Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
• • 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

Definitions

• the present invention relates to a compound, a liquid crystal composition containing the compound, and an element using the liquid crystal composition.
• the liquid crystal composition is used for mobile terminals such as smartphones and tablet devices, and display applications such as TVs and window displays.
• display applications such as TVs and window displays.
• an antenna for transmitting and receiving radio waves between a mobile body such as a car and a communication satellite is drawing attention.
• satellite communication uses a parabolic antenna, but when used in a mobile body, the parabolic antenna must be directed toward the satellite at any time, and a large moving part is required.
• the antenna using the liquid crystal composition can change the transmission / reception direction of radio waves by operating the liquid crystal, it is not necessary to move the antenna itself, and the shape of the antenna can be made flat.
• the refractive index anisotropy ⁇ n of the liquid crystal composition required for these applications is, for example, about 0.4, which is much larger than ⁇ n required for display applications. Therefore, it is required that the compound added to and used in the liquid crystal composition has a large ⁇ n, has high compatibility with the liquid crystal composition, and does not easily decrease the voltage holding ratio when the element is manufactured.
• a compound having a thienothiophene structure has been reported as a compound having a large ⁇ n.
• these compounds have problems such as low compatibility when added to a liquid crystal composition for an antenna, and lowering the voltage holding ratio of the device when the device is manufactured (non-).
• Patent Document 1 Patent Documents 1 and 2). Therefore, there has been a demand for the development of a compound having a large ⁇ n, high compatibility with a liquid crystal composition, and a voltage retention rate that does not easily decrease when an element is manufactured.
• the problem to be solved by the present invention is that it has a large refractive index anisotropy ⁇ n, has high compatibility with a liquid crystal composition, and when an element is manufactured by adding it to a liquid crystal composition, the voltage retention rate of the element can be determined. It is an object of the present invention to provide a compound which is difficult to lower, a liquid crystal composition containing the compound, and an element using the liquid crystal composition.
• the present invention has the following general formula (I).
• R 1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom, and the alkyl
• a 1 and A 2 each represent a hydrocarbon ring or a heterocycle having 3 to 16 carbon atoms which may be independently substituted, but when a plurality of A 1s are present, they are the same but different.
• a x is the following formula (Ax-1) and formula (Ax-2).
• the broken line represents the bond position
• X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• Y 1 , Y 3 , Y 4 and Y 6 are independent of each other.
• Y 2 and Y 5 are independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and an arbitrary hydrogen atom.
• a compound whose structure represented by is not the same, and provides a liquid crystal composition containing the compound and an element using the liquid crystal composition.
• the compound of the present invention has a large refractive index anisotropy ⁇ n, has high compatibility with the liquid crystal composition, and does not easily lower the voltage retention rate of the element when the element is manufactured by adding it to the liquid crystal composition. Therefore, it is useful as a material for elements such as high-frequency phase shifters, phased array antennas, image recognition devices, ranging devices, liquid crystal display elements, liquid crystal lenses, and birefringent lenses for displaying stereoscopic images.
• the present invention provides a compound represented by the general formula (I), a liquid crystal composition containing the compound, and an element using the liquid crystal composition.
• R 1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom.
• R 1 is a hydrogen atom, and any hydrogen atom in the group is replaced with a halogen atom.
• R 1 is an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkenyl having 2 to 5 carbon atoms. It is particularly preferable to represent a group or an alkynyl group having 3 to 7 carbon atoms.
• a 1 and A 2 represent hydrocarbon rings or heterocycles having 3 to 16 carbon atoms which may be independently substituted, but when a plurality of A 1s are present, they are the same. it may be different even if the a 2 there are a plurality thereof may be the same or different. From the viewpoint of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis, and availability of raw materials, A 1 and A 2 are independently unsubstituted or one.
• the broken line represents the bonding position, and when a plurality of L 1s are present, they may be the same or different.
• a 1 and A 2 are plural. If present, they may be the same or different, and even more so, each independently represents a group selected from formulas (A-1) to formulas (A-7) and formulas (A-12).
