoms, 1 or non-adjacent 2 or more-CH groups in the alkyl group₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

n^M1represents 0, 1,2,3 or 4,

A^M1and A^M2Each independently represents a group selected from the group consisting of,

(a14)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-or-S-. ) And

(b14)1, 4-phenylene (1 CH or not adjacent thereto but more than 2-CH which may be substituted by-N.)

The hydrogen atoms on the above-mentioned group (a14) and group (b14) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^M1and Z^M2Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-, -COO-, -OCO-or-C ≡ C-,

n^M1is 2,3 or 4 and A^M2When plural, they may be the same or different, and n^M1Is 2,3 or 4 and thus Z^M1When a plurality of them exist, they may be the same or different,

X^M1and X^M3Each independently represents a hydrogen atom, a chlorine atom or a fluorine atom,

X^M2represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2, 2-trifluoroethyl group. )

In the general formula (M), R^M1The alkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms or the alkenyloxy group having 2 to 8 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms or the alkenyloxy group having 2 to 5 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is more preferable, the alkyl group having 2 to 5 carbon atoms or the alkenyl group having 2 to 3 carbon atoms is further preferable, and the alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

When reliability is important, R^M1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.

[ solution 84]

A^M1And A^M2Each independently is preferably aromatic when an increase in Δ n is required, is preferably aliphatic for improving the response speed, and preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably having the following structure,

[ solution 85]

More preferably, the following structure is shown.

[ solution 86]

Z^M1And Z^M2Each independently preferably represents-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-or a single bond, further preferably-CF₂O-、-CH₂CH₂-or a single bond, particularly preferably-CF₂O-or a single bond.

n^M1Preferably 0, 1,2 or 3, preferably 0, 1 or 2, and when emphasis is placed on improvement of Δ ∈, preferably 0 or1, when Tni is regarded as important, 1 or 2 is preferable.

In the composition of the present invention, the content of the compound represented by the general formula (M) is desirably adjusted depending on the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.

The lower limit of the preferred content of the compound represented by formula (M) is 0%, 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the composition of the present invention. The upper limit of the preferred content relative to the total amount of the composition of the present invention is, for example, 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25% in one embodiment of the present invention.

The compound represented by the general formula (M) is preferably represented by the following general formula (M-1) or general formula (M-2).

[ solution 87]

(in the formula, R³¹Represents an alkyl group having 1 to 5 carbon atoms, a carbon atomAlkenyl group having 2 to 5 sub-atoms or alkoxy group having 1 to 4 carbon atoms, X³¹And X³²Each independently represents a hydrogen atom or a fluorine atom, Y³¹Represents a fluorine atom or OCF₃，M³¹～M³³Each independently represents trans-1, 4-cyclohexylene or 1, 4-phenylene, 1 or 2-CH groups in the trans-1, 4-cyclohexylene₂May be substituted by-O-in such a way that oxygen atoms are not directly adjacent, 1 or 2 hydrogen atoms in the phenylene radical may be substituted by fluorine atoms, n³¹And n³²Each independently represents 0, 1 or 2, n⁴¹+n⁴²Represents 1,2 or 3. )

Specifically, the compounds represented by the general formula (M-1) are preferably compounds represented by the following general formulae (M-1-a) to (M-1-f).

[ solution 88]

(in the formula, R³¹、X³¹、X³²And Y³¹Represents R in the general formula (M)³¹、X³¹、X³²And Y³¹Same meaning as X³⁴～X³⁹Each independently represents a hydrogen atom or a fluorine atom. )

Specifically, the compounds represented by the general formula (M-2) are preferably compounds represented by the following general formulae (M-2-a) to (M-2-n).

[ solution 89]

[ solution 90]

(in the formula, R³¹、X³¹、X³²And Y³¹Represents R in the general formula (M)³¹、X³¹、X³²And Y³¹Same meaning as X³⁴～X³⁹Each independentlyRepresents a hydrogen atom or a fluorine atom. )

The compounds represented by the general formula (M) are preferably represented by the following general formulae (M-3) to (M-26).

