WO2018225522A1 - 液晶化合物及びその組成物 - Google Patents

液晶化合物及びその組成物 Download PDF

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WO2018225522A1
WO2018225522A1 PCT/JP2018/019966 JP2018019966W WO2018225522A1 WO 2018225522 A1 WO2018225522 A1 WO 2018225522A1 JP 2018019966 W JP2018019966 W JP 2018019966W WO 2018225522 A1 WO2018225522 A1 WO 2018225522A1
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general formula
group
compound represented
same meaning
atom
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PCT/JP2018/019966
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French (fr)
Japanese (ja)
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宗矩 櫻井
健太 東條
豊 門本
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Dic株式会社
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Priority to CN201880021620.XA priority Critical patent/CN110461852B/zh
Priority to JP2019523444A priority patent/JP6635228B2/ja
Publication of WO2018225522A1 publication Critical patent/WO2018225522A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a compound having a condensed ring that is useful as an organic electronic material, medical pesticide, or a liquid crystal display element material, and a liquid crystal composition using these compounds.
  • Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, etc., including watches and calculators.
  • Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type.
  • There is a drive system such as.
  • the liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage.
  • the liquid crystal composition is selected from several to several tens of kinds of compounds in order to optimize the dielectric anisotropy ( ⁇ ) and the refractive index anisotropy ( ⁇ n) according to the individual display elements, It
  • the liquid crystal composition When the liquid crystal composition is used as a display element or the like, it is required to exhibit a stable nematic phase in a wide temperature range. In order to maintain a nematic phase in a wide temperature range, it is required that individual components constituting the liquid crystal composition have high miscibility with other components and have a high clearing point (T ni ). . Moreover, when using a liquid crystal composition as a display element etc., it is calculated
  • R 1 and R 2 each 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, Each independently represents 0 or 1)
  • the problem to be solved by the present invention is to provide a compound having a high T ni and having a large ⁇ , and a liquid crystal composition and a liquid crystal display device comprising the compound as a constituent member.
  • the present invention has the general formula (i)
  • X i1 and X i2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group
  • Y i1 and Y i2 each independently represent —O—, —S—, —SO—, —SOO—, —CF 2 —, —CO—, —CX i3 X i4 —, wherein Y i1 and Y any one or more of i2 represents —O—, —S—, —SO—, —SOO—;
  • X i3 and X i4 each independently represent the same meaning as X i1 , W i1
  • W i2 represents a single bond or —CL i9 L i10 —
  • L i1 , L i2 , L i3 , L i4 , L i5 , L i6 , L i7 , L i8 , L i9 and L i10 are each independently a hydrogen atom, bromine atom, iodine atom, hydroxyl group, carbon number 1 To 15 alkyl groups, alkenyl groups of 2 to 15 carbon atoms, or
  • R i1 represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or carbon. Represents an alkenyloxy group having 2 to 15 atoms
  • a i1 represents (a) a 1,4-cyclohexylene group (one —CH 2 — present in this group or two or more non-adjacent —CH 2 — represents —O— or —S—).
  • (B) 1,4-phenylene group (one —CH ⁇ present in this group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ , present in this group)
  • One hydrogen atom may be substituted with a fluorine atom.
  • a hydrogen atom present in these groups may be substituted with a fluorine atom, or present in a naphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group.
  • n i1 represents 1 or 2, but when n i1 represents 2 and a plurality of A i1 and Z i1 exist, they may be the same or different.
  • the compound represented by the general formula (i) provided by the present invention has a high clearing point (T ni ). Therefore, a stable nematic phase can be exhibited in a wide temperature range by using the compound represented by the general formula (i) as a component of the liquid crystal composition.
  • the compound represented by the general formula (i) provided by the present invention exhibits a large
  • X i1 and X i2 each independently preferably represent a fluorine atom, and in order to exhibit a more negative ⁇ , it is more preferable that both X i1 and X i2 represent a fluorine atom.
  • Y i1 and Y i2 each independently preferably represent an oxygen atom or a sulfur atom, and it is more preferable that both Y i1 and Y i2 represent an oxygen atom or a sulfur atom in order to exhibit a more negative ⁇ .
  • both are preferably oxygen atoms.
  • Y i2 is -CH 2 - - either Y i1 and Y i2 is -CH 2 in the case of emphasizing gamma 1 and more preferably from.
  • both are preferably sulfur atoms.
  • W i2 preferably represents a single bond or —CH 2 CH 2 —.
  • L i1 and L i2 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms.
  • An alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is particularly preferable.
  • L i1 and L i2 are preferably different, and the alkoxy group or alkenyloxy group is preferably one of L i1 and L i2 , Is particularly preferably L i1 .
  • the hydrogen atom present in L i1 and L i2 may be substituted with a fluorine atom, but is preferably not substituted with a fluorine atom.
  • R i1 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce ⁇ 1, and an alkyl group having 1 to 5 carbon atoms or the number of carbon atoms Particularly preferred are 2 to 5 alkenyl groups. Moreover, it is preferable that it is linear. In order to increase
  • R i1s are different from each other, and any one of R i1s having a plurality of alkoxy groups or alkenyloxy groups exists.
  • the alkoxy group or alkenyloxy group is particularly preferably R i1 in L i1 .
