CN111187628A - Liquid crystal compound, composition and liquid crystal display element - Google Patents
Liquid crystal compound, composition and liquid crystal display element Download PDFInfo
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- CN111187628A CN111187628A CN201911059918.2A CN201911059918A CN111187628A CN 111187628 A CN111187628 A CN 111187628A CN 201911059918 A CN201911059918 A CN 201911059918A CN 111187628 A CN111187628 A CN 111187628A
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
- C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
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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
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 Tni,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 Tni,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,
Rim1and Rim2Each independently represents a hydrogen atom, a methyl, ethyl or propyl group, or Rim1And Rim2Are linked to each other to form a cyclic structure represented by-CH2-CH2-、-CH2-CH2-CH2-, or-CH2-C(CH3)2-CH2-,
Xim1Represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,
Xim2represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group,
Yim1represents-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]
(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,
Rim3and Rim4Each independently represents a hydrogen atom, a methyl, ethyl or propyl group, or Rim3And Rim4Are linked to each other to form a cyclic structure represented by-CH2-CH2-、-CH2-CH2-CH2-, or-CH2-C(CH3)2-CH2-,
Xim3Represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,
Xim4represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group,
Yim2represents-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]
(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,
Riaand RibEach 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). )
RicAnd RidEach 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-ZnXim5(in the formula, Xim5Represents a chlorine atom, a bromine atom or an iodine atom. ). )
For example, when R isiaAnd RibIs a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group, RicAnd Ridis-BR5R6or-ZnXim5In 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 RiaAnd RibIs hydroxy, RicAnd RidIn 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,
RN11、RN12、RN21、RN22、RN31and RN32Each 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-,
AN11、AN12、AN21、AN22、AN31and AN32Each 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,
ZN11、ZN12、ZN21、ZN22、ZN31and ZN32Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
XN21represents a hydrogen atom or a fluorine atom,
TN31represents-CH2-or an oxygen atom,
nN11、nN12、nN21、nN22、nN31and nN32Each independently represents an integer of 0 to 3, nN11+nN12、nN21+nN22And nN31+nN32Each independently is 1,2 or 3, AN11~AN32、ZN11~ZN32When 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), RN11、RN12、RN21、RN22、RN31And RN32Each 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 RN11And RN12The 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 RN21And RN22Wherein 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 usedN31And RN32The 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]
AN11、AN12、AN21、AN22、AN31And AN32Independently 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.
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Each 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.
XN21Preferably a fluorine atom.
TN31Preferably an oxygen atom.
nN11+nN12、nN21+nN22And nN31+nN32Preferably 1 or 2, preferably nN11Is 1 and nN12A combination of 0, nN11Is 2 and nN12A combination of 0, nN11Is 1 and nN12Is a combination of 1, nN11Is 2 and nN12Is a combination of 1, nN21Is 1 and nN22A combination of 0, nN21Is 2 and nN22A combination of 0, nN31Is 1 and nN32A combination of 0, nN31Is 2 and nN32Is 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 usedniWhen 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, RN11、RN12And ZN12Each independently represents R in the general formula (N-1)N11、RN12And ZN12The 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, RN11、RN12、Ai11And Zi1Each independently represents R in the general formula (i-1)N11、RN12、Ai11And Zi1The same meaning is used. )
[ solution 48]
(in the formula, RN11、RN12、Ai11、Ai12And Zi1Each independently represents R in the general formula (i-1)N11、RN12、Ai11、Ai12And Zi1The same meaning is used. )
[ solution 49]
(in the formula, mi13Represents 1, RN11、RN12、Ai11、Ai12、Ai13、Zi1、Zi2And mi11Each independently represents R in the general formula (i-1)N11、RN12、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, RN11And RN12Each independently represents R in the general formula (i-1)N11And RN12The 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]
(in the formula, RN11And RN12Each independently represents R in the general formula (i-1)N11And RN12The same meaning is used. )
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]
(in the formula, RN11And RN12Each independently represents R in the general formula (i-1)N11And RN12The same meaning is used. )
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, RN11And RN12Each independently represents R in the general formula (N-1)N11And RN12The 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, RN11、RN12、Aii1And mii1Represents R in the general formula (ii)N11、RN12、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, RN11、RN12And Aii1Represents R in the general formula (ii)N11、RN12And 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, RN11And RN12Represents R in the general formula (ii)N11And RN12The 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, RN11And RN12Represents R in the general formula (ii)N11And RN12The 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]
(in the formula, RN11And RN12Represents R in the general formula (ii)N11And RN12The same meaning is used. )
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, RN11、RN12、AN11、AN12And ZN11Each independently represents R in the general formula (N-1)N11、RN12、AN11、AN12And ZN11Same meaning as XLC3b1~XLC3b4Represents a hydrogen atom or a fluorine atom, XLC3b1And XLC3b2Or XLC3b3And XLC3b4Each represents a fluorine atom, mLC3b1Represents 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, RN11And RN12Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
RN11And RN12The 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]
(in the formula, RN11And RN12Each independently represents R in the general formula (N-1)N11And RN12The same meaning is used. )
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, RN21And RN22Each independently represents R in the general formula (N-2)N21And RN22The 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, RN31And RN32Each independently represents R in the general formula (N-3)N31And RN32The 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, RL1And RL2Each 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-,
nL1represents 0, 1,2 or 3,
AL1、AL2and AL3Each 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,
ZL1and ZL2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-N-CH-, -CH-, -CF-or-C ≡ C-,
nL1is 2 or 3 or AL2When plural, they may be the same or different, and nL1Is 2 or 3 and thus ZL2When 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 usedniWhen 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 selectedL1And RL2All 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 RL1And RL2When 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.
