WO2022198557A1

WO2022198557A1 - Compound, liquid crystal composition and high-frequency phase shifter

Info

Publication number: WO2022198557A1
Application number: PCT/CN2021/082968
Authority: WO
Inventors: Jia MA; Masanao Hayashi; Zhimin Li; Jinqiu LI
Original assignee: DIC Corp; Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2021-03-25
Filing date: 2021-03-25
Publication date: 2022-09-29
Anticipated expiration: 2023-09-25
Also published as: JP2023547538A; CN116867790A; JP7428296B2; TWI867229B; TW202248403A

Abstract

Providing a compound represented by the general formula (I), which contains, in its structure, a thieno [3, 2-b] thiophene-2, 5-diyl group having a sulfur atom bonded at the 2-position; and providing a liquid crystal composition containing the compound and a device using the liquid crystal composition. The disclosed compound has a large refractive index anisotropy Δn and a high compatibility with a liquid crystal composition, and exhibits a large dielectric constant anisotropy in a high frequency region; and therefore, it is useful as a material for a device of a high-frequency phase shifter, a phased array antenna, an image recognition device, distance measuring equipment, a liquid crystal display device, a liquid crystal lens, a birefringent lens for stereoscopic image display, or the like.

Description

COMPOUND, LIQUID CRYSTAL COMPOSITION AND HIGH-FREQUENCY PHASE SHIFTER

[Technical Field]

The present invention relates to a compound, a liquid crystal composition containing the compound, and a device using the liquid crystal composition.

[Background Art]

A liquid crystal composition is used for mobile terminals such as smartphones and tablet devices, and display applications such as TVs and window displays. As a new application of such a liquid crystal composition, an antenna for transmitting and receiving radio waves between a communication satellite and a mobile body such as a car is drawing attention.

Conventionally, satellite communications use a parabolic antenna; however, when used in a mobile body, the parabolic antenna must be directed toward a satellite at any time, and is required to have a large movable portion. However, an antenna using a liquid crystal composition is capable of changing transmission-reception directions of radio waves by operating liquid crystal, and therefore, movement of the antenna itself is not necessary and the antenna is allowed to have a planar shape.

A refractive index anisotropy Δn of liquid crystal compositions required for these applications is, for example, about 0.4, which is much larger than Δn required for display applications.

Therefore, a compound to be added to and used in a liquid crystal composition is required to have a large Δn and a high compatibility with the liquid crystal composition.

Conventionally, a compound having a thienothiophene structure has been reported as a compound having a large Δn. However, these compounds disadvantageously have low compatibility when added to a liquid crystal composition used for antennas and have precipitation caused by long-term storage (Non-Patent Literature 1 and Patent Literatures 1 and 2) . Further, compounds having a thienothiophene structure and a thioisocyano group have been reported, but these compounds have a low dielectric constant anisotropy in a high frequency region and insufficient phase modulation characteristics (Patent Literatures 3 and 4) . Therefore, there has been demand for the development of a compound having a large Δn and a high compatibility with a liquid crystal composition, and exhibiting a large dielectric constant anisotropy in a high frequency region.

[Citation List]

[Non-Patent Literature]

[Non-Patent Document 1] Chemistry of Materials, 2009, Vol. 21, No. 13, pp. 2727-2732

[Patent Literature]

[Patent Literature 1] CN103472116A

[Patent Literature 2] JP2012-167068A

[Patent Literature 3] CN106518890A

[Patent Literature 4] WO2020/120586A1

[Summary of Invention]

[Problems to be Solved by the Invention]

The problem to be solved by the present invention is to provide: a compound that has a large refractive index anisotropy (Δn) and a high compatibility with a liquid crystal composition, and exhibits a large dielectric constant anisotropy (Δε) in a high frequency region; a liquid crystal composition containing the compound; and a device using the liquid crystal composition.

[Means for Solving the Problems]

As a result of intensive studies to solve the above problems, the present inventors have developed a specific compound. That is, the present invention provides a compound represented by the following general formula (I) ,

[Chemical formula 1]

(in the formula, R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein an arbitrary hydrogen atom in the alkyl group may be substituted with a halogen atom, and one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-or -C≡C- with the proviso that oxygen atoms are not bonded to each other;

A ¹ and A ² each independently represent a hydrocarbon ring or a heterocycle having 3 to 16 carbon atoms which may be substituted; when multiple A ¹s are present, the A ¹s may be the same or different; and when multiple A ²s are present, the A ²s may be the same or different;

Z ¹, Z ² and Z ³ each independently represent a divalent linking group or a single bond; when multiple Z ¹s are present, the Z ¹s may be the same or different; and when multiple Z ²s are present, the Z ²s may be the same or different;

m1 and m2 each independently represent an integer from 0 to 3; and

A ^x represents a hydrogen atom, a fluorine atom, a chlorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein an arbitrary hydrogen atom in the alkyl group is optionally substituted with a halogen atom; one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-or -C≡C-with the proviso that oxygen atoms are not bonded to each other; or A ^x represents a structure selected from the group consisting of (Ax-1) to (Ax-5) ,

(in the formulas, the broken line represents a binding position, and Y ¹ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or an alkyl group or alkoxy group having 1 to 8 carbon atoms in which an arbitrary hydrogen atom may be substituted with a fluorine atom, and when multiple Y ¹s are present, they may be the same or different; Y ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms in which an arbitrary hydrogen atom may be substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, CF=CF- or -C≡C- with the proviso that oxygen atoms are not bonded to each other) , wherein when A ^x is a structure selected from the group consisting of the formulas (Ax-1) to (Ax-5) , m1+m2 represents an integer from 0 to 3; and when A ^x is not a structure selected from the group consisting of the formulas (Ax-1) to (Ax-5) , m1+m2 represents an integer from 1 to 4) ;

and provides a liquid crystal composition containing the compound and a device using the liquid crystal composition.