  • the hydrogen atom present in R i1 may be substituted with a fluorine atom, but is preferably not substituted with a fluorine atom.
  • a 1 is a trans-1,4-cyclohexylene group, an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, or a 3-fluoro group for decreasing ⁇ 1.
  • a 1,4-phenylene group is preferred, and a trans-1,4-cyclohexylene group is particularly preferred.
  • it may be a trans-1,4-cyclohexylene group, a 2-fluoro-1,4-phenylene group or a 3-fluoro-1,4-phenylene group. preferable.
  • an unsubstituted 1,4-phenylene group, an unsubstituted 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, or an unsubstituted naphthalene-2,6-diyl group It is preferable that In order to exhibit negatively large ⁇ , a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 2,3-difluoro-1,4-phenylene group is preferable.
  • the total number of fluorine atoms present in A i1 is preferably 1 to 4, preferably 1 to 3. It is particularly preferred.
  • Z i1 is preferably a single bond, —CH 2 CH 2 —, —CH 2 O— or —OCH 2 —, and preferably a single bond or —CH 2 CH 2 — in order to decrease ⁇ 1. Is more preferable.
  • a single bond, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C— is preferable, and a single bond, —CH ⁇ CH— or —C ⁇ C— -Is more preferable.
  • a single bond, —CH 2 CH 2 —, —CH 2 O— or —OCH 2 — is preferable.
  • a single bond is preferable.
  • n i1 When n i1 represents 2, it is preferable that any one or more of a plurality of Z i1 represent a single bond. n i1 is preferably 1 when ⁇ 1 is important. When importance is attached to Tni , it is preferably 2.
  • L i3 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy 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.
  • an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms is preferable.
  • Particularly preferred is an alkenyl group of ⁇ 5. Moreover, it is preferable that it is linear.
  • L i1 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms
  • L i3 is
  • L i4 and L i5 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and more preferably a hydrogen atom.
  • L i6 and L i7 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms.
  • An alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is particularly preferable.
  • L i8 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy 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.
  • an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms is preferable.
  • Particularly preferred is an alkenyl group of ⁇ 5. Moreover, it is preferable that it is linear.
  • L i2 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms
  • L i8 is
  • L i9 and L i10 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and more preferably a hydrogen atom.
  • the number of the groups is preferably 2 or less in order to increase the miscibility with other liquid crystal components.
  • it is preferably present at the positions of L i1 and L i2 , L i1 and L i8 , L i3 and L i2 , or L i3 and L i8.
  • two groups exist in the general formula (i) it is preferably present at the positions of L i1 and L i2 .
  • it does not become a structure where hetero atoms are directly bonded.
  • compounds represented by the following general formulas (i-1) to (i-946) are preferable.
  • particularly preferred compounds are (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), (i-7), (I-8), (i-9), (i-10), (i-11), (i-12).
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • R i1 and R i2 are the general formula (i) represents the same meaning as R i1.
  • the compound represented by the general formula (i) is, for example, the general formula (i-r1)
  • X i2 , Y i2 , W i1 , L i2 and L i5 represent the same meaning as X i2 , Y i2 , W i1 , L i2 and L i5 in general formula (i), respectively, but a plurality of X i2 may be different even in the same
  • R i3 and R i4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R i3 and R i4 are bonded to each other to form a cyclic structure —CH 2 —CH 2 —, —CH 2 -CH 2 -CH 2- or -CH 2 -C (CH 3 ) 2 -CH 2-
  • a broken line indicates that a bond may not exist or may exist.
  • X i1 , Y i1 , L i1 , L i3 , L i4 and W i2 represent the same meanings as X i1 , Y i1 , L i1 , L i3 , L i4 and W i2 in general formula (i), respectively.
  • X i3 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group.
  • X i1 , X i2 , Y i1 , Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 are X i1 , X i2 , Y i1 in the general formula (i)).
  • Y i2 , W i1 , W i2 , L i1 , L i2 , L i3 , L i4 and L i5 each represent the same meaning, but a plurality of X i2 may be the same or different
  • a broken line indicates that a bond may not exist or may exist.
  • L i2 are as defined L i2 in the general formula (i).
  • a compound represented by general formula (ir-7) Is reacted with a compound represented by general formula (ir-7) in the presence of a transition metal catalyst, a copper catalyst and a base.
  • L i1 , L i2 , X i1 and X i2 represent the same meaning as L i1 , L i2 , X i1 and X i2 in the general formula (i)
  • R i3 and R i4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R i3 and R i4 are bonded to each other to form a cyclic structure —CH 2 —CH 2 —, —CH 2 -CH 2 -CH 2- or -CH 2 -C (CH 3 ) 2 -CH 2-
  • L i11 represents the same meaning as L i1
  • X i3 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulf
  • a compound represented by general formula (S-3) is obtained by reacting a compound represented by general formula (S-1) with a compound represented by (S-2) in the presence of a transition metal catalyst and a base. Can do. Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably.
  • the reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred. Further, water may be used as necessary in order to allow the reaction to proceed appropriately.
  • 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred.
  • water may be used as necessary in order to allow the reaction to proceed
  • Any base can be used as long as it allows the reaction to proceed suitably.