• A-1 formulas
• A-3 formulas
• A-7 formulas
• L 1 is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropyl.
• L 1 is a fluorine atom, a chlorine atom, or any hydrogen atom in the group is a fluorine atom.
• L 1 is a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms. It is more preferable to represent a cyclic alkyl group, and it is particularly preferable that L 1 represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms.
• Z 1 , Z 2 and Z 3 each independently represent a divalent linking group or a single bond, but when there are a plurality of Z 1, they may be the same or different. well, they if Z 2 there are a plurality may be the same or different.
• Z 1, Z 2 and Z 3 are those when there are a plurality of which may be the same or different and each independently -CF 2 O- , -OCF 2- , -C ⁇ C- or a single bond is even more preferred, and if there are multiple Z 1 , Z 2 and Z 3, they may be the same or different and are independent of each other. It is particularly preferable to represent -C ⁇ C- or a single bond.
• m1 and m2 independently represent integers from 0 to 3, while m1 + m2 represent integers from 0 to 3. From the viewpoints of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis and availability of raw materials, m1 and m2 independently represent 0, 1 or 2, respectively, and m1 + m2 is 0. It is preferable to represent an integer from 3 to 3, m1 and m2 independently represent 0, 1 or 2, m1 + m2 more preferably represent 0, 1 or 2, and m1 and m2 independently represent 0 or 2, respectively. It is more preferable that m1 + m2 represents 0, 1 or 2, m1 and m2 each independently represent 0 or 1, and m1 + m2 particularly preferably represent 0 or 1.
• a x is the following formula (Ax-1) and Formula (Ax-2)
• the broken line represents the bond position
• X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• Y 1 , Y 3 , Y 4 and Y 6 are independent of each other.
• Y 2 and Y 5 are independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and an arbitrary hydrogen atom.
• An alkyl group having 1 to 8 carbon atoms may be present, an alkoxy group having 1 to 7 carbon atoms may be substituted with an arbitrary hydrogen atom, and an arbitrary hydrogen atom may be substituted with a fluorine atom.
• Y 2 and Y 5 have the above-mentioned structure.
• a thioisocyano group (-NCS) is used as Y 2 and Y 5 , the voltage retention rate may decrease depending on the electron-conjugated state with the thienothiophene structure.
• X 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• Y 11 , Y 31 , Y 41 and Y 61 are independent hydrogen atoms and fluorine atoms, respectively.
• it represents a chlorine atom
• Y 21 and Y 51 are independent fluorine atoms, chlorine atoms, cyano groups, nitro groups, pentafluorosulfanyl groups, and the number of carbon atoms in which any hydrogen atom may be substituted with a fluorine atom.
• a x is the following formula ( Ax-1-ii)
• X 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• Y 12 and Y 32 independently represent a hydrogen atom, a fluorine atom or a chlorine atom
• Y 22 is a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is replaced with a fluorine atom.
• a x is the following formula (Ax-1-iv)
• Y 14 and Y 34 each independently represent a hydrogen atom or a fluorine atom, and Y 24 represents a fluorine atom or a cyano group). preferable.
• the compound represented by the general formula (I) is in the formula.
• the structures represented by are not the same structure. This is because when the two structures bonded to both ends of the thieno [3,2-b] thiophene-2,5-diyl group are the same, the crystal state of the compound is high because the structure of the compound is highly symmetric. This is because it becomes energetically stable, crystals are likely to precipitate from the liquid crystal composition, and storage stability is likely to be lowered.
• the compound represented by the general formula (I) has a wide temperature range indicating a liquid crystal phase, dielectric anisotropy, compatibility with a liquid crystal composition, refractive index anisotropy, voltage retention, and ease of synthesis. And from the viewpoint of availability of raw materials, the following general formula (Ii)
• R 11 is a hydrogen atom, any hydrogen atom in the group may be replaced with a halogen atom, and one or two or more -CH 2- in the group are independently -O-.
• a 11 and A 21 are independently 1,4-phenylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, phenanthrene-2,7-diyl group, benzothiophene-2,5, respectively.