[Advantageous Effect (s) of Invention]

The compound of the present invention has a large refractive index anisotropy Δn and a high compatibility with a liquid crystal composition, and exhibits a large dielectric constant anisotropy in a high frequency region; and therefore, it is useful as a material for a device of a high-frequency phase shifter, a phased array antenna, an image recognition device, distance measuring equipment, a liquid crystal display device, a liquid crystal lens, a birefringent lens for stereoscopic image display, or the like.

[Description of Embodiments]

The present invention provides a compound represented by the general formula (I) , a liquid crystal composition containing the compound, and a device using the liquid crystal composition. In the general formula (I) , R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms; and an arbitrary hydrogen atom in the alkyl group may be substituted with a halogen atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-, wherein oxygen atoms are not bonded to each other. From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the voltage holding ratio, the easiness of synthesis and the availability of raw materials, R ¹ preferably represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group may be substituted with a halogen atom and one -CH ₂- or two or more -CH ₂-’s in the group may be each independently substituted with -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-; R ¹ more preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms wherein an arbitrary hydrogen atom in the group may be substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the group may be each independently substituted with -O-, -CH=CH- or -C≡C-; R ¹ further preferably 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, an alkenyloxy group having 2 to 7 carbon atoms or an alkynyl group having 2 to 8 carbon atoms; and R ¹ particularly preferably 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.

In the general formula (I) , A ¹ and A ² each independently represent a hydrocarbon ring or heterocycle having 3 to 16 carbon atoms that may be substituted wherein: when multiple A ¹s are present, they may be the same or different; and when multiple A ²s are present, they may be the same or different. From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the dielectric constant anisotropy, the voltage holding ratio, the easiness of synthesis, and the availability of raw materials, A ¹ and A ² may be each independently unsubstituted or substituted with one or more substituents L ¹ and preferably represent a group selected from the group consisting of:

(a) a 1, 4-cyclohexylene group (wherein one -CH ₂- or two or more nonadjacent -CH ₂-’s present in the group may be substituted with -O- or -S-) ;

(b) a 1, 4-phenylene group (wherein one -CH= or two or more nonadjacent -CH=’s present in the group may be substituted with -N=) ;

(c) a 1, 4-cyclohexenylene group, a bicyclo [2.2.2] octane-1, 4-diyl group, a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 1, 2, 3, 4-tetrahydronaphthalene-2, 6-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, a decahydronaphthalene-2, 6-diyl group, an anthracene-2, 6-diyl group, an anthracene-1, 4-diyl group, an anthracene-9, 10-diyl group, or a phenanthrene-2, 7-diyl group (wherein a hydrogen atom present in the groups may be substituted with a fluorine atom or a chlorine atom, and one -CH= or two or more -CH=’s present in a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 1, 2, 3, 4-tetrahydronaphthalene-2, 6-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, an anthracene-2, 6-diyl group, an anthracene-1, 4-diyl group, an anthracene-9, 10-diyl group or a phenanthrene-2, 7-diyl group may be substituted with -N=) ; and

(d) a thiophene-2, 5-diyl group, a benzothiophene-2, 5-diyl group, a benzothiophene-2, 6-diyl group, a dibenzothiophene-3, 7-diyl group, a dibenzothiophene-2, 6-diyl group, or a thieno [3, 2-b] thiophene-2, 5-diyl group (wherein one -CH= or two or more nonadjacent -CH='s present in the group may be substituted with -N=) . When multiple A ¹s and A ²s are present, they may be the same or different, and they may be each independently unsubstituted or substituted with one or more substituents L ¹; and they more preferably represent a group selected from a 1, 4-phenylene group, a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 5, 6, 7, 8 tetrahydronaphthalene-1, 4-diyl group, a phenanthrene-2, 7-diyl group, a benzothiophene-2, 5-diyl group, a benzothiophene-2, 6-diyl group, a benzothiazole-2, 5-diyl group, a benzothiazole-2, 6-diyl group, a dibenzothiophene-3, 7-diyl group, a dibenzothiophene-2, 6-diyl group or a thieno [3, 2-b] thiophene-2, 5-diyl group. When multiple A ¹s and A ²s are present, they may be the same or different; and further preferably, they each independently represent a group selected from the following formulas (A-1) to (A-17) .

[Chemical formula 2]

(In the formula, the broken line represents a binding position, and when multiple L ¹s are present, they may be the same or different. ) When multiple A ¹s and A ²s are present, they may be the same or different; and further more preferably, A ¹ and A ² each independently represent a group selected from the formulas (A-1) to (A-7) , (A-12) , (A-15) and (A-17) . When multiple A ¹s and A ²s are present, they may be the same or different; and particularly preferably, A ¹ and A ² each independently represent a group selected from the formulas (A-1) , and (A-3) to (A-7) . L ¹ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms wherein one -CH ₂- or two or more -CH ₂-’s may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- with the proviso that oxygen atoms are not directly bonded to each other, wherein an arbitrary hydrogen atom in the alkyl group represents a group that may be substituted with a fluorine atom. From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the dielectric constant anisotropy, the voltage holding ratio, the easiness of synthesis and the availability of raw materials, L ¹ preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group may be substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the group may be each independently substituted with -O-, -S-, -CH=CH, -CF=CF- or -C≡C-. L ¹ more preferably 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 wherein an arbitrary hydrogen atom in the group may be substituted with a fluorine atom and -CH ₂- in the group may be substituted with -O-. L ¹ further preferably 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. L ¹ particularly preferably represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms.