  • Carbonates such as potassium carbonate, sodium carbonate and cesium carbonate; phosphates such as tripotassium phosphate and potassium dihydrogen phosphate; Are preferable, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferable.
  • the reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
  • the compound represented by the general formula (S-4) can be obtained by intramolecular reaction of the compound represented by the general formula (S-3). This intramolecular reaction can be performed by deprotonating —Y i3 —H of the general formula (S-3) with a base to generate an anion.
  • 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 and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred.
  • Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
  • reaction solvent Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether
  • chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane
  • examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene
  • examples of polar solvents include N, N-dimethylformamide
  • Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
  • ether solvents such as tetrahydrofuran and diethyl ether
  • polar solvents such as N, N-dimethylformamide are more preferable.
  • each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.
  • the reaction temperature can be from the freezing point of the solvent to the reflux temperature range, but is preferably 0 ° C to 150 ° C, more preferably 30 ° C to 120 ° C.
  • the compound represented by the general formula (S-5) can be obtained by oxidizing the compound represented by the general formula (S-4). This oxidation can be carried out by deprotonation with an organometallic reagent, reaction with a trialkyl borate to form a boron compound, and subsequent action of an oxidizing agent.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagent examples include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramerpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • trialkyl borate trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling.
  • combination of trialkyl borate and organometallic reagent any of the above-mentioned combinations are possible, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred.
  • the reaction temperature during boriding is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
  • the obtained boron compound may be isolated once or may be reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed and converted into a boric acid compound and then reacted with an oxidizing agent.
  • the oxidizing agent it is preferable to use hydrogen peroxide, peracetic acid or performic acid.
  • the reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C.
  • water may be contained in the solvent at the time of reaction with an oxidizing agent.
  • the compound represented by the general formula (S-7) can be obtained by reacting the hydroxyl group of the general formula (S-5) with the base as a phenolate with the general formula (S-6).
  • 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 and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred.
  • Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably.
  • Ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether, and examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane
  • examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene
  • examples of polar solvents include N, N-dimethylformamide
  • Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
  • ether solvents such as tetrahydrofuran and diethyl ether
  • polar solvents such as N, N-dimethylformamide are more preferable.
  • each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.
  • the reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C.
  • the generated phenolate may be isolated once and then reacted with the compound represented by the general formula (S-5), or may be reacted without isolation, but it is not isolated for ease of work. It is better to react.
  • the compound represented by the general formula (S-8) can be obtained by halogenating the compound represented by the general formula (S-7). This halogenation can be performed by deprotonation with an organometallic reagent and then reacting with bromine or iodine to form a halogen compound.
  • reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagents examples include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide.
  • N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • a compound represented by general formula (S-10) by reacting a compound represented by general formula (S-8) with a compound represented by (S-9) in the presence of a transition metal catalyst, a copper catalyst and a base. Can be obtained. Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably.
  • phosphine-type ligands such as a triphenylphosphine
  • Any copper catalyst may be used as long as it allows the reaction to proceed suitably, but copper (I) chloride, copper (I) bromide, copper iodide (I), copper acetate (I), etc.
  • a monovalent copper catalyst is preferred, and copper (I) iodide is more preferred.
  • the reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but 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, polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane are preferred, and tetrahydrofuran, ethanol, toluene and N, N-dimethylformamide are more preferred. . Further, water may be used as necessary in order to allow the reaction to proceed appropriately.
  • 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
  • the reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
  • the compound represented by the general formula (S-11) can be obtained by simultaneously performing deprotection with an acid and intramolecular reaction in the presence of water in the compound represented by the general formula (S-10).
  • Any acid can be used as long as it allows the reaction to proceed suitably, but inorganic acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, and the like are preferable, and hydrochloric acid is more preferable.
  • inorganic acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as p-toluenesulfonic acid, and the like are preferable, and hydrochloric acid is more preferable.
  • any solvent can be used as long as it allows the reaction to proceed suitably, but water-soluble solvents such as tetrahydrofuran, ethanol, methanol, isopropyl alcohol and the like are preferable.
  • the reaction temperature may be any temperature that allows the reaction to proceed suitably, but a temperature from room temperature to the boiling point of the solvent is preferred.
  • the compound represented by the general formula (S-12) can be obtained by reacting the compound represented by the general formula (S-11) with hydrogen gas in the presence of a metal catalyst in an organic solvent.
  • Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc.
  • Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol or butanol, and ester solvents such as ethyl acetate or butyl acetate are preferred, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate are preferred.
  • acids such as hydrochloric acid, acetic acid, or a sulfuric acid, as needed.
  • the reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.
  • the metal catalyst to be used may be any metal catalyst that allows the reaction to proceed suitably, but is preferably palladium carbon, ruthenium carbon, platinum black or platinum oxide, and more preferably palladium carbon.
  • the hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa.
  • R i3 and R i4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, or R i3 and R i4 are bonded to each other to form a cyclic structure —CH 2 —CH 2 —, —CH 2 -CH 2 -CH 2- or -CH 2 -C (CH 3 ) 2 -CH 2-
  • X i3 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesul
  • the compound represented by the general formula (S-14) can be obtained by boronizing the compound represented by the general formula (S-13). This boronation can be performed by deprotonation with an organometallic reagent and then reacting with a trialkyl borate to form a boron compound.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagents examples include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide.