[ solution 91]

[ solution 92]

The composition of the present invention preferably contains 1 or 2 or more compounds represented by the general formula (K). These compounds correspond to compounds with positive dielectricity (Δ ∈ is positive in sign and its absolute value is greater than 2.).

[ solution 93]

(in the formula, R^K1Represents an alkyl group having 1 to 8 carbon atoms, 1 or non-adjacent 2 or more-CH groups in the alkyl group₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,

n^K1represents 0, 1,2,3 or 4,

A^K1and A^K2Each independently represents a group selected from the group consisting of,

(a15)1, 4-cyclohexylene radical (1 CH present in this radical)₂-or 2 or more-CH not adjacent₂-may be substituted by-O-or-S-. ) And

(b15)1, 4-phenylene (1 CH or not adjacent thereto but more than 2-CH which may be substituted by-N.)

The hydrogen atoms on the above-mentioned group (a15) and group (b15) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,

Z^K1and Z^K2Each independently represents a single bond, -CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-, -COO-, -OCO-or-C ≡ C-,

n^K1is 2,3 or 4 and A^K2When plural, they may be the same or different, and n^K1Is 2,3 or 4 and thus Z^K1When a plurality of them exist, they may be the same or different,

X^K1and X^K3Each independently represents a hydrogen atom, a chlorine atom or a fluorine atom,

X^K2represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2, 2-trifluoroethyl group. )

In the general formula (K), R^K1The alkyl group having 1 to 8 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms or the alkenyloxy group having 2 to 8 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the alkenyl group having 2 to 5 carbon atoms or the alkenyloxy group having 2 to 5 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is more preferable, the alkyl group having 2 to 5 carbon atoms or the alkenyl group having 2 to 3 carbon atoms is further preferable, and the alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

When reliability is important, R^K1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.

[ solution 94]

A^K1And A^K2Each independently is preferably aromatic when an increase in Δ n is required, is preferably aliphatic for improving the response speed, and preferably represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, more preferably having the following structure,

[ solution 95]

More preferably, the following structure is shown.

[ solution 96]

Z^K1And Z^K2Each independently preferably represents-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-or a single bond, further preferably-CF₂O-、-CH₂CH₂-or a single bond, particularly preferably-CF₂O-or a single bond.

n^K1Preferably 0, 1,2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasis is placed on improvement of Δ ∈ and preferably 1 or 2 when Tni is emphasized.

In the composition of the present invention, the content of the compound represented by the general formula (K) needs to be appropriately adjusted depending on the required performances such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, dropping marks, burn-in, dielectric anisotropy, and the like.

The lower limit of the preferred content of the compound represented by formula (K) is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the composition of the present invention. The upper limit of the preferred content relative to the total amount of the composition of the present invention is, for example, 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25% in one embodiment of the present invention.

The compound represented by the general formula (K) is preferably represented by the following general formula (K-1) or general formula (K-2).

[ solution 97]

(in the formula, R⁴¹Represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, X⁴¹And X⁴²Each independently represents a hydrogen atom or a fluorine atom, Y⁴¹Represents a fluorine atom or OCF₃，M⁴¹～M⁴²、M³³Each independently represents trans-1, 4-cyclohexylene or 1, 4-phenylene, 1 or 2-CH groups in the trans-1, 4-cyclohexylene₂May be substituted by-O-in such a way that oxygen atoms are not directly adjacent, 1 or 2 hydrogen atoms in the phenylene radical may be substituted by fluorine atoms, n⁴¹And n⁴²Each independently represents 0, 1 or 2, n⁴¹+n⁴²Represents 1,2 or 3. )

Specifically, the compounds represented by the general formula (K-1) are preferably compounds represented by the following general formulae (K-1-a) to (K-1-d).

[ solution 98]

(in the formula, R⁴¹、X⁴¹、X⁴²And Y⁴¹R in the general formula (K)⁴¹、X⁴¹、X⁴²And Y⁴¹Same meaning as X⁴⁴～X⁴⁹Each independently represents a hydrogen atom or a fluorine atom. )

Specifically, the compounds represented by the general formula (K-2) are preferably compounds represented by the following general formulae (K-2-a) to (K-2-g).