In the general formula (I) , Z ¹, Z ² and Z ³ each independently represent a divalent linking group or a single bond, but when multiple Z ¹s are present, they may be the same or different; and when multiple Z ²s are present, they may be the same or different. From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the dielectric constant anisotropy, the voltage holding ratio, the easiness of synthesis and the availability of raw materials, Z ¹, Z ² and Z ³, each independently, preferably represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH ₂O-, -OCH ₂-, -CF ₂O-, -OCF ₂-, -CH=CHCOO-, -OCOCH=CH-, -CH=C (CH ₃) COO-, -OCOC (CH ₃) =CH-, -CH ₂-CH (CH ₃) COO-, -OCOCH (CH ₃) -CH ₂-, -OCH ₂CH ₂O-, -N=N-, -C=N-N=C-, -CH=N-, -N=CH-, -C≡C-C≡C- or an alkylene group having 2 to 20 carbon atoms, wherein one -CH ₂- or two or more -CH ₂-’s in the alkylene group represent a group that may be substituted with -O-, -S-, -COO- or -OCO-. When multiple Z ¹s, Z ²s and Z ³s are present, they may be the same or different; and more preferably, they each independently represent -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -CF ₂O-, -OCF ₂-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C- or a single bond. When multiple Z ¹s, Z ²s and Z ³s are present, they may be the same or different; and further preferably, they each independently represent -CF ₂O-, -OCF ₂-, -CH=CH-, -CF=CF-, -N=N-, -C≡C-, -C≡C-C≡C- or a single bond. When multiple Z ¹s, Z ²s and Z ³s are present, they may be the same or different; and further more preferably, they each independently represent -CF ₂O-, -OCF ₂-, -N=N-, -C≡C-, -C≡C-C≡C- or a single bond. When multiple Z ¹s, Z ²s and Z ³s are present, they may be the same or different; and particularly preferably, they each independently represent -C≡C- or a single bond.

In the general formula (I) , m1 and m2 each independently represent an integer from 0 to 3, and m1+m2 is preferably an integer from 0 to 4; in particular, when A ^x is a structure selected from the group consisting of the formulas (Ax-1) to (Ax-5) , m1+m2 is preferably an integer from 0 to 3, further preferably an integer from 0 to 2. In addition, when A ^x is not a structure selected from the group consisting of (Ax-1) to (Ax-5) , m1+m2 is preferably an integer from 1 to 4, more preferably an integer from 1 to 3. From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the dielectric constant anisotropy, the voltage holding ratio, the easiness of synthesis, and the availability of raw materials, it is preferred that m1 and m2 each independently represent 0, 1, or 2 and m1+m2 represents an integer from 1 to 3; it is more preferred that m1 and m2 each independently represent 0, 1 or 2 and m1+m2 represents 1 or 2; it is further preferred that m1 and m2 each independently represent 0 or 1 and m1+m2 represents 1 or 2; and it is particularly preferred that m1 and m2 each independently represent 0 or 1 and m1+m2 represents 1.

Since the compound represented by the general formula (I) includes a thieno [3, 2-b] thiophene-2, 5-diyl group having a sulfur atom bonded at the 2-position in the structure, it can effectively enhance Δn due to the conjugated structure of a high electron density derived from 3 sulfur atoms and simultaneously shows an excellent effect of exhibiting a large dielectric constant anisotropy in a high frequency region. Further, since the general formula (I) has two or more ring structures in total in the molecule, it forms a rod-like molecular structure as the entire compound thereby to improve the liquid crystallinity and increase Tni, and therefore, addition thereof to a liquid crystal composition can effectively broaden the liquid crystal phase temperature range while maintaining a high compatibility.

In the general formula (I) , A ^x represents a hydrogen atom, a fluorine atom, a chlorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and an arbitrary hydrogen atom in the alkyl group may be substituted with a halogen atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- with the proviso that oxygen atoms are not bonded to each other. Alternatively, A ^x represents a structure selected from the group consisting of the following formulas (Ax-1) to (Ax-5) .

(In the formulas, the broken line represents a binding position, Y ¹ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or an alkyl group or alkoxy group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom wherein: when multiple Y ¹s are present, the Y ¹s are may be the same or different; Y ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- with the proviso that oxygen atoms are not bonded to each other. ) From the viewpoints of the compatibility with a liquid crystal composition, the refractive index anisotropy, the dielectric constant anisotropy, the voltage holding ratio, the easiness of synthesis and the availability of raw materials, A ^x preferably represents a structure selected from the group consisting of the following formulas (Ax-1-i) to (Ax-5-i) .

(In the formula, the broken line represents a binding position, Y ¹¹ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group or alkoxy group having 1 to 8 carbon atoms wherein when multiple Y ¹¹s are present, they may be the same or different, and Y ²¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CH=CH-, -CF=CF- or -C≡C- with the proviso that oxygen atoms are not bonded to each other) . A ^x further preferably represents the formula (Ax-1-i) or (Ax-2-i) . In addition, A ^x particularly preferably represents a group selected from the following formula (Ax-1-ii) .

[Chemical formula 3]

(In the formula, the broken line represents a binding position; and

Y ¹³ each independently represents a hydrogen atom, a fluorine atom or a chlorine atom) .

Further, in the compound represented by the general formula (I) , from the viewpoint of the solubility in a liquid crystal composition, the partial structure represented by

[Chemical formula 4]

and the partial structure represented by

[Chemical formula 5]

are preferably different from each other.

From the viewpoints of the width of a temperature range exhibiting a liquid crystal phase, the dielectric constant anisotropy, the compatibility with a liquid crystal composition, the refractive index anisotropy, the voltage holding ratio, the easiness of synthesis and the availability of raw materials, the compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-i) ,

[Chemical formula 6]

(in the formula, R ¹¹ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group is optionally substituted with a halogen atom and one -CH ₂- or two or more -CH ₂-’s in the group are each independently and optionally substituted with -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-;

A ¹¹ and A ²¹ each independently represent a 1, 4-phenylene group, a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, a phenanthrene-2, 7-diyl group, a benzothiophene-2, 5-diyl group, a benzothiophene-2, 6-diyl group, a benzothiazole-2, 5-diyl group, a benzothiazole-2, 6-diyl group, a dibenzothiophene-3, 7-diyl group, a dibenzothiophene-2, 6-diyl group or a thieno [3, 2-b] thiophene-2, 5-diyl group, wherein when multiple A ¹¹s are present, they may be the same or different;

when multiple A ²¹s are present, they may be the same or different; and these groups may be unsubstituted or substituted with one or more substituents L ¹¹;