• a x1 is the following formula (Ax-1-i) and formula (Ax-2-i).
• X 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• Y 11 , Y 31 , Y 41 and Y 61 are independent hydrogen atoms and fluorine atoms, respectively.
• it represents a chlorine atom
• Y 21 and Y 51 are independent fluorine atoms, chlorine atoms, cyano groups, nitro groups, pentafluorosulfanyl groups, and the number of carbon atoms in which any hydrogen atom may be substituted with a fluorine atom.
• an alkoxy group having 1 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom and 2 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom.
• any hydrogen atom in the group may be replaced with a fluorine atom, and one or two or more -CH 2- in the group are independently -O- and -CH, respectively.
• a 12 and A 22 are independently expressed from the following equations (A-ii-1) to (A-ii-14).
• the broken line represents the bonding position, and when a plurality of L 12s are present, they may be the same or different.), But when there are a plurality of A 12s, they are the same. may be be different also, they if a 22 there are a plurality may be the same or different and
• L 12 a fluorine atom or any hydrogen atom in the group may be substituted with a fluorine atom, and -CH 2- in the group may be substituted by -O-, which is a direct number of carbon atoms 1 to 10.
• m12 and m22 independently represent 0, 1 or 2
• m12 + m22 represent 0, 1 or 2, respectively.
• X 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• Y 12 and Y 32 independently represent a hydrogen atom, a fluorine atom or a chlorine atom
• Y 22 is a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is replaced with a fluorine atom.
• R 13 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, or a carbon atom.
• Represents the alkynyl group of the numbers 2 to 8 A 13 and A 23 are independently expressed in the following formulas (A-iii-1) to (A-iii-7) and (A-iii-12).
• L 13 represents a fluorine atom or a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms.
• m13 and m23 independently represent 0 or 1, and m13 + m23 represent 0, 1 or 2, respectively.
• X 13 represents a hydrogen atom, a methyl group or an ethyl group.
• Y 13 and Y 33 independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y 23 represents a fluorine atom, a chlorine atom or a cyano group.
• R 14 represents an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 3 to 7 carbon atoms.
• a 14 and A 24 are the following formulas (A-iv-1), formulas (A-iv-3) to formulas (A-iv-7).
• L 14 represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms.
• Z 14 , Z 24 and Z 34 each independently represent -C ⁇ C- or a single bond.
• Y 14 and Y 34 independently represent a hydrogen atom or a fluorine atom, and Y 24 represents a fluorine atom or a cyano group, respectively.
• Examples thereof include compounds represented by.
• the compound of the present invention can be produced by the following production method.
• Manufacturing method 1 Production of a compound represented by the following formula (s-7)
• R 14 represents an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 3 to 7 carbon atoms
• A. 14 and A 24 represent groups selected from the above formulas (A-iv-1), formulas (A-iv-3) to formulas (A-iv-7), and Y 14 and Y 34 are independent of each other.
• Y 24 represents a fluorine atom or a cyano group.
• the compound represented by the formula (s-3) By reacting the compound represented by the formula (s-2) with, for example, N-iodosuccinimide, the compound represented by the formula (s-3) can be obtained.
• the compound represented by the general formula (s-5) By reacting the compound represented by the formula (s-3) with the compound represented by the general formula (s-4), the compound represented by the general formula (s-5) can be obtained.
• the reaction method include a method of cross-coupling in the presence of a metal catalyst and a base.
• the metal catalyst include [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, and dichlorobis [di-tert-butyl (p-dimethylaminophenyl) phosphino] palladium. (II), tetrakis (triphenylphosphine) palladium (0) and the like can be mentioned.
• ligands such as triphenylphosphine and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl may be added.
• the base include potassium carbonate, potassium phosphate, cesium carbonate and the like.
• the compound represented by the general formula (s-7) By reacting the compound represented by the general formula (s-5) with the compound represented by the general formula (s-6), the compound represented by the general formula (s-7) can be obtained.
• the reaction method include a Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base.