[ solution 99]

The compound represented by the general formula (K) is preferably represented by the following general formulae (K-3) to (K-5).

[ solution 100]

In the case where the dielectric anisotropy (. DELTA.. di-elect cons.) at 25 ℃ of the composition of the present invention has a positive value, the dielectric anisotropy (. DELTA.. di-elect cons.) at 25 ℃ of the composition of the present invention is 1.5 to 20.0, preferably 1.5 to 18.0, more preferably 1.5 to 15.0, further preferably 1.5 to 11, particularly preferably 1.5 to 8.

The composition having a positive value of dielectric anisotropy (. DELTA.. di-elect cons.) preferably contains a compound represented by the general formula (J) and a compound represented by the general formula (L). More specifically, the compound represented by the general formula (M) and the compound represented by the general formula (L-1) are preferably contained, and the compound represented by the general formula (M-1) and/or the general formula (M-2) and the compound represented by the general formula (L-1-1) are preferably contained.

In the composition of the present invention, the total content of the compound represented by the general formula (I), the compound represented by the general formula (J), and the compound represented by the general formula (L) is preferably 50% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more, preferably 97% or more, preferably 98% or more, preferably 99% or more, and preferably substantially no other compound, as the lower limit of the content in the composition. The upper limit is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and preferably substantially free of other compounds. The term "substantially" does not include compounds which are not intentionally contained, such as impurities which are inevitably produced during production.

In the composition of the present invention, the total content of the compound represented by the general formula (I), the compound represented by the general formula (M), and the compound represented by the general formula (L) is preferably 50% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more, preferably 97% or more, preferably 98% or more, preferably 99% or more, and preferably substantially no other compound, as the lower limit of the content in the composition. The upper limit is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and preferably substantially free of other compounds.

In the composition of the present invention, the total content of the compound represented by the general formula (I), the compound represented by the general formula (J), and the compound represented by the general formula (L-1) is preferably 5% or more, preferably 10% or more, preferably 13% or more, preferably 15% or more, preferably 18% or more, preferably 20% or more, preferably 23% or more, preferably 25% or more, preferably 28% or more, preferably 30% or more, preferably 33% or more, preferably 35% or more, preferably 38% or more, preferably 40% or more, as the lower limit of the content in the composition. The upper limit is preferably 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, preferably 83% or less, preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, preferably 40% or less.

In the case where the dielectric anisotropy (. DELTA.. di-elect cons.) at 25 ℃ of the composition of the present invention has a negative value, the dielectric anisotropy (. DELTA.. di-elect cons.) at 20 ℃ of the composition of the present invention is-2.0 to-8.0, preferably-2.0 to-6.0, more preferably-2.0 to-5.0, and particularly preferably-2.5 to-4.5.

The composition having a negative dielectric anisotropy (. DELTA.. di-elect cons.) preferably contains the compounds represented by the general formulae (N-1) to (N-3) and the compound represented by the general formula (L). More specifically, the compound represented by the general formula (N-1) and the compound represented by the general formula (L-1) are preferably contained, and the compound represented by the general formula (N-1) and the compound represented by the general formula (L-1-1) are preferably contained.

In the composition of the present invention, the total content of the compound represented by the general formula (I), the compounds represented by the general formulae (N-1) to (N-3), and the compound represented by the general formula (L) is preferably 50% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more, preferably 97% or more, preferably 98% or more, preferably 99% or more, and preferably substantially no other compound, as a lower limit in the composition. The upper limit is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and preferably substantially free of other compounds.

In the composition of the present invention, the total content of the compound represented by the general formula (I), the compound represented by the general formula (N-1) and the compound represented by the general formula (L) is preferably 50% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more, preferably 97% or more, preferably 98% or more, preferably 99% or more, and preferably substantially no other compound, as the lower limit of the content in the composition. The upper limit is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and preferably substantially free of other compounds.