L ¹¹ represents a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 20 carbon atoms, or branched or cyclic alkyl group having 3 to 20 carbon atoms wherein an artibrary hydrogen atom in the group is optionally substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the group are each independently and optionally substituted with -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-, wherein when multiple L ¹¹s are present, the L ¹¹s are optionally the same or different;

Z ¹¹, Z ²¹ and Z ³¹ each independently represent -OCH ₂-, -CH ₂O-, -SCH ₂-, -CH ₂S-, -CH ₂CH ₂-, -CF ₂O-, -OCF ₂-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C-or a single bond wherein: when multiple Z ¹¹s are present, the Z ¹¹s are optionally the same or different; and when multiple Z ²¹s are present, the Z ²¹s are optionally the same or different;

m11 and m21 each independently represent 0, 1 or 2;

A ^x1 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group is optionally substituted with a halogen atom and one -CH ₂- or two or more -CH ₂-’s in the group are each independently optionally substituted with -O-, -S-, -CH=CH-, -CF=CF- or -C≡C-, or A ^x1 represents a structure selected from the group consisting of the following formulas (Ax-1-i) to (Ax-5-i) ,

(in the formula, the broken line represents a binding position; Y ¹¹ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group or alkoxy group having 1 to 8 carbon atoms wherein when multiple Y ¹¹s are present, the Y ¹¹s may be the same or different; and Y ²¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom is optionally substituted with a fluorine atom and one -CH ₂- or two or more -CH ₂-’s in the alkyl group may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CH=CH-, -CF=CF- or -C≡C- with the proviso that oxygen atoms are not bonded to each other) , wherein: when A ^x1 is a structure selected from the group consisting of the formulas (Ax-1-i) to (Ax-5-i) , m11+m21 represents an integer from 0 to 2; and when A ^x1 is not a structure selected from the group consisting of the formulas (Ax-1-i) to (Ax-5-i) , m11+m21 represents an integer from 1 to 3) .

In addition, the compound represented by the general formula (I) is more preferably a compound represented by the following general formula (I-ii) ,

[Chemical formula 7]

(in the formula, R ¹² represents a linear or branched alkyl group having 1 to 12 carbon atoms wherein an arbitrary hydrogen atom in the group may be substituted with a fluorine atom, and one -CH ₂-or two or more -CH ₂-’s in the group may be each independently substituted with -O-, -CH=CH- or -C≡C-;

A ¹² and A ²² each independently represent a group selected from the following formulas (A-ii-1) to (A-ii-17) ,

[Chemical formula 8]

(in the formulas, the broken line represents a binding position, and when multiple L ¹²s are present, the L ¹²s are optionally the same or different) wherein: when multiple A ¹²s are present, the A ¹²s are optionally the same or different; and when multiple A ²²s are present, the A ²²s are optionally the same or different;

L ¹² 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 wherein an arbitrary hydrogen atom in the group is optionally substituted with a fluorine atom and -CH ₂-in the group is optionally substituted with -O-;

Z ¹², Z ²² and Z ³² each independently represent -OCH ₂-, -CH ₂O-, -SCH ₂-, -CH ₂S-, -CH ₂CH ₂-, -CF ₂O-, -OCF ₂-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C- or a single bond wherein: when multiple Z ¹²s are present, the Z ¹²s are optionally the same or different; and when multiple Z ²²s are present, the Z ²²s are optionally the same or different;

m12 and m22 each independently represent 0, 1 or 2, and m12+m22 represents an integer from 0 to 2;

A ^x2 represents a structure selected from the formulas (Ax-1-i) and (Ax-2-i) ) . The compound represented by the general formula (I) is further preferably a compound represented by the following general formula (I-iii) ,

[Chemical formula 9]

(in the formula, R ¹³ 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, an alkenyloxy group having 2 to 7 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms;

A ¹³ and A ²³ each independently represent the following formulas (A-iii-1) to (A-iii-7) , (A-iii-12) , (A-iii-15) and (A-iii-17) ;

[Chemical formula 10]

(in the formulas, the broken line represents a binding position, and when multiple L ¹³s are present, the L ¹³s are optionally the same or different) ;

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;

Z ¹³, Z ²³ and Z ³³ each independently represent -CF ₂O-, -OCF ₂-, -N=N-, -CH=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C- or a single bond;

m13 and m23 each independently represent 0 or 1;

Y ¹³ each independently represents a hydrogen atom, a fluorine atom or a chlorine atom) . In particular, the compound represented by the general formula (I) is particularly preferably a compound represented by the following general formula (I-iv-1) or (I-iv-2) ,

[Chemical formula 11]

(in the formulas, 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 ²⁴ represents a group selected from the following formulas (A-iv-1) , and (A-iv-3) to (A-iv-7) ;

[Chemical formula 12]

(in the formulas, the broken line represents a binding position, and when multiple L ¹⁴s are present, they may be the same or different) ;

L ¹⁴ represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms;

Z ²⁴ and Z ³⁴ independently represent -C≡C-, -C≡C-C≡C-or a single bond; and

Y ¹⁴ and Y ³⁴ each independently represent a hydrogen atom or a fluorine atom) .

Specific examples of the compound represented by the general formula (I) include compounds represented by the following formulas (I-1) to (I-69) .

[Chemical formula 13]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

[Chemical formula 20]

[Chemical formula 21]

[Chemical formula 22]

The compound of the present invention can be produced by the following production method.

(Production method 1) Production of a compound represented by the following formula (s-5)

[Chemical formula 23]

(In the formulas, R ^1s, A ^1s, A ^2s, Z ^1s, Z ^2s, Z ^3s, m1s, m2s and A ^xs have the same meanings as R ¹, A ¹, A ², Z ¹, Z ², Z ³, m1, m2 and A ^x in the above general formula (I) . )

Reaction of a compound represented by the formula (s-1) with a compound represented by the formula (s-15) and sulfur provides a compound represented by the formula (s-2) .

Reaction of the compound represented by the formula (s-2) with, for example, N-bromosuccinimide, provides a compound represented by the formula (s-3) .

The compound represented by the formula (s-3) is reacted with trimethylsilylacetylene and then, reacted with tetrafluoroammonium fluoride (TBAF) , and thereby, a compound represented by the general formula (s-4) is obtained. Examples of the reaction method include Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base.