• the palladium catalyst include the above.
• Specific examples of the copper catalyst include copper (I) iodide.
• Specific examples of the base include triethylamine and the like.
• Alkyl represents an alkyl group
• Y 14 and Y 34 independently represent a hydrogen atom or a fluorine atom
• Y 24 represents a fluorine atom or a cyano group.
• the compound represented by the formula (s-10) can be obtained by reacting the compound represented by the formula (s-8) with the compound represented by the formula (s-9) in the presence of Lewis acid.
• Lewis acid include aluminum chloride (III) and the like.
• the compound represented by the formula (s-11) can be obtained by reducing the carbonyl group of the compound represented by the formula (s-10).
• Examples of the reaction method include a method using aluminum chloride (III) and lithium aluminum hydride.
• the compound represented by the formula (s-12) can be obtained by reacting the compound represented by the formula (s-11) with, for example, N-bromosuccinimide.
• the compound represented by the general formula (s-14) By reacting the compound represented by the formula (s-12) with the compound represented by the general formula (s-13), the compound represented by the general formula (s-14) can be obtained.
• the reaction method include a Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst, the copper catalyst and the base include the above.
• Reaction conditions other than those described in each step include, for example, Experimental Chemistry Course (edited by the Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Belstein Handbook of Basic Chemistry (A John Wiley & Sons, Inc., Publication). Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) as described in the literature, such as or SciFinder (Chemical Abstracts Service, American Those listed in databases such as Chemical Society) and Reaxys (Elsevier Ltd.) can be mentioned.
• the functional group can be protected as needed in each process.
• Protecting groups include, for example, GREENE'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE co-authored, A John Wiley, Inc., A John Wiley, Inc., Protecting Group, etc.) The group is mentioned.
• purification can be performed as needed in each process.
• the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment.
• the purifying agent include silica gel, alumina, activated carbon and the like.
• the compound represented by the general formula (I) is preferably used by being added to the liquid crystal composition.
• the liquid crystal composition may contain one compound represented by the general formula (I), and a plurality of compounds represented by the general formula (I). May be contained.
• the liquid crystal composition of the present invention contains a compound represented by the general formula (I)
• the total content of the compounds represented by the general formula (I) in the liquid crystal composition is 5% by mass or more. It is more preferably 10% by mass or more and 95% by mass or less, further preferably 15% by mass or more and 90% by mass or less, and 20% by mass or more and 85% by mass or less. Is particularly preferable.
• the total content of the compounds represented by the general formula (I) is expressed in the general formula (I) when the liquid crystal composition contains one compound represented by the general formula (I). It means the content of the compound represented, and when the liquid crystal composition contains a plurality of compounds represented by the general formula (I), the total content of the plurality of compounds represented by the general formula (I) is summed up. means.
• the liquid crystal composition containing the compound represented by the general formula (I) preferably has a refractive index anisotropy ( ⁇ n) of 0.15 or more and 1.00 or less.
• the refractive index anisotropy ( ⁇ n) is 0.20 or more, preferably 0.95 or less, and 0.25 or more. It is more preferably 0.90 or less, more preferably 0.30 or more and 0.85 or less, and particularly preferably 0.35 or more and 0.80 or less.
• a liquid crystal composition containing a compound represented by the general formula (I) can be applied to a high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image.
• the liquid crystal composition containing the compound represented by the general formula (I) preferably has a dielectric anisotropy ( ⁇ ) of 2 or more and 60 or less.
• the dielectric anisotropy ( ⁇ ) is preferably 2.5 or more and preferably 50 or less. It is more preferably 3 or more and 40 or less, and particularly preferably 3.5 or more and 30 or less.
• the liquid crystal composition containing the compound represented by the general formula (I) is preferably used for a high frequency device.
• the frequency range is preferably 1 MHz or more and 1 THz or less, more preferably 1 GHz or more and 500 GHz or less, further preferably 2 GHz or more and 300 GHz or less, and 5 GHz or more and 150 GHz or less. It is particularly preferable to have.
• liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (IV).