  • N-Butyllithium, sec-butyllithium and lithium diisopropylamide are preferred from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide capable of efficient deprotonation are more preferred.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • trialkyl borate trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling.
  • combination of trialkyl borate and organometallic reagent any of the above-mentioned combinations are possible, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred.
  • the reaction temperature during boriding is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
  • a compound represented by general formula (S-16) is obtained by reacting a compound represented by general formula (S-14) with a compound represented by (S-15) in the presence of a transition metal catalyst and a base. Can do. Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably.
  • the reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred. Further, water may be used as necessary in order to allow the reaction to proceed appropriately.
  • 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred.
  • water may be used as necessary in order to allow the reaction to proceed
  • Any base can be used as long as it allows the reaction to proceed suitably.
  • Carbonates such as potassium carbonate, sodium carbonate and cesium carbonate; phosphates such as tripotassium phosphate and potassium dihydrogen phosphate; Are preferable, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferable.
  • the reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
  • the compound represented by the general formula (S-17) can be obtained by intramolecular reaction of the compound represented by the general formula (S-16). This intramolecular reaction can be carried out by deprotonation of —Y i3 —H of the general formula (S-16) with a base to generate an anion.
  • 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 and alkali metals. Phosphate, alkali metal phosphate, alkali metal carbonate, alkali metal hydroxide, alkali metal amide and alkali metal are preferred, and alkali metal phosphate, alkali metal hydride and alkali metal carbonate are more preferred.
  • Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
  • reaction solvent Any reaction solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether
  • chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane
  • examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene
  • examples of polar solvents include N, N-dimethylformamide
  • Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
  • ether solvents such as tetrahydrofuran and diethyl ether
  • polar solvents such as N, N-dimethylformamide are more preferable.
  • each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.
  • the reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C.
  • the compound represented by the general formula (S-18) can be obtained by halogenating the compound represented by the general formula (S-17). This halogenation can be performed by deprotonation with an organometallic reagent and then reacting with bromine or iodine to form a halogen compound.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents examples include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagents examples include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide.
  • N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • a compound represented by general formula (S-20) is obtained by reacting a compound represented by general formula (S-18) with a compound represented by (S-19) in the presence of a transition metal catalyst and a base. Can do. Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably.
  • the reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred. Further, water may be used as necessary in order to allow the reaction to proceed appropriately.
  • 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred.
  • water may be used as necessary in order to allow the reaction to proceed
  • Any base can be used as long as it allows the reaction to proceed suitably.
  • Carbonates such as potassium carbonate, sodium carbonate and cesium carbonate; phosphates such as tripotassium phosphate and potassium dihydrogen phosphate; Are preferable, and potassium carbonate, cesium carbonate, and tripotassium phosphate are more preferable.
  • the reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred. (Manufacturing method 3)
  • L i2, X i1, X i2 , Y i2 and W i1 represent the same meaning in the general formula (i) and L i2, X i1, X i2 , Y i2 and W i1, X i5 represents chlorine, bromine, iodine, benzenesulfonyloxy group, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyloxy group; Y i3 represents —O— or —S—, R i2 represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms.
  • the compound represented by the general formula (S-21) can be obtained by oxidizing the compound represented by the general formula (S-17). This oxidation can be carried out by deprotonation with an organometallic reagent, reaction with a trialkyl borate to form a boron compound, and subsequent action of an oxidizing agent.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagent examples include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramerpiperidide. N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • trialkyl borate trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate are preferably used, but trimethyl borate and triisopropyl borate are more preferred from the viewpoint of availability and handling.
  • combination of trialkyl borate and organometallic reagent any of the above-mentioned combinations are possible, but the combination of sec-butyl lithium and trimethyl borate, and the combination of lithium diisopropylamide and triisopropyl borate are preferable, and lithium diisopropyl A combination of amide and triisopropyl borate is more preferred.
  • the reaction temperature during boriding is preferably -100 ° C to -20 ° C, more preferably -78 ° C to -40 ° C.
  • the obtained boron compound may be isolated once or may be reacted with an oxidizing agent without isolation. Further, the obtained boron compound may be hydrolyzed and converted into a boric acid compound and then reacted with an oxidizing agent.
  • the oxidizing agent hydrogen peroxide water, peracetic acid or performic acid is preferably used.
  • the reaction temperature is preferably -78 ° C to 70 ° C, more preferably 0 ° C to 50 ° C.
  • water may be contained in the solvent at the time of reaction with an oxidizing agent.
  • the compound represented by the general formula (S-23) can be obtained by reacting the compound represented by the general formula (S-21) with the compound represented by the general formula (S-22). This reaction can be carried out by reacting the hydroxyl group of the general formula (S-21) with the base as a phenolate with the general formula (S-22).
  • the base used in this case is a metal hydride, metal carbonate, metal Mention may be made of phosphates, metal hydroxides, metal carboxylates, metal amides and metals, among which alkali metal hydrides, alkali metal phosphates, alkali metal phosphates, alkali metal carbonates, alkali metals Hydroxides, alkali metal amides and alkali metals are preferred, and alkali metal phosphates, alkali metal hydrides and alkali metal carbonates are more preferred.