Specific examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0) . Specific examples of the copper catalyst include copper (I) iodide. Specific examples of the base include triethylamine.

Reaction of the compound represented by the formula (s-4) with a compound represented by the formula (s-16) provides a compound represented by the general formula (s-5) . Examples of the reaction method include Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst include those described above. Specific examples of the copper catalyst include copper iodide (I) . Specific examples of the base include triethylamine.

(Production method 2) Production of a compound represented by the following formula (s-10)

[Chemical formula 24]

(In the formulas, R ^1s, A ^1s, Z ^1s, m1s and Y ^1s have the same meanings as R ¹, A ¹, Z ¹, m1 and Y ¹ in the above general formula (I) . )

Reaction of a compound represented by the formula (s-3) with a compound represented by the general formula (s-6) provides a compound represented by the general formula (s-7) . Examples of the reaction method include a method of cross-coupling in the presence of a metal catalyst and a base. Specific examples of the metal catalyst include

[1, 1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, dichlorobis [di-tert-butyl (p-dimethylaminophenyl) phosphino] p alladium (II) , and tetrakis (triphenylphosphine) palladium (0) . When palladium (II) acetate is used as the metal catalyst, a ligand such as triphenylphosphine or

2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl may be added. Specific examples of the base include potassium carbonate, potassium phosphate, and cesium carbonate.

Reaction of the compound represented by the general formula (s-7) with, for example, hydroxylamine, provides a compound represented by the general formula (s-8) .

Reaction of the compound represented by the general formula (s-8) with, for example, N-chlorosuccinimide, provides a compound represented by the general formula (s-9) .

Reaction of the compound represented by the general formula (s-9) with, for example, thiourea, provides a compound represented by the general formula (s-10) .

The above-mentioned Production Method 1 shows the production method of the compound wherein A ^x in the above general formula (I) is represented by the above formula (Ax-1) , but the compound wherein A ^x in the above general formula (I) is represented by the above formula (Ax-2) can be synthesized by the same method as the compound represented by the general formula (s-10) . (Production method 3) Production of a compound represented by the following formula (s-14)

[Chemical formula 25]

Reaction of a compound represented by the formula (s-1) with sulfur in the presence of, for example, n-butyllithium, provides a compound represented by the formula (s-11) .

Reaction of the compound represented by the formula (s-11) with, for example, N-bromosuccinimide, provides a compound represented by the formula (s-12) .

The compound represented by the formula (s-12) is reacted with trimethylsilylacetylene and then reacted with tetrafluoroammonium fluoride (TBAF) , and thereby, a compound represented by the general formula (s-13) can be obtained. Examples of the reaction method includes a Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium (0) . Specific examples of the copper catalyst include copper (I) iodide. Specific examples of the base include triethylamine.

Compounds represented by the formula (s-13) are reacted with each other together with 1, 8-diazabicyclo [5, 5, 0] undeca-7-ene (DBU) , N, N, N', N'-tetramethylethylenediamine and copper iodide, and thereby, a compound represented by the general formula (s-14) can be obtained.

Examples of reaction conditions other than those described in each step include those described in literature such as Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd. ) , Organic Syntheses (A John Wiley & Sons, Inc., Publication) , Beilstein Handbook of Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co. K) , Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc. ) or the like, or those listed in databases such as SciFinder (Chemical Abstracts Service, American Chemical Society) , Reaxys (Elsevier Ltd. ) or the like.

In each step, a functional group can be protected as needed. Examples of a protective group include protective groups described in GREENE'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ( (Fourth Edition) , co-authored by PETER G.M. WUTS, and THEODORA W. GREENE, A John Wiley & Sons, Inc., Publication) or the like. In addition, purification can be performed as needed in each step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purifying agent include silica gel, alumina, and activated carbon.

The compound represented by the general formula (I) is preferably used by addition to a liquid crystal composition. When a liquid crystal composition contains a compound represented by the general formula (I) , it may contain one compound represented by the general formula (I) , or it may contain a plurality of compounds represented by the general formula (I) . When 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 preferably 5%by mass or more, 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 particularly preferably 20%by mass or more and 85%by mass or less. When the liquid crystal composition contains one compound represented by the general formula (I) , "the total content of the compounds represented by the general formula (I) " used herein means a content of the compound represented by the general formula (I) ; and when the liquid crystal composition contains a plurality of compounds represented by the general formula (I) , it means a total of contents of the plurality of compounds represented by the general formula (I) .

The liquid crystal composition containing the compound represented by the general formula (I) preferably has a refractive index anisotropy (Δn, wavelength for measurement: 589 nm) of 0.15 or more and 1.00 or less. From the viewpoints of the liquid crystal phase temperature range, driving voltage, rotational viscosity and elastic modulus of the liquid crystal composition, the refractive index anisotropy (Δn) is preferably 0.20 or more and 0.95 or less, more preferably 0.25 or more and 0.90 or less, further preferably 0.30 or more and 0.85 or less, and particularly preferably 0.35 or more and 0.80 or less. When the liquid crystal composition containing a compound represented by the general formula (I) is used for a high-frequency phase shifter, a phased array antenna, an image recognition device, distance measuring equipment, a liquid crystal display device, 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 constant anisotropy at 1 kHz (Δε (1 kHz) ) of 2 or more and 60 or less. From the viewpoints of the liquid crystal phase temperature range, the storage stability, the weather resistance, the driving voltage, the rotation viscosity and the elastic modulus of a liquid crystal composition, the dielectric constant anisotropy at 1 kHz (Δε (1 kHz) ) is preferably 2.5 or more and 50 or less, 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 particularly preferably 5 GHz or more and 150 GHz or less.

The liquid crystal composition containing the compound represented by the general formula (I) preferably contains a compound represented by the following general formula (VI) .