• R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.
• a 3 is the formula from the following formula (A6-1) (A6-8)
• Y 7 , Y 9 , Y 10 and Y 12 independently represent a hydrogen atom, a fluorine atom or a chlorine atom
• Y 8 and Y 11 independently represent a fluorine atom.
• R 21 represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.
• Can be different m31 represents an integer from 1 to 3 and represents Ay1 is the following formula (Ay-1-i) and formula (Ay-2-i).
• the broken line represents the bond position
• Y 71 , Y 91 , Y 101 and Y 121 independently represent a hydrogen atom, a fluorine atom or a chlorine atom
• Y 81 and Y 111 independently represent a fluorine atom.
• R 22 represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.
• a 32 represents a group selected from the above formulas (A6-1) to formula (A6-5), but when there are a plurality of A 32s, they may be the same or different.
• m32 represents 1, 2 or 3 Y 72 and Y 92 independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y 82 is a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is fluorine.
• R 23 represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
• a 33 represents a group selected from the above formulas (A6-1) to formula (A6-5), but when there are a plurality of A 33s, they may be the same or different.
• Z 43 is -CF 2 O -, - OCF 2 -, - C ⁇ C- or represents a single bond, they if Z 43 there are a plurality may be the same or different and m33 represents 1, 2 or 3 Y 73 and Y 93 independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y 83 represents a fluorine atom, a chlorine atom, a cyano group or a thioisocyano group. ) Is more preferable, and the compound represented by the general formula (VI) is from the following general formula (VI-iv-1) to the general formula (VI-iv-21).
• R 614 is a compound represented by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. preferable.
• liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (III).
• R 31 and R 32 are independently alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, or carbon atoms 2 to 7 respectively.
• Represents the alkenyloxy group of A 31 and A 32 are independently expressed by the following equations (A3-1) to (A3-8).
• the broken line represents the bonding position.
• m31 represents an integer from 1 to 4.
• the compound represented by the general formula (III) is represented by the following general formula (III-i).
• R 311 and R 321 each independently have an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 2 to 4 carbon atoms.
• Represents the alkenyloxy group of A 311 and A 321 are independently derived from the following equations (A31-1) to (A31-6).
• R 312 and R 322 are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of A 312 and A 322 are independently derived from the following equations (A32-1) to (A32-4).
• R 313 and R 323 independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
• a 313 and A 323 are independently represented by the following equations (A33-1) and (A33-2), respectively.
• R 314 and R 324 independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms). It is particularly preferable that the compound is a compound.
• the compound represented by the general formula (I) may be added to a liquid crystal composition having a neutral or negative dielectric anisotropy ( ⁇ ).
• the liquid crystal composition containing the compound represented by the general formula (I) preferably has a dielectric anisotropy ( ⁇ ) of ⁇ 20 or more and 2 or less.
• Permittivity anisotropy ( ⁇ ) should be -15 or more and 1.5 or less from the viewpoint of liquid crystal phase temperature range, storage stability, weather resistance, driving voltage, rotational viscosity and elastic modulus of the liquid crystal composition. It is preferably -10 or more and 1 or less, and particularly preferably -5 or more and 0.5 or less.
• the liquid crystal composition When the dielectric anisotropy ( ⁇ ) of the liquid crystal composition containing the compound represented by the general formula (I) is neutral or negative, the liquid crystal composition has the following general formula (IV).
• R 41 and R 42 are independently alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, or carbon atoms 2 to 7 respectively.
• Represents the alkenyloxy group of A 41 and A 42 are independently expressed by the following equations (A4-1) to (A4-11).
• the broken line represents the bonding position.
• a 41s when there are a plurality of A 41s, they may be the same or different, and when there are a plurality of A 42s, they are the same.
• Z 41 and Z 42 are independently -O-, -S-, -OCH 2- , -CH 2 O-, -CH 2 CH 2- , -CO-, -COO-, -OCO-, -CO.
• m41 and m42 independently represent integers from 0 to 3, while m41 + m42 represent integers from 1 to 3. ) May be contained.