  • Lithium hydride, sodium hydride and potassium hydride as alkali metal hydrides, tripotassium phosphate as alkali metal phosphates, sodium carbonate, sodium bicarbonate, cesium carbonate, potassium carbonate as alkali metal carbonates And potassium hydrogen carbonate can be preferably mentioned.
  • Any reaction solvent may be used as long as it allows the reaction to proceed suitably.
  • Ether solvents, chlorine solvents, hydrocarbon solvents, aromatic solvents, polar solvents, and the like can be preferably used.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether and t-butyl methyl ether, and examples of chlorine solvents include dichloromethane, 1,2-dichloroethane and carbon tetrachloride.
  • hydrocarbon solvents examples include pentane, hexane, cyclohexane, heptane, and octane
  • examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene
  • examples of polar solvents include N, N-dimethylformamide
  • Preferable examples include N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.
  • ether solvents such as tetrahydrofuran and diethyl ether
  • polar solvents such as N, N-dimethylformamide are more preferable.
  • each said solvent may be used independently, or 2 or more types of solvents may be mixed and used.
  • the reaction temperature can be in the range from the freezing point of the solvent to the reflux temperature, preferably from 0 ° C to 150 ° C, more preferably from 30 ° C to 120 ° C.
  • the phenolate produced may be isolated once and then reacted with the compound represented by the general formula (S-22), or it may be reacted without isolation, but it is not isolated for ease of work. It is better to react. (Manufacturing method 4)
  • L i1 , L i2 , X i1 , X i2 , Y i2 and W i11 have the same meaning as L i1 , L i2 , X i1 , X i2 , Y i2 and W i1 in the general formula (i)).
  • Y i3 represents —O— or —S—.
  • the compound represented by the general formula (S-25) can be obtained by reacting the compound represented by the general formula (S-17) with the compound represented by the general formula (S-24). This reaction can be carried out by deprotonation with an organometallic reagent and reaction with general formula (S-24).
  • reaction solvent may be used as long as it allows the reaction to proceed suitably, and examples thereof include ether solvents and hydrocarbon solvents.
  • ether solvents include 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, diethyl ether, and t-butyl methyl ether.
  • hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, and octane. Of these, tetrahydrofuran is preferred.
  • organometallic reagents include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, lithium diisopropylamide and lithium 2,2,4,4-tetramethylpiperidide.
  • N-Butyllithium, sec-butyllithium, and lithium diisopropylamide are preferable from the viewpoint of ease of handling, and sec-butyllithium and lithium diisopropylamide that can be efficiently deprotonated are more preferable.
  • a base such as potassium tert-butoxide or tetramethylethylenediamine may be used as an additive together with the organometallic reagent.
  • the reaction temperature for deprotonation is preferably from ⁇ 100 ° C. to ⁇ 20 ° C., more preferably from ⁇ 78 ° C. to ⁇ 40 ° C.
  • a compound represented by the general formula (S-26) can be obtained by dehydrating the compound represented by the general formula (S-25).
  • Examples of the dehydration method include a method of heating in the presence of an acid.
  • Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and potassium bisulfate, organic acids such as acetic acid, trifluoroacetic acid, and p-toluenesulfonic acid, and Lewis acids such as boron trifluoride.
  • the hydroxyl group can be reacted with p-toluenesulfonic acid chloride, trifluoromethanesulfonic acid chloride, triphosgene, etc.
  • the compound represented by the general formula (S-27) can be obtained by reacting the compound represented by the general formula (S-26) with hydrogen gas in an organic solvent in the presence of a metal catalyst.
  • Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc.
  • Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol or butanol, and ester solvents such as ethyl acetate or butyl acetate are preferred, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate are preferred.
  • acids such as hydrochloric acid, acetic acid, or a sulfuric acid, as needed.
  • the reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.
  • the metal catalyst to be used may be any metal catalyst that allows the reaction to proceed suitably, but is preferably palladium carbon, ruthenium carbon, platinum black or platinum oxide, and more preferably palladium carbon.
  • the hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa. (Manufacturing method 5)
  • R i3 represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH 2 — or two or more non-adjacent ones present in the alkyl group or alkenyl group.
  • —CH 2 — may be replaced by —C ⁇ C—, —O—, —S—, —COO—, —OCO— or —CO—, and the hydrogen atom present in the alkyl or alkenyl group is fluorine.
  • the compound represented by the general formula (S-29) can be obtained by reacting the compound represented by the general formula (S-18) with the compound represented by (S-28) in the presence of a transition metal catalyst. .
  • Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably.
  • phosphine-type ligands such as a triphenylphosphine, as needed.
  • the reaction solvent to be used may be any as long as it allows the reaction to proceed suitably, but 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred.
  • 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 preferred, and tetrahydrofuran, ethanol and toluene are more preferred.
  • the reaction temperature may be any number of times as long as the reaction proceeds suitably, but is preferably from room temperature to the temperature at which the solvent used is refluxed, more preferably from 40 ° C to the temperature at which the solvent is refluxed. A temperature from 60 ° C. to the reflux of the solvent is particularly preferred.
  • the general formula (i) At least one compound represented by formula (1), but it is preferable to contain at least one of the following second to fourth components as other components.