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 65]
Wherein, by reacting RL1And RL2The 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 nL1When 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 AL1、AL2And AL3When 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, ZL1And ZL2Preferably 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, RL1And RL2Each independently represents R in the general formula (L)L1And RL2The same meaning is used. )
RL1And RL2Preferably, 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 compositionniWhen 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, RL11Represents a hydrogen atom or a methyl group, RL2Represents 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 speedniIn 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, RL121And RL122Each 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 speedniIn 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, RL2Is 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, RL31Represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, RL32Represents 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 isL31Preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, RL32Preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, RL31More 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 RL32Each 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, RL51And RL52Each 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, XL51And XL52Each independently represents a fluorine atom or a hydrogen atom, XL51And XL52One 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, RN1And RN2Each 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. )
RN1And RN2Preferably 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, RJ1Represents 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-,
nJ1represents 0, 1,2,3 or 4,
AJ1、AJ2and AJ3Each 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,
ZJ1and ZJ2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-OCF2-、-CF2O-, -COO-, -OCO-or-C ≡ C-,
nJ1is 2,3 or 4 and AJ2When plural, they may be the same or different, and nJ1Is 2,3 or 4 and thus ZJ1When a plurality of them exist, they may be the same or different,
XJ1represents 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), RJ1The 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, RJ1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.
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 to which the alkenyl group is bonded.)
[ solution 80]
AJ1、AJ2And AJ3Each 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]
ZJ1And ZJ2Each 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.
XJ1Preferably a fluorine atom or a trifluoromethoxy group, preferably a fluorine atom.
nJ1Preferably 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.
When reliability is important, RJ1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.
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, RM1Represents 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-,
nM1represents 0, 1,2,3 or 4,
AM1and AM2Each 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,
ZM1and ZM2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-OCF2-、-CF2O-, -COO-, -OCO-or-C ≡ C-,
nM1is 2,3 or 4 and AM2When plural, they may be the same or different, and nM1Is 2,3 or 4 and thus ZM1When a plurality of them exist, they may be the same or different,
XM1and XM3Each independently represents a hydrogen atom, a chlorine atom or a fluorine atom,
XM2represents 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), RM1The 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, RM1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.
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 to which the alkenyl group is bonded.)
[ solution 84]
AM1And AM2Each 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]
ZM1And ZM2Each 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.
nM1Preferably 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.
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 (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.
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 (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]
(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. )
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, RK1Represents 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-,
nK1represents 0, 1,2,3 or 4,
AK1and AK2Each 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,
ZK1and ZK2Each independently represents a single bond, -CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-OCF2-、-CF2O-, -COO-, -OCO-or-C ≡ C-,
nK1is 2,3 or 4 and AK2When plural, they may be the same or different, and nK1Is 2,3 or 4 and thus ZK1When a plurality of them exist, they may be the same or different,
XK1and XK3Each independently represents a hydrogen atom, a chlorine atom or a fluorine atom,
XK2represents 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), RK1The 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, RK1The alkyl group is preferred, and the alkenyl group is preferred when importance is attached to the reduction of viscosity.
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 to which the alkenyl group is bonded.)
[ solution 94]
AK1And AK2Each 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]
ZK1And ZK2Each 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.
nK1Preferably 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 (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.
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 (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]
(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. )
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 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. )
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.
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.
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 inventionNI) 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 higherNIHigh. In the case of liquid crystal television applications, TNIPreferably 70 ℃ to 80 ℃, in the case of mobile phone applications, TNIPreferably 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.
Tn-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 (8)
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,
Ai1and Ai2Each independently represents a group selected from the group consisting of,
(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,
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 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.
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CN113913194A (en) * | 2021-10-22 | 2022-01-11 | 北京云基科技有限公司 | Fluorine-containing liquid crystal compound and application thereof |
WO2022228071A1 (en) * | 2021-04-27 | 2022-11-03 | 江苏和成显示科技有限公司 | Liquid crystal compound, liquid crystal composition thereof, and liquid crystal display device |
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WO2022228071A1 (en) * | 2021-04-27 | 2022-11-03 | 江苏和成显示科技有限公司 | Liquid crystal compound, liquid crystal composition thereof, and liquid crystal display device |
CN113913194A (en) * | 2021-10-22 | 2022-01-11 | 北京云基科技有限公司 | Fluorine-containing liquid crystal compound and application thereof |
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