[Chemical formula 26]

(In the formula, 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 represents a group selected from the following formulas (A6-1) to (A6-8) ;

[Chemical formula 27]

(in the formulas, the broken line represents a binding position) wherein when multiple A ³s are present, they may be the same or different; and

Z ⁴ represents -O-, -S-, -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH ₂-, -CH ₂S-, -CF ₂O-, -OCF ₂-, -CF ₂S-, -SCF ₂-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂CH ₂-, -OCO-CH ₂CH ₂-, -CH ₂CH ₂-COO-, -CH ₂CH ₂-OCO-, -COO-CH ₂-, -OCO-CH ₂-, -CH ₂-COO-, -CH ₂-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond, wherein when multiple Z ⁴s are present, they may be the same or different;

m3 represents an integer from 1 to 4; and

A ^y represents a group selected from the following formulas (Ay-1) and (Ay-2)

[Chemical formula 28]

(in the formula, the broken line represents a binding position, Y ⁷, Y ⁹, Y ¹⁰ and Y ¹² each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸ and Y ¹¹ each independently represent a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfanyl group, an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom is substituted with a fluorine atom, an alkoxy group having 1 to 7 carbon atoms wherein an arbitrary hydrogen atom is substituted with a fluorine atom, an alkenyl group having 2 to 8 carbon atoms wherein an arbitrary hydrogen atom is substituted with a fluorine atom, or an alkenyloxy group having 2 to 7 carbon atoms wherein an arbitrary hydrogen atom is substituted with a fluorine atom wherein one -CH ₂-or two or more -CH ₂-’s are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-) ) .

From the viewpoints of the liquid crystal phase temperature range, the refractive index anisotropy, the dielectric constant anisotropy, the rotation viscosity and the elastic modulus of a liquid crystal composition, the compound represented by the general formula (VI) is preferably a compound represented by the following general formula (VI-i) ,

[Chemical formula 29]

(in the formula, 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;

A ³¹ represents a group selected from the formulas (A6-1) to (A6-6) , wherein when multiple A ³¹s are present, they are optionally the same or different;

Z ⁴¹ represents -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -COO-, -OCO-, -CF ₂O-, -OCF ₂-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CH=N-N=CH-, -CF=CF-, -N=N-, -C≡C-or a single bond wherein when multiple Z ⁴¹s are present, they may be the same or different;

m31 represents an integer from 1 to 3; and

A ^y1 represents a group selected from the following formulas (Ay-1-i) and (Ay-2-i) ,

[Chemical formula 30]

(in the formulas, the broken line represents a binding position, Y ⁷¹, Y ⁹¹, Y ¹⁰¹ and Y ¹²¹ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸¹ and Y ¹¹¹ each independently represent a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfanyl group, an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom, an alkoxy group having 1 to 7 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom, an alkenyl group having 2 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom or an alkenyloxy group having 2 to 7 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom) ) . The compound represented by the general formula (VI) is more preferably a compound represented by the following general formula (VI-ii) ,

[Chemical formula 31]

(in the formula, 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 (A6-5) wherein when multiple A ³²s are present, they may be the same or different;

Z ⁴² represents -CF ₂O-, -OCF ₂-, -CH=CH-, -CF=CF-, -N=N-, -C≡C-or a single bond wherein when multiple Z ⁴²s are present, they may be the same or different;

m32 represents 1, 2 or 3;

Y ⁷² and Y ⁹² each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸² represents a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfanyl group, an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom, an alkoxy group having 1 to 7 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom, an alkenyl group having 2 to 8 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom or an alkenyloxy group having 2 to 7 carbon atoms wherein an arbitrary hydrogen atom may be substituted with a fluorine atom) . The compound represented by the general formula (VI) is further preferably a compound represented by the following general formula (VI-iii) ,

[Chemical formula 32]

(in the formula, 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 (A6-5) , wherein when multiple A ³³s are present, they may be the same or different;

Z ⁴³ represents -CF ₂O-, -OCF ₂-, -N=N-, -C≡C- or a single bond, wherein when multiple Z ⁴³s are present, they may be the same or different;

m33 represents 1, 2 or 3; and

Y ⁷³ and Y ⁹³ each 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) . The compound represented by the general formula (VI) is particularly preferably a compound represented by the following general formulas (VI-iv-1) to (VI-iv-21) ,

[Chemical formula 33]

[Chemical formula 34]

[Chemical formula 35]

[Chemical formula 36]

[Chemical formula 37]

(in the formulas, R ⁶¹⁴ 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) .

The liquid crystal composition containing the compound represented by the general formula (I) may contain a compound represented by the following general formula (III) ,

[Chemical formula 38]

(in the formula, R ³¹ and R ³² each independently represent 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; and A ³¹ and A ³² each independently represent a group selected from the following formulas (A3-1) to (A3-8) ,

[Chemical formula 39]

(in the formulas, the broken line represents a binding position) wherein when multiple A ³²s are present, they may be the same or different; and

m31 represents an integer from 1 to 4) .

From the viewpoints of the liquid crystal phase temperature range, refractive index anisotropy, dielectric constant anisotropy, rotational viscosity and elastic modulus of a liquid crystal composition, the compound represented by the general formula (III) is preferably a compound represented by the following general formula (III-i) ,

[Chemical formula 40]

(in the formula, R ³¹¹ and R ³²¹ each independently represent 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; and A ³¹¹ and A ³²¹ each independently represent a group selected from the following formulas (A31-1) to (A31-6) ,

[Chemical formula 41]

(in the formulas, the broken line represents a binding position) , wherein when multiple A ³²¹s are present, they may be the same or different; and

m311 represents an integer from 1 to 3) . The compound represented by the general formula (III) is more preferably a compound represented by the following general formula (III-ii) ,

[Chemical formula 42]

(in the formula, R ³¹² and R ³²² each independently represent 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 ³¹² and A ³²² each independently represent a group selected from the following formulas (A32-1) to (A32-4) ,

[Chemical formula 43]

(in the formulas, the broken line represents a binding position) wherein when multiple A ³²²s are present, they may be the same or different; and

m312 represents 1 or 2) . The compound represented by the general formula (III) is further preferably a compound represented by the following general formula (III-iii) ,

(in the formula, R ³¹³ and R ³²³ each 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 each independently represent a group selected from the following formulas (A33-1) and (A33-2) ,

[Chemical formula 44]

(in the formulas, the broken line represents a binding position) wherein when multiple A ³²³s are present, they may be the same or different; and

m313 represents 1 or 2) ) . The compound represented by the general formula (III) is particularly preferably a compound represented by the following general formulas (III-iv-1) to (III-iv-10) ,

[Chemical formula 45]

[Chemical formula 46]

(in the formulas, R ³¹⁴ and R ³²⁴ each 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) .