  • the second component is a so-called n-type liquid crystal compound having a negative dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC3) to (LC5).
  • R LC31, R LC32, R LC41 , R LC42, R LC51 and R LC52 is 1 to 15 carbon atoms independently, one in the alkyl group or two or more —CH 2 — may be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C— so that the oxygen atom is not directly adjacent.
  • one or more hydrogen atoms in the group may be optionally substituted by a halogen atom, a LC31, a LC32, a LC41, a LC42, a LC51 and a LC52 each independently any of the following Structure
  • one or more —CH 2 — in the cyclohexylene group may be substituted with an oxygen atom
  • one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom
  • one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 ).
  • Z LC31, Z LC32, Z LC41, Z LC42, Z LC51 and Z LC51 each independently represent a single bond
  • -CH CH -, - C ⁇ C -, - CH 2 CH 2 -, - ( CH 2 ) 4 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—
  • Z 5 represents —CH 2 — or an oxygen atom
  • X LC41 represents Represents a hydrogen atom or a fluorine atom
  • m LC31 , m L C32, m LC41, m LC42, m LC51 and m LC52 each independently represent 0 ⁇ 3, m LC31 + m LC32, m LC41 + m LC42 and m LC51 + m LC52 is 1, 2 or 3,
  • a LC31 ⁇ When a plurality of A LC52 and Z
  • R LC31 to R LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,
  • a LC31 to A LC52 each independently preferably has the following structure:
  • Z LC31 to Z LC51 each independently has a single bond, —CH 2 O—, —COO—, —OCO— , —CH 2 CH 2 —, —CF 2 O—, —OCF 2 — or —OCH 2 —. preferable.
  • LC3 is the following general formula (LC3-a) and general formula (LC3-b)
  • R LC31 , R LC32 , A LC31 and Z LC31 each independently represent the same meaning as R LC31 , R LC32 , A LC31 and Z LC31 in the general formula (LC3)
  • X LC3b1 to X LC3b6 are Represents a hydrogen atom or a fluorine atom
  • at least one of X LC3b1 and X LC3b2 or X LC3b3 and X LC3b4 represents a fluorine atom
  • m LC3a1 is 1, 2 or 3
  • m LC3b1 is 0 or
  • a plurality of A LC31 and Z LC31 may be the same or different, provided that they are represented by the general formula (LC3-b) in the general formula (LC3-a)
  • a compound selected from the group of compounds represented by the formula: Rukoto is preferable.
  • R LC31 and R LC32 each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.
  • a LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group.
  • 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.
  • Z LC31 is a single bond, -CH 2 O -, - COO -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.
  • the general formula (LC3-a) preferably represents the following general formula (LC3-a1) to general formula (LC3-a4).
  • R LC31 and R LC32 each independently represent the same meaning as R LC31 and R LC32 in General Formula (LC3).
  • R LC31 and R LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R LC31 has 1 carbon atom. More preferably, it represents an alkyl group of ⁇ 7 , and R LC32 represents an alkoxy group of 1 to 7 carbon atoms.
  • the general formula (LC3-b) is preferably represented by the following general formula (LC3-b1) to general formula (LC3-b12).
  • the general formula (LC3-b1), the general formula (LC3-b6), the general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is Most preferably it represents.
  • R LC31 and R LC32 each independently represent the same meaning as R LC31 and R LC32 in General Formula (LC3).
  • R LC31 and R LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R LC32 represents an alkyl group having 2 carbon atoms.
  • LC4 is general formula (LC4-a) to general formula (LC4-c)
  • general formula (LC5) is general formula (LC5-a) to general formula (LC5-c).
  • R LC41, R LC42 and X LC41 each independently represent the same meaning as R LC41, R LC42 and X LC41 in the general formula (LC4)
  • R LC51 and R LC52 is the general independently It represents the same meaning as R LC51 and R LC52 in formula (LC5)
  • R LC41, R LC42, R LC51 and R LC52 each independently represents an alkyl group of 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents ⁇ 7 alkenyloxy groups.
  • Z LC4a1 to Z LC5c1 each independently preferably represents a single bond, —CH 2 O—, —COO—, —OCO— , —CH 2 CH 2 —, and more preferably represents a single bond.
  • the third component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formula (LC6).
  • R LC61 and R LC62 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more of —CH 2 — in the alkyl group is not directly adjacent to an oxygen atom. And may be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C—, and one or more hydrogen atoms in the alkyl group May be optionally halogen-substituted, and A LC61 to A LC63 each independently represent
  • one or more —CH 2 CH 2 — in the cyclohexylene group may be substituted with —CH ⁇ CH—, —CF 2 O—, —OCF 2 —, -One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom
  • Z LC61 and Z LC62 each independently represent a single bond, —CH ⁇ CH—, Represents —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—
  • m Lc6 represents 0-3.
  • R LC61 and R LC62 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,
  • a LC61 to A LC63 each independently preferably has the following structure:
  • Z LC61 and Z LC62 are each independently preferably a single bond, —CH 2 CH 2 —, —COO— , —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—.
  • R LC61 and R LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms) It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this.
  • the fourth component is a so-called p-type liquid crystal compound having a positive dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC1) and (LC2).