• the compound represented by the general formula (IV) is represented by the following general formula (IV-i).
• R 411 and R 421 are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of Although A 411 and A 421 each independently represent a group selected from the formula (A4-9) from the above equation (A4-1), they if A 411 there are a plurality optionally be the same or different If there are multiple A 421s, they may be the same or different.
• n411 and m421 independently represent integers from 0 to 3, while m411 + m421 represent integers from 1 to 3.
• R 412 and R 422 are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of Although A 412 and A 422 each independently represent a group selected from the formula (A4-7) from the above equation (A4-1), they if A 412 there are a plurality optionally be the same or different If there are multiple A 422s, they may be the same or different.
• Z 412 and Z 422 independently form -OCH 2- , -CH 2 O-, -CH 2 CH 2- , -COO-, -OCO-, -CF 2 O-, -OCF 2- or single bond.
• Z 412s when there are a plurality of Z 412s, they may be the same or different, and when there are a plurality of Z 422s, they may be the same or different.
• m412 and m422 independently represent 0, 1 or 2, while m412 + m422 represent 1 or 2.
• the compound represented by the general formula (IV) is the following general formula (IV-iii).
• R 413 and R 423 independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, respectively.
• a 413 and A 423 each independently represent a group selected from the formula (A4-5) from the above equation (A4-1), they if A 413 there are a plurality optionally be the same or different If there are multiple A 423s, they may be the same or different.
• Z 413 and Z 423 independently represent -OCH 2- , -CH 2 O-, -CH 2 CH 2- or a single bond, but if there are multiple Z 413s, they are the same but different.
• m413 and m423 independently represent 0, 1 or 2, while m413 + m423 represent 1 or 2.
• the compound represented by the general formula (IV) is from the following general formula (IV-iv-1) to the general formula (IV-iv-8).
• R 414 and R 424 independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms). It is particularly preferable that the compound is a compound.
• a stabilizer may be added to the liquid crystal composition containing the compound represented by the general formula (I) in order to improve its storage stability.
• stabilizers examples include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, ⁇ -naphthylamines, ⁇ -naphthols, nitroso compounds and the like. Be done.
• the amount added is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable.
• one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination.
• the following general formula (X1) is used as a stabilizer.
• Sp x1 has one -CH 2- or two or more non-adjacent -CH 2- independently of -O-, -S-, -CO-, -COO-, and -OCO.
• a x1 is from the following formula (Ax1-1) to formula (Ax1-8).
• Sp x11 is a carbon in which one -CH 2- or two or more non-adjacent-CH 2 -s may be independently substituted with -O-, -COO- or -OCO-, respectively.
• a x11 is the following formula (Ax11-1) and formula (Ax11-2).
• the broken line represents the bonding position.
• a x11 represents -COO-, -OCO-, -OCO-CH 2 CH 2- , -CH 2 CH 2- COO- or a single bond, but if there are multiple Z x11s , they are different even if they are the same. May be mx11 represents 0 or 1 and represents mx21 represents 0 or 1. ) Is preferable, and the compound represented by the general formula (X1) is from the following general formula (X1-ii-1) to the general formula (X1-ii-4).
• Sp x12 represents an alkylene group or a single bond having 1 to 20 carbon atoms. It is particularly preferable that the compound is represented by.
• liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (X2).
• R x21 , R x22 , R x23 and R x24 each independently represent a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
• Sp x21 , Sp x22 , Sp x23 and Sp x22 each independently represent a spacer group or a single bond.
• mx21 represents 0 or 1 and represents mx22 represents 0 or 1
• mx23 represents 0 or 1.
• the compound represented by the general formula (X2) is represented by the following general formula (X2-i).
• R x211 , Rx221 , Rx231 and Rx241 independently represent a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, respectively.
• Sp x211 , Sp x221 , Sp x231 and Sp x221 may each independently replace any hydrogen atom in the group with a fluorine atom, and one -CH 2- or two or more non-adjacent hydrogen atoms.