Further, the compound represented by the general formula (I) may be added to and used for a liquid crystal composition having a neutral or negative dielectric constant anisotropy (Δε) . In that case, the liquid crystal composition containing the compound represented by the general formula (I) preferably has a dielectric constant anisotropy (Δε) of -20 or more and 2 or less. From the viewpoints of the liquid crystal phase temperature range, the storage stability, the weather resistance, the driving voltage, the rotation viscosity and the elastic modulus of a liquid crystal composition, the dielectric constant anisotropy (Δε) is preferably -15 or more and 1.5 or less, more preferably -10 or more and 1 or less, and particularly preferably -5 or more and 0.5 or less.

When a liquid crystal composition containing the compound represented by the general formula (I) has a neutral or negative dielectric constant anisotropy (Δε) , the liquid crystal composition may contain a compound represented by the following general formula (IV) ,

[Chemical formula 47]

(in the formula, R ⁴¹ and R ⁴² each independently represent 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 ⁴¹ and A ⁴² each independently represent a group selected from the following formulas (A4-1) to (A4-11) ,

[Chemical formula 48]

(in the formulas, the broken line represents a binding position) wherein: when multiple A ⁴¹s are present, they may be the same or different; and when multiple A ⁴²s are present, they may be the same or different;

Z ⁴¹ and Z ⁴² each independently represent -O-, -S-, -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH ₂-, -CH ₂S-, -CF ₂O-, -OCF ₂-, -CF ₂S-, -SCF ₂-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂CH ₂-, -OCO-CH ₂CH ₂-, -CH ₂CH ₂ -COO-, -CH ₂CH ₂-OCO-, -COO-CH ₂-, -OCO-CH ₂-, -CH ₂-COO-, -CH ₂-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond, wherein: when multiple Z ⁴¹s are present, they may be the same or different; and when multiple Z ⁴²s are present, they may be the same or different;

m41 and m42 each independently represent an integer from 0 to 3, and m41+m42 represents an integer from 1 to 3) .

From the viewpoints of the liquid crystal phase temperature range, the refractive index anisotropy, the dielectric constant anisotropy, the rotation viscosity and the elastic modulus of a liquid crystal composition, the compound represented by the general formula (IV) is preferably a compound represented by the following general formula (IV-i) ,

[Chemical formula 49]

(in the formula, R ⁴¹¹ and R ⁴²¹ each independently represent 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 ⁴¹¹ and A ⁴²¹ each independently represent a group selected from the formulas (A4-1) to (A4-9) , wherein: when multiple A ⁴¹¹s are present, they may be the same or different; and when multiple A ⁴²¹s are present, they may be the same or different;

Z ⁴¹¹ and Z ⁴²¹ each independently represent -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -COO-, -OCO-, -CF ₂O-, -OCF ₂-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond, wherein: when multiple Z ⁴¹¹s are present, they may be the same or different; and when multiple Z ⁴²¹s are present, they may be the same or different;

m411 and m421 each independently represent an integer from 0 to 3 and m411+m421 represents an integer from 1 to 3) . The compound represented by the general formula (IV) is more preferably a compound represented by the following general formula (IV-ii) ,

[Chemical formula 50]

(in the formula, R ⁴¹² and R ⁴²² each independently represent 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 ⁴¹² and A ⁴²² each independently represent a group selected from the formulas (A4-1) to (A4-7) , wherein: when multiple A ⁴¹²s are present, they may be the same or different; and when multiple A ⁴²²s are present, they may be the same or different;

Z ⁴¹² and Z ⁴²² each independently represent -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -COO-, -OCO-, -CF ₂O-, -OCF ₂- or a single bond, wherein: when multiple Z ⁴¹²s are present, they may be the same or different; and when multiple Z ⁴²²s are present, they may be the same or different;

m412 and m422 each independently represent 0, 1 or 2 and m412+m422 represents 1 or 2) . The compound represented by the general formula (IV) is further preferably a compound represented by the following general formula (IV-iii) ,

[Chemical formula 51]

(in the formula, R ⁴¹³ and R ⁴²³ each 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 ⁴¹³ and A ⁴²³ each independently represent a group selected from the formulas (A4-1) to (A4-5) , wherein when multiple A ⁴¹³s are present, they may be the same or different; and when multiple A ⁴²³s are present, they may be the same or different;

Z ⁴¹³ and Z ⁴²³ each independently represent -OCH ₂-, -CH ₂O-, -CH ₂CH ₂- or a single bond, wherein: when multiple Z ⁴¹³s are present, they may be the same or different; and when multiple Z ⁴²³s are present, they may be the same or different; and

m413 and m423 independently represent 0, 1 or 2 and m413+m423 represents 1 or 2) . The compound represented by the general formula (IV) is particularly preferably a compound represented by the following general formulas (IV-iv-1) to (IV-iv-8) ,

[Chemical formula 52]

[Chemical formula 53]

(in the formulas, R ⁴¹⁴ and R ⁴²⁴ each 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 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. Examples of stabilizers usable therefor include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and nitroso compounds. When a stabilizer is used, the amount to be added relative to the composition is in the range of preferably 0.005%by mass to 1%by mass, more preferably 0.02%by mass to 0.8%by mass, and further preferably 0.03%by mass to 0.5%by mass. Further, one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Examples of the stabilizer include a compound represented by the following general formula (X1) ,

[Chemical formula 54]