The refractive index anisotropy (. DELTA.n) of the composition of the present invention at 25 ℃ is 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In more detail, it is preferably 0.10 to 0.13 when corresponding to a thin cell gap, and 0.08 to 0.10 when corresponding to a thick cell gap. In the present invention, Δ n is marked to be large when 0.09 or more.

The viscosity (η) of the composition of the invention at 25 ℃ is from 10 to 50 mPas, more preferably from 10 to 40 mPas, and particularly preferably from 10 to 35 mPas.

Rotational tack at 20 ℃ (γ) of the compositions of the invention₁) Is from 50 to 160 mPas, preferably from 55 to 160 mPas, preferably from 60 to 160 mPas, preferably from 80 to 130 mPas.

Nematic phase-isotropic liquid phase transition temperature (T) of the composition of the invention_NI) From 60 ℃ to 120 ℃, more preferably from 70 ℃ to 100 ℃, and particularly preferably from 70 ℃ to 85 ℃. In the present invention, the symbol T denotes a temperature of 60 ℃ or higher_NIHigh. In the case of liquid crystal television applications, T_NIPreferably 70 ℃ to 80 ℃, in the case of mobile phone applications, T_NIPreferably 80 ℃ to 90 ℃, T in the case of outdoor Display applications such as PID (Public Information Display)_NIPreferably from 90 ℃ to 110 ℃.

The composition of the present invention may contain, in addition to the above-mentioned compounds, a conventional nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, infrared absorber, polymerizable monomer, or light stabilizer (HALS) other than the compound of the present invention.

For example, the composition of the present invention may contain, as a typical nematic liquid crystal or smectic liquid crystal, a compound having a dielectric anisotropy (Δ ∈) at 25 ℃ of from +2.0 to +50.0 in an amount of from 0% by mass to 50% by mass, preferably from 1% by mass to 30% by mass, preferably from 3% by mass to 30% by mass, and preferably from 5% by mass to 20% by mass.

A display device using a composition containing the compound of the present invention can be applied to liquid crystal display devices of various modes such as VA mode, PSVA mode, PSA mode, IPS mode, FFS mode, ECB mode, and the like.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "%" in the compositions containing the compounds of the following examples and comparative examples means "% by mass". The phase transition temperature was measured by using a polarizing microscope equipped with a temperature control stage and a Differential Scanning Calorimeter (DSC) in combination.

The following abbreviations are used below.

an amphos: di-tert-butyl (4-dimethylaminophenyl) phosphine

Bu: n-butyl

DMF: n, N-dimethylformamide

DMSO, DMSO: dimethyl sulfoxide

dppf: 1, 1' -bis (diphenylphosphino) ferrocene

Et: ethyl radical

Me: methyl radical

NMP: n-methyl-2-pyrrolidone

Pent: n-pentyl group

pin：-O-C(CH₃)₂-C(CH₃)₂-O-

Pr: n-propyl radical

Tf: trifluoromethanesulfonyl radical

THF: tetrahydrofuran (THF)

Example 1 Synthesis of Compound G-1-5

[ solution 101]

(Synthesis of Compound G-1-2)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a cooling tube, compound G-1-1(25.3G), 4-bromoresorcinol (25G), bis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride (0.49G) and THF (100mL) were charged under a nitrogen atmosphere, and the temperature was raised to 60 ℃. To the reaction mixture was added dropwise a 2M aqueous sodium carbonate solution (100 mL). After stirring at 60 ℃ for 3 hours, heating was stopped and the temperature of the solution was returned to room temperature. Then, 10% hydrochloric acid (100mL) was added. The organic layer was separated and the aqueous layer was further re-extracted with ethyl acetate (200 mL). The obtained organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and dried under vacuum to obtain compound G-1-2 (37.7G).