• R x212 and R x222 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, respectively.
• Sp x212 and Sp x222 each independently replace one -CH 2- or two or more non-adjacent -CH 2-s with -O-, -COO- or -OCO-, respectively. It represents a linear alkylene group or a single bond having 1 to 10 carbon atoms which may be used.
• mx212 represents 0 or 1.
• Is more preferable, and the compound represented by the general formula (X2) is represented by the following general formula (X2-iii).
• R x213 and Rx223 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, respectively.
• Sp x213 is a linear chain having 1 to 10 carbon atoms in which one -CH 2- or two or more non-adjacent -CH 2-s may be independently replaced with -COO- or -OCO-. Represents a alkylene group. ) Is particularly preferable.
• the ring structure contained in the 1,4-cyclohexylene group, the decahydronaphthalene-2,6-diyl group and the 1,3-dioxane-2,5-diyl group is either a trans form or a cis form, respectively.
• the content of each trans form is preferably higher than that of the cis form, and the content of the trans form in the ring structure is more preferably 80% or more.
• the content of the trans body in the ring structure is more preferably 90% or more, the content of the trans body in the ring structure is even more preferably 95% or more, and the content of the trans body in the ring structure is 98. % Or more is particularly preferable.
• each element may be replaced with an isotope of the same element.
• each compound is UPLC (Waters ACQUITY UPLC, BEH C 18 (100 x 2.1 mm x 1.7 ⁇ m), acetonitrile / water or acetonitrile / water containing 0.1% formic acid, PDA, column temperature 40 ° C.), GPC ( Shimadzu HPLC Prominence, Shodex KF-801 (300 mm x 8 mm x 6 ⁇ m) + KF-802 (300 mm x 8 mm x 6 ⁇ m), acetonitrile, RI, UV (254 nm), column temperature 40 ° C.), GC (Agient 6890A, J & W DB- Determined by 1, 30 m x 0.25 mm x 0.25 ⁇ m, carrier gas He, FID, 100 ° C (1 minute) ⁇ temperature rise 10 ° C / min ⁇ 300 ° C (12 minutes)) or 1 H NMR (JEOL, 400 MHz). did. (Example 1) Production of
• reaction mixture was poured into water and extracted with toluene.
• the organic layer is washed successively with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane), activated carbon treatment and recrystallization (acetone / methanol) to obtain the formula (I-1). 2.8 g of the represented compound was obtained.
• the compound represented by the formula (I-2-3) is obtained by sequentially washing the organic layer with 5% hydrochloric acid and a saline solution, and then purifying the organic layer by column chromatography (silica gel, dichloromethane / hexane) and activated carbon treatment. 0 g was obtained.
• the organic layer is sequentially washed with water and brine, and then purified by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallized (ethyl acetate / hexane), thereby represented by the formula (I-6-4). 5.3 g of the compound to be obtained was obtained.
• the organic layer is represented by the formula (I-7-6) by sequentially washing with water and brine, and then purifying by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol). 7.3 g of compound was obtained.
• Example 1 the compound represented by the formula (I-1-4) is the compound represented by the formula (I-7-7), and the compound represented by the formula (I-1-5) is represented by the formula (I-1-5).
• a compound represented by the formula (I-7) was produced by the same method except that the compound represented by -7-8) was replaced.
• MS (EI): m / z 468 (Example 8) Production of a compound represented by the formula (I-8)
• Example 1 the compound represented by the formula (I-1-4) is the compound represented by the formula (I-9-1), and the compound represented by the formula (I-1-5) is represented by the formula (I-1-5).
• a compound represented by the formula (I-9) was produced by the same method except that it was replaced with the compound represented by -9-2).
• MS (EI): m / z 472 (Example 10) Production of a compound represented by the formula (I-10)
• the organic layer is represented by the formula (I-10-3) by sequentially washing with water and a saline solution and then purifying by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol). 5.0 g of the compound was obtained.
• the compound 4 represented by the formula (I-10) is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / hexane) after sequentially washing the organic layer with water and saline. 0.0 g was obtained.