  • R LC11 and R LC21 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more of —CH 2 — in the alkyl group is not directly adjacent to an oxygen atom. And may be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C—, and one or more hydrogen atoms in the alkyl group May be optionally substituted with a halogen atom, and A LC11 and A LC21 are each independently any one of the following structures:
  • one or more —CH 2 — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group may be substituted. May be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 ).
  • X LC11, X LC12, X LC21 ⁇ X LC23 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF 3 or -OCF 3
  • Y LC11 and Y LC21 are each independently a hydrogen atom, fluorine atom, a chlorine atom, a cyano group, -CF 3
  • LC11 and m LC21 each independently represents an integer of 1 to 4, and when there are
  • R LC11 and R LC21 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms.
  • Group, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and a straight chain is more preferable, and the alkenyl group most preferably represents the following structure.
  • a LC11 and A LC21 each independently preferably have the following structure.
  • Y LC11 and Y LC21 are each independently preferably a fluorine atom, a cyano group, —CF 3 or —OCF 3 , preferably a fluorine atom or —OCF 3 , and particularly preferably a fluorine atom.
  • Z LC11 and Z LC21 are preferably a single bond, —CH 2 CH 2 —, —COO—, —OCO— , —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O— , —CH 2 CH 2 —, —OCH 2 —, —OCF 2 — or —CF 2 O— are preferred, and a single bond, —OCH 2 — or —CF 2 O— is more preferred.
  • m LC11 and m LC21 are preferably 1, 2 or 3, preferably 1 or 2 when emphasizing storage stability at low temperature and response speed, and 2 or 3 for improving the upper limit of the nematic phase upper limit temperature. Is preferred.
  • LC1 is represented by the following general formula (LC1-a) to general formula (LC1-c)
  • R LC11, Y LC11, X LC11 and X LC12 each independently represent the same meaning as R LC11, Y LC11, X LC11 and X LC12 in the general formula (LC1)
  • a LC1a1, A LC1a2 and A LC1b1 represents a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group
  • XLC1b1 , XLC1b2 , XLC1c1 to XLC1c4 Are each independently a hydrogen atom, a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 ), and are preferably one or more compounds selected from the group consisting of compounds represented by:
  • R LC11 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
  • X LC11 to X LC1c4 are each independently preferably a hydrogen atom or a fluorine atom.
  • Y LC11 is preferably independently a fluorine atom, —CF 3 or —OCF 3 .
  • the general formula (LC1) is changed from the following general formula (LC1-d) to the general formula (LC1-m).
  • R LC11, Y LC11, X LC11 and X LC12 each independently represent the same meaning as R LC11, Y LC11, X LC11 and X LC12 in the general formula (LC1), A LC1d1, A LC1f1, A LC1g1 , A LC1j1 , A LC1k1 , A LC1k2 , A LC1m1 to A LC1m3 are 1,4-phenylene group, trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3- It represents dioxane-2,5-diyl group, X LC1d1, X LC1d2, X LC1f1, X LC1f2, X LC1g1, X LC1g2, X LC1h1, X LC1h2, X LC1i1, X LC1i2, X LC1 LC1
  • R LC11 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
  • X LC11 to X LC1m2 are each independently preferably a hydrogen atom or a fluorine atom.
  • Y LC11 is preferably independently a fluorine atom, —CF 3 or —OCF 3 .
  • Z LC1d1 to Z LC1m1 are each independently preferably —CF 2 O— or —OCH 2 —.
  • the general formula (LC2) is changed from the following general formula (LC2-a) to the general formula (LC2-g).
  • R LC21 , Y LC21 , X LC21 to X LC23 each independently represents the same meaning as R LC21 , Y LC21 , X LC21 to X LC23 in the general formula (LC2), and X LC2d1 to X LC2d4 , X LC2e1 to X LC2e4 , X LC2f1 to X LC2f4 and X LC2g1 to X LC2g4 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 , and Z LC2a1 , Z LC2b1 , Z LC2c1 , Z LC2d1 , Z LC2e1 , Z LC2f1 and Z LC2g1 are each independently a single bond, —CH ⁇ CH—, —CF ⁇ CF— , —C ⁇ C— , —CH
  • R LC21 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
  • X LC21 to X LC2g4 are each independently preferably a hydrogen atom or a fluorine atom
  • Y LC21 is preferably each independently a fluorine atom, —CF 3 or —OCF 3 .
  • Z LC2a1 to Z LC2g4 are each independently preferably —CF 2 O— or —OCH 2 —.
  • the composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.
  • the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less with respect to the total mass of the composition. Preferably, it is more preferably 1% or less, and most preferably not substantially contained.
  • the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. % Or less, preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.
  • the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group as the total mass of the composition is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and still more preferably not contained.
  • a hydrogen atom to reduce the content of the compound having the optionally substituted 2-methyl-1,4-diyl group halogen in the molecule is preferably 10% or less, more preferably 8% or less with respect to the total mass of the composition. It is preferably 5% or less, more preferably 3% or less, and still more preferably substantially not contained.
  • substantially not contained in the present application means that it is not contained except for an unintentionally contained product.
  • the alkenyl group when the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the alkenyl group has 2 to 5 carbon atoms.
  • the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. Preferably not.