(Synthesis of Compound G-1-3)

Compound G-1-2(37.7G) and NMP (260mL) were charged and stirred in a reaction vessel equipped with a stirrer, a thermometer and a cooling tube under a nitrogen atmosphere. Potassium carbonate (28.5g) was added thereto, and the solution was heated to 180 ℃ over 1 hour and a half. After stirring at 180 ℃ for 22 hours, the mixture was cooled to room temperature, and 10% hydrochloric acid (160mL), water (80mL) and ethyl acetate (420mL) were added. The organic layer was separated, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, ethyl acetate (50mL) and hexane (150mL) were added, and the solution obtained by dissolution was passed through a column packed with silica gel (40g) and alumina (40g), and further passed through a mixed solvent of ethyl acetate (110mL) and hexane (330 mL). The obtained column-passing solution was concentrated and then dried in vacuo to obtain Compound G-1-3 (35G).

[ solution 102]

(Synthesis of Compound G-1-4)

Compound G-1-3(20G), pyridine (10.5G) and methylene chloride (72mL) were charged into a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel under a nitrogen atmosphere, stirred and cooled to 10 ℃. Then, trifluoromethanesulfonic anhydride (30.3g) was added dropwise at 0 ℃ over 30 minutes. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 25 ℃ and stirred for 1 hour. Then, 10% hydrochloric acid (100mL) was added dropwise at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with dichloromethane (200 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, methylene chloride (100mL) was added, and the solution obtained by dissolution was passed through a column packed with silica gel (25g) and alumina (25g), and further passed through methylene chloride (300 mL). The obtained column-passing solution was concentrated and then dried in vacuo to obtain Compound G-1-4 (14.5G).

(Synthesis of Compound G-1-5)

In a reaction vessel equipped with a stirrer and a thermometer, compound G-1-4(7.0G), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) (0.80G) and THF (56mL) were added under nitrogen atmosphere and stirred, followed by cooling to 0 ℃. A solution of methyl zinc chloride/THF (54mL) was added dropwise over 30 minutes at 0 deg.C. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 45 ℃ and stirred for 1 hour. Then, after cooling to 20 ℃ a saturated aqueous ammonium chloride solution (50mL) was added dropwise thereto at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated, and the aqueous layer was further extracted with ethyl acetate (100 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (70mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-5 (2.4G).

MS m/z：223[M⁺]

Example 2 Synthesis of Compound G-1-6

[ solution 103]

(Synthesis of Compound G-1-6)

In a reaction vessel equipped with a stirrer and a thermometer, compound G-1-4(5.0G), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) (0.57G) and THF (40ml) were charged under nitrogen atmosphere and cooled to 0 ℃. An ethyl zinc chloride/THF solution (39mL) was added dropwise over 30 minutes at 0 deg.C. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 45 ℃ and stirred for 1 hour. Then, after cooling to 20 ℃ a saturated aqueous ammonium chloride solution (50mL) was added dropwise thereto at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with ethyl acetate (120 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (70mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-6 (1.7G).

MS m/z：237[M⁺]

Example 3 Synthesis of Compound G-1-7

[ solution 104]

(Synthesis of Compound G-1-7)

Compound G-1-3(5G), potassium carbonate (6.1G), bromoethane (2.9G), and NMP (20mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere and stirred. The solution temperature was heated to 100 ℃ over 1 hour. After stirring at 100 ℃ for 8 hours, it was cooled to room temperature, 10% hydrochloric acid (25mL) was added and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with toluene (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (80mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-7 (2.1G).

MS m/z：253[M⁺]

Example 4 Synthesis of Compound G-1-8

[ solution 105]

(Synthesis of Compound G-1-8)

Compound G-1-3(5G), potassium carbonate (6.1G), bromopropane (3.2G), and NMP (20mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere and stirred. The solution temperature was heated to 100 ℃ over 1 hour. After stirring at 100 ℃ for 8 hours, it was cooled to room temperature, 10% hydrochloric acid (25mL) was added and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with toluene (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (80mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-8 (2.3G).

MS m/z：267[M⁺]

Example 5 Synthesis of Compound G-1-9

[ solution 106]

(Synthesis of Compound G-1-9)

Compound G-1-3(5G), potassium carbonate (6.1G), bromopentane (4.0G), and NMP (20mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere and stirred. The solution temperature was heated to 100 ℃ over 1 hour. After stirring at 100 ℃ for 8 hours, the mixture was cooled to room temperature, 10% hydrochloric acid (25mL) was added, and toluene (50mL) was further added. The organic layer was separated and the aqueous layer was further extracted with toluene (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (80mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-9 (1.9G).