• MS (EI): m / z 406 (Example 11) Production of a compound represented by the formula (I-11)
• the organic layer is represented by the formula (I-11-6) by sequentially washing with water and a saline solution and then purifying by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol). 4.9 g of compound was obtained.
• Example 8 the compound represented by the formula (I-8-1) is the compound represented by the formula (I-15-1), and the compound represented by the formula (I-8-2) is the compound represented by the formula (I-8-2).
• a compound represented by the formula (I-15-3) was produced by the same method except that the compound represented by -15-2) was replaced.
• Example 14 the compound represented by the formula (I-14-1) is the compound represented by the formula (I-15-3), and the compound represented by the formula (I-14-2) is represented by the formula (I-14-2).
• a compound represented by the formula (I-15) was produced by the same method except that the compound represented by -15-4) was replaced.
• MS (EI): m / z 410 (Example 16) Production of a compound represented by the formula (I-16)
• Example 7 the compound represented by the formula (I-7-7) is the compound represented by the formula (I-16-5), and the compound represented by the formula (I-7-8) is the compound represented by the formula (I-7-8).
• a compound represented by the formula (I-16) was produced by the same method except that the compound represented by -16-6) was replaced.
• MS (EI): m / z 502 (Example 17) Production of a compound represented by the formula (I-17)
• the organic layer is represented by the formula (I-18-5) by sequentially washing with water and saline and then purifying by column chromatography (silica gel, toluene / heptane) and recrystallization (toluene / ethanol). 6.3 g of compound was obtained.
• Example 6 the compound represented by the formula (I-6-1) is the compound represented by the formula (I-18-5), and the compound represented by the formula (I-6-2) is the compound represented by the formula (I-6-2).
• a compound represented by the formula (I-18) was produced by the same method except that the compound represented by -18-6) was replaced.
• MS (EI): m / z 481 (Example 19) Production of a compound represented by the formula (I-19)
• the organic layer is represented by the formula (I-19-6) by sequentially washing with water and saline and then purifying by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol). 7.0 g of the compound was obtained.
• the compound represented by the formula (I-20) 8 is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) after sequentially washing the organic layer with water and saline. .1 g was obtained.
• MS (EI): m / z 584 (Example 21 and Comparative Example 1) In the examples, the following abbreviations are used for the description of the liquid crystal compound. (Ring structure)
• each compound to be evaluated was evaluated.
• 2 mL of each obtained liquid crystal composition was sealed in a glass vial under an argon atmosphere, and the state after storage at 10 ° C. for 4 weeks was visually evaluated.
• the evaluation results are shown in the table below.
• the compound of the present invention is less likely to precipitate when added to the liquid crystal composition and has high compatibility with the liquid crystal composition.
• Each liquid crystal composition to be evaluated was enclosed in a TN cell having a thickness of 8.5 ⁇ m.
• a rectangular voltage of 30 V at a frequency of 100 Hz was applied to each of the obtained liquid crystal cells at 50 ° C. for 50 hours.
• the voltage holding ratio was measured for each liquid crystal cell, and the difference ( ⁇ V HR ) in the voltage holding ratio before and after the voltage was applied was calculated.
• ⁇ V HR the difference in the voltage holding ratio before and after the voltage was applied was calculated.
• the voltage holding ratio was measured at a frequency of 60 Hz and an applied voltage of 1 V and 333 K. The results are shown in the table below.
• the device using the liquid crystal composition to which the compound of the present invention is added is less likely to cause a decrease in the voltage retention rate.
• each obtained liquid crystal composition in the high frequency region was evaluated.
• a transmission delay method Cut back type stripline method relative permittivity / dielectric loss tangent measuring device manufactured by KEYCOM
• each physical property value is defined as follows.
• the compound of the present invention has a large refractive index anisotropy ⁇ n, has high compatibility with the liquid crystal composition, and has a voltage retention rate of the element when the element is manufactured by adding it to the liquid crystal composition. It is useful as a material for elements such as a high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image.
• elements such as a high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image.

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