  • the average elastic constant (K AVG ) of the liquid crystal composition used in the present invention is preferably 10 to 25, and the lower limit thereof is preferably 10, preferably 10.5, preferably 11 and preferably 11.5.
  • 12 is preferable, 12.3 is preferable, 12.5 is preferable, 12.8 is preferable, 13 is preferable, 13.3 is preferable, 13.5 is preferable, 13.8 is preferable, 14 is preferable, 14 .3 is preferred, 14.5 is preferred, 14.8 is preferred, 15 is preferred, 15.3 is preferred, 15.5 is preferred, 15.8 is preferred, 16 is preferred, 16.3 is preferred, 16 .5, 16.8 is preferable, 17 is preferable, 17.3 is preferable, 17.5 is preferable, 17.8 is preferable, and 18 is preferable.
  • 25 is preferable, 24.5 is preferable, 24 is preferable, 23.5 is preferable, 23 is preferable, 22.8 is preferable, 22.5 is preferable, 22.3 is preferable, 22 is preferable, and 21.8 is 21.5 is preferred, 21.3 is preferred, 21 is preferred, 20.8 is preferred, 20.5 is preferred, 20.3 is preferred, 20 is preferred, 19.8 is preferred, 19.5 is preferred 19.3 is preferred, 19 is preferred, 18.8 is preferred, 18.5 is preferred, 18.3 is preferred, 18 is preferred, 17.8 is preferred, 17.5 is preferred, 17.3 is preferred 17 is preferable. When importance is placed on reducing power consumption, it is effective to reduce the amount of light from the backlight, and it is preferable to improve the light transmittance of the liquid crystal display element.
  • the liquid crystal composition of the present invention has a refractive index anisotropy ( ⁇ n) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.12. Particularly preferred. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.
  • the liquid crystal composition of the present invention has a viscosity ( ⁇ ) at 20 ° C. of 10 to 30 mPa ⁇ s, more preferably 10 to 25 mPa ⁇ s, and particularly preferably 10 to 22 mPa ⁇ s.
  • the liquid crystal composition of the present invention has a rotational viscosity ( ⁇ 1 ) at 20 ° C. of 60 to 200 mPa ⁇ s, more preferably 60 to 120 mPa ⁇ s, and particularly preferably 60 to 100 mPa ⁇ s. .
  • the liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T ni ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C. In addition, it is preferable to show a nematic liquid crystal at 20 ° C.
  • T ni nematic phase-isotropic liquid phase transition temperature
  • the liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, an infrared absorber, a polymerizable monomer, or a light stabilizer in addition to the above-described compounds. Good.
  • the liquid crystal display device using the liquid crystal composition containing the compound of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving.
  • the present invention can be applied to liquid crystal display elements in various modes such as a mode, a PSVA mode, a PSA mode, an IPS mode, an FFS mode, or an ECB mode.
  • % in the compositions of the following Examples and Comparative Examples means “% by mass”.
  • the phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).
  • T n-i nematic phase - represents the transition temperature of the isotropic phase.
  • the reaction mixture was warmed to room temperature, 10% hydrochloric acid (150 ml) and hexane (100 ml) were added and stirred, and the resulting organic layers were combined, washed with water and saturated brine, and anhydrous sodium sulfate. And dried.
  • the obtained solution was concentrated to obtain 29.5 g. While stirring the resulting solid in THF (150 ml) and sodium hydrogen carbonate (0.42 g), 30% aqueous hydrogen peroxide (14.9 g) was added dropwise at room temperature and stirred for 12 hours. The solution temperature was cooled to 0 ° C. and 15% aqueous sodium thiosulfate solution (150 ml) was added.
  • Example 325 Preparation of Liquid Crystal Composition-1 Host liquid crystal (H) showing the following physical properties Was prepared. All the values are actually measured values.
  • T n-i (nematic phase - isotropic liquid phase transition temperature): 73.8 ° C.
  • ⁇ dielectric anisotropy at 25 ° C.
  • ⁇ 2.79 ⁇ n (refractive index anisotropy at 25 ° C.): 0.101 ⁇ 1 (rotational viscosity coefficient at 25 ° C.): 118
  • MA liquid crystal composition
  • the extrapolated value of each physical property value of) was as follows.
  • the prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state for one month or more at room temperature.
  • liquid crystal display device manufactured using the liquid crystal composition (MA) showed excellent display characteristics, maintained stable display characteristics for a long time, and showed high reliability.
  • Example 326 Preparation of liquid crystal composition-2 A liquid crystal composition (MB) comprising 90% of the base liquid crystal (H) and 10% of the compound (1-8-203) obtained in Example 2 was prepared. From this composition (M-B), the extrapolated T n-i of the compound obtained in Example 2 (1-8-203), extrapolated [Delta] [epsilon], extrapolation [Delta] n, the extrapolation gamma 1 values below It is as follows.
  • Extrapolation T n-i 38.9 °C Extrapolation ⁇ : ⁇ 17.9 Extrapolation ⁇ n: 0.198 Extrapolation ⁇ 1 : 372 mPa ⁇ s Further, the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for one month or more at room temperature.
  • liquid crystal display device manufactured using the liquid crystal composition (MB) exhibited excellent display characteristics, maintained stable display characteristics over a long period of time, and exhibited high reliability.

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