MS m/z：295[M⁺]

Example 6 Synthesis of Compound G-1-10

[ solution 107]

(Synthesis of Compound G-1-10)

Compound G-1-3(4G), potassium carbonate (4.9G), methyl iodide (2.8G), and NMP (32mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere and stirred. The solution temperature was heated to 50 ℃ over 1 hour. After stirring at 50 ℃ for 3 hours, the mixture was cooled to room temperature, 10% hydrochloric acid (25mL) was added, and toluene (50mL) was further added. The organic layer was separated, and the aqueous layer was further extracted with toluene (50 ml). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (80mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-10 (2.0G).

MS m/z：239[M⁺]

Example 7 Synthesis of Compound G-1-15

[ solution 108]

(Synthesis of Compound G-1-12)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a cooling tube, compound G-1-11(7.69G), 4-bromoresorcinol (5G), bis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride (0.09G) and THF (40mL) were charged under a nitrogen atmosphere, and the temperature was raised to 60 ℃. To the reaction mixture was added dropwise a 2M aqueous sodium carbonate solution (13 mL). After stirring at 60 ℃ for 2 hours, heating was stopped and the temperature of the solution was returned to room temperature. Then, 10% hydrochloric acid (15mL) was added. The organic layer was separated and the aqueous layer was further re-extracted with ethyl acetate (100 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, ethyl acetate (10mL) and hexane (90mL) were added, the solution obtained by dissolution was passed through a column packed with silica gel (10g) and alumina (10g), and further passed through a mixed solvent of ethyl acetate (20mL) and hexane (180 mL). The obtained column-passing solution was concentrated and then dried in vacuo to obtain Compound G-1-12 (7.2G).

(Synthesis of Compound G-1-13)

Compound G-1-12(7.2G), potassium carbonate (6.1G), and NMP (56mL) were charged and stirred in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube under a nitrogen atmosphere. The solution temperature was heated to 160 ℃ over 1 hour. After stirring at 160 ℃ for 12 hours, the mixture was cooled to room temperature, 10% hydrochloric acid (20mL) and toluene (100mL) were added to the mixture, and the organic layer was separated and the aqueous layer was extracted with toluene (100 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, methylene chloride (100mL) was added, and the solution obtained by dissolution was passed through a column packed with silica gel (10g) and alumina (10g), and further passed through methylene chloride (200 mL). The obtained column-passing solution was concentrated and then dried in vacuo to obtain Compound G-1-13 (6.5G).

[ solution 109]

(Synthesis of Compound G-1-14)

Compound G-1-13(4G), pyridine (1.54G), and methylene chloride (32mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel under a nitrogen atmosphere, stirred, and cooled to 10 ℃. Then, trifluoromethanesulfonic anhydride (4.4g) was added dropwise at 0 ℃ over 30 minutes. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 25 ℃ and stirred for 1 hour. Then, 10% hydrochloric acid (50mL) was added dropwise at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with dichloromethane (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After the obtained solution was concentrated, methylene chloride (50mL) was added to the concentrated solution, and the dissolved solution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-14 (4.8G).

(Synthesis of Compound G-1-15)

In a reaction vessel equipped with a stirrer and a thermometer, compounds G-1 to 14(4.8G), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) (0.44G) and THF (40mL) were added under nitrogen atmosphere and stirred, followed by cooling to 0 ℃. A solution of butylzinc chloride in THF (30mL) was added dropwise at 0 ℃ over 30 minutes. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 45 ℃ and stirred for 1 hour. Then, after cooling to 20 ℃ a saturated aqueous ammonium chloride solution (50mL) was added dropwise thereto at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated, and the aqueous layer was further extracted with ethyl acetate (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (70mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-15 (2.4G).

MS m/z：347[M⁺]

Example 8 Synthesis of Compound G-1-16

[ solution 110]

(Synthesis of Compound G-1-16)

Compound G-1-13(2.5G), potassium carbonate (1.68G), bromobutane (1.3G) and NMP (20mL) were charged into a reaction vessel equipped with a stirrer, a thermometer and a cooling tube under a nitrogen atmosphere and stirred. The solution temperature was heated to 100 ℃ over 1 hour. After stirring at 100 ℃ for 8 hours, the mixture was cooled to room temperature, 10% hydrochloric acid (25mL) was added, and toluene (50mL) was further added. The organic layer was separated and the aqueous layer was further extracted with toluene (50 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (80mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-16 (1.2G).

MS m/z：363[M⁺]

Example 9 Synthesis of Compound G-1-20

[ solution 111]

(Synthesis of Compound G-1-18)

Compound G-1-17(20G), pyridine (9.9G), and methylene chloride (160mL) were charged into a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel under a nitrogen atmosphere, stirred, and cooled to 10 ℃. Then, trifluoromethanesulfonic anhydride (28.2g) was added dropwise at 0 ℃ over 30 minutes. After stirring at 0 ℃ for 30 minutes, the temperature was raised to 25 ℃ and stirred for 1 hour. Then, 10% hydrochloric acid (100mL) was added dropwise at 20 ℃ to 30 ℃ and stirred for 30 minutes. The organic layer was separated and the aqueous layer was further extracted with dichloromethane (200 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After the obtained solution was concentrated, methylene chloride (200mL) was added to the concentrated solution, and the dissolved solution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-18 (37.2G).

(Synthesis of Compound G-1-19)

In a reaction vessel equipped with a stirring device and a thermometer, compounds G-1 to 18(20G), bis (pinacolato) diboron (15.6G), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) (1.4G), potassium acetate (16.4G), and DMSO (160mL) were added under nitrogen atmosphere and stirred, and the temperature of the solution was heated to 80 ℃ over 1 hour. After stirring at 80 ℃ for 24 hours, the mixture was cooled to room temperature, water (100mL) and toluene (200mL) were added to the mixture, the organic layer was separated, and the aqueous layer was extracted with toluene (200 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, hexane (200mL) was added, and the solution obtained by dissolution was passed through a column packed with silica gel (10g) and alumina (10g), and further passed through hexane (300 mL). The obtained column-passed solution was concentrated to dryness to obtain Compound G-1-19 (14.0G).

[ solution 112]

(Synthesis of Compound G-1-20)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a cooling tube, compound G-1-4(10G), compound G-1-19(10.8G), bis [ di-tert-butyl (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride (0.4G) and THF (40mL) were charged under a nitrogen atmosphere, and the temperature was raised to 60 ℃. To the reaction mixture was added dropwise a 2M aqueous sodium carbonate solution (28 mL). After stirring at 60 ℃ for 3 hours, heating was stopped and the temperature of the solution was returned to room temperature. Then, 10% hydrochloric acid (100mL) was added. The organic layer was separated and the aqueous layer was further re-extracted with toluene (300 mL). The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The resulting solution was concentrated, toluene (100mL) was added thereto, the solution obtained by dissolution was passed through a silica gel column, and the obtained column-passed solution was concentrated and dried to obtain compound G-1-20 (5.1G).

MS m/z：431[M⁺]

(measurement of refractive index anisotropy (. DELTA.n))

A mother liquid crystal (LC-1) having the following composition was prepared. The mother liquid crystal (LC-1) showed the following physical property values, which were all measured values.

T_n-i(nematic-isotropic liquid phase transition temperature): 72 deg.C

Δ ε (dielectric anisotropy at 25 ℃): -3.30

Δ n (refractive index anisotropy at 25 ℃): 0.086

[ solution 113]

A liquid crystal composition comprising 90% of the mother liquid crystal (LC-1) and 10% of the compound obtained in examples and comparative examples was prepared. The Δ n value at 25 ℃ of the composition was measured, and the Δ n of the compounds obtained in examples and comparative examples was determined based on the amount of change in the matrix liquid crystal (LC-1). The results are shown in Table 1. As comparative example 1, the following compound was used.

[ chemical formula 114]

[ Table 1]

Compound (I)	Δn
		Example 1	0.169
Example 2	0.168
		Example 3	0.177
Example 6	0.178
		Comparative example 1	0.159

Claims

1. A compound represented by the general formula (I),

[ solution 1]

In the formula, Rⁱ¹And Rⁱ²Each independently represents a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -BR¹R²An alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, formula-BR¹R²In, R¹And R²Each independently represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or R¹And R²Are linked to each other to form a cyclic structure, and represent-O- (CR)³R⁴)_n-O-, of the formula-O- (CR)³R⁴)_nin-O-, R³And R⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 2 or 3, and a plurality of CR's are present³R⁴May be the same or different; 1-CH present in the alkyl group having 1 to 15 carbon atoms or the alkenyl group having 2 to 15 carbon atoms₂-or 2 or more-CH not adjacent₂Each independently may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -SOO-O-or-C.ident.C-, and further, a hydrogen atom present in the alkyl group of carbon atoms 1 to 15 or the alkenyl group of carbon atoms 2 to 15 may be substituted by a fluorine atom,

(a)1, 4-cyclohexylene radical, 1 CH present in this radical₂-or 2 or more-CH not adjacent₂-may be substituted by-O-or-S-;

(b)1, 4-phenylene in which 1 CH ═ or nonadjacent 2 or more-CH ═ can be substituted by-N ═ and hydrogen atoms present in the group can be substituted by halogen atoms;

(c)1, 4-cyclohexenylene, naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl or decahydronaphthalene-2, 6-diyl, wherein hydrogen atoms present in these groups may be substituted by halogen atoms, and further, 1-CH ═ or not adjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by — N ═ may be substituted; and

(d) dibenzofuran-3, 7-diyl, dibenzothiophene-3, 7-diyl or fluorene-2, 7-diyl,

Yⁱ¹represents-O-, -S-, -SO-, -SOO-, -CF₂-, -CO-or-CH₂-，

Yⁱ²represents-O-, -S-, -SO-, -SOO-, -CF₂-、-CO-、-CH₂-or a single bond,

wherein the following compounds are excluded:

nⁱ¹、mⁱ¹and lⁱ¹Represents 0, Yⁱ¹represents-CH₂-，Yⁱ²Represents a single bond and Rⁱ¹And Rⁱ²At least one of them represents a C1-15 alkyl group;

nⁱ¹represents 1, mⁱ¹And lⁱ¹Represents 0, Yⁱ¹represents-O-, Yⁱ²Represents a single bond, Aⁱ¹Represents 2-O-substituted 1, 4-cyclohexylene or 1, 4-phenylene, Zⁱ¹Represents a single bond and Rⁱ¹A compound which represents an alkyl group having 1 to 15 carbon atoms; and

nⁱ¹represents 1, mⁱ¹And lⁱ¹Represents 0, Yⁱ¹represents-CH₂-，Yⁱ²Represents a single bond, Aⁱ¹Represents 1, 4-cyclohexylene or 1, 4-phenylene substituted by a fluorine atom, Zⁱ¹represents-CH₂CH₂-, -C.ident.C-or a single bond and Rⁱ¹A compound which represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms.

2. A compound according to claim 1, formula (I), wherein Rⁱ¹And Rⁱ²Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

3. The compound according to claim 1 or 2, wherein in the formula (I), lⁱ¹Represents 0 and Yⁱ²Represents a single bond.

4. A compound according to claim 1 or 2, formula (I) wherein Y isⁱ¹represents-O-or-S-.

5. The compound according to claim 1 or 2, wherein in formula (I), nⁱ¹And mⁱ¹Both represent 0.

6. A composition comprising 1 or 2 or more compounds according to any one of claims 1 to 5.

7. The composition of claim 6, exhibiting a liquid crystalline phase.

8. A liquid crystal display element using the composition according to claim 6 or 7.