(in the formula, Sp ^x1 represents an alkylene group having 1 to 20 carbon atoms wherein one -CH ₂- or two or more nonadjacent -CH ₂-’s may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, or a single bond; A ^x1 represents a group selected from the following formulas (Ax1-1) to (Ax1-8) ,

[Chemical formula 55]

(in the formulas, the broken line represents a binding position) wherein when multiple A ^x1s are present, they may be the same or different;

Z ^x1 represents -O-, -S-, -OCH ₂-, -CH ₂O-, -CH ₂CH ₂-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH ₂-, -CH ₂S-, -CF ₂O-, -OCF ₂-, -CF ₂S-, -SCF ₂-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂CH ₂-, -OCO-CH ₂CH ₂-, -CH ₂CH ₂-COO-, -CH ₂CH ₂-OCO-, -COO-CH ₂-, -OCO-CH ₂-, -CH ₂-COO-, -CH ₂-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C- or a single bond, wherein when multiple Z ^x1s are prsent, they may be the same or different; and

mx1 represents 0 or 1 and

mx2 represents an integer from 0 to 4) .

From the viewpoints of the voltage holding ratio and the compatibility with a liquid crystal composition, the compound represented by the general formula (X1) is preferably a compound represented by the following general formula (X1-i) ,

[Chemical formula 56]

(in the formula, Sp ^x11 represents an alkylene group having 1 to 20 carbon atoms in which one -CH ₂-or two or more nonadjacent -CH ₂-’s may be each independently substituted with -O-, -COO- or -OCO-, or a single bond;

A ^x11 represents a group selected from the following formulas (Ax11-1) and (Ax11-2) ,

[Chemical formula 57]

(in the formulas, the broken line represents a binding position) wherein when multiple A ^x11s are present, they may be the same or different;

Z ^x11 represents -COO-, -OCO-, -OCO-CH ₂CH ₂-, -CH ₂CH ₂-COO- or a single bond, wherein when multiple Z ^x11s are present, they may be the same or different; and

mx11 represents 0 or 1 and

mx21 represents 0 or 1) . The compound represented by the general formula (X1) is particularly preferably a compound represented by the following general formulas (X1-ii-1) to (X1-ii-4) ,

[Chemical formula 58]

(in the formulas, Sp ^x12 represents an alkylene group having 1 to 20 carbon atoms or a single bond) .

Examples of the liquid crystal composition containing the compound represented by the general formula (I) include a compound represented by the following general formula (X2) ,

[Chemical formula 59]

(in the formula, 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 ^x24 each independently represent a spacer group or a single bond; and

mx21 represents 0 or 1,

mx22 represents 0 or 1, and

mx23 represents 0 or 1) .

From the viewpoints of the voltage retention rate and the compatibility with the liquid crystal composition, the compound represented by the general formula (X2) is preferably a compound represented by the following general formula (X2-i) ,

[Chemical formula 60]

(in the formula, R ^x211, R ^x221, R ^x231 and R ^x241 each 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;

Sp ^x211, Sp ^x221, Sp ^x231 and Sp ^x224 each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms in which an arbitrary hydrogen atom in the group may be substituted with a fluorine atom, and one -CH ₂- or two or more nonadjacent -CH ₂-’s may be each independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-, or a single bond; and

mx211 represents 0 or 1,

mx221 represents 0 or 1, and

mx231 represents 0 or 1) . The compound represented by the general formula (X2) is more preferably a compound represented by the following general formula (X2-ii) ,

[Chemical formula 61]

(in the formula, R ^x212 and R ^x222 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;

Sp ^x212 and Sp ^x222 each independently represent a linear alkylene group having 1 to 10 carbon atoms in which one -CH ₂-or two or more nonadjacent -CH ₂-’s may be each independently substituted with -O-, -COO-or -OCO-, or a single bond; and

mx212 represents 0 or 1) . The compound represented by the general formula (X2) is particularly preferably a compound represented by the following general formula (X2-iii) ,

[Chemical formula 62]

(in the formula, R ^x 213 and R ^x 223 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; and

Sp ^x213 represents a linear alkylene group having 1 to 10 carbon atoms in which one -CH ₂-or two or more nonadjacent -CH ₂-’s may be each independently substituted with -COO-or -OCO-) .

In the present invention, ring structures contained in a 1, 4-cyclohexylene group, a decahydronaphthalene-2, 6-diyl group and a 1, 3-dioxane-2, 5-diyl group each may be either of a trans form and a cis form. However, from the viewpoint of the liquid crystallinity, the content of trans form is preferably higher than that of the cis form for each of the above groups, the content of the trans form in the ring structure is more preferably 80%or more; the content of the trans form in the ring structure is further preferably 90%or more; the content of the trans form in the ring structure is further more preferably 95%or more; and the content of the trans form in the ring structure is particularly preferably 98%or more. Further, in the present invention, the following notation (CY-1) signifies trans form and/or cis form of a 1, 4-cyclohexylene group.

[Chemical formula 63]

(In the formula, the broken line represents a binding position. ) Further, in the present invention, each element may be substituted with an isotope of the same element.

[Examples]

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In addition, "%" used for the compositions of Examples and Comparative Examples described below means "mass %. " When a substance unstable to oxygen and/or water is handled in each process, it is preferred to carry out operations in an inert gas such as nitrogen gas or argon gas. The purity of each compound was determined by UPLC (Waters ACQUITY UPLC, BEH C ₁₈ (100 x 2.1 mm x 1.7 μm) , acetonitrile/water or 0.1%formic acid-containing acetonitrile/water, PDA, column temperature: 40℃) , GPC (Shimadzu Corporation, HPLC Prominence, Shodex KF-801 (300 mm x 8 mm x 6 μm) + KF-802 (300 mm x 8 mm x 6 μm) , tetrahydrofuran, RI, UV (254 nm) , column temperature: 40℃) , GC (Agilent 6890A, J&W DB-1, 30 m x 0.25 mm x 0.25 μm, carrier gas He, FID, 100℃ (1 minute) -> temperature increase 10℃/min -> 300℃ (12 minutes) ) or ¹H NMR (JEOL, 400 MHz) .

An extrapolation value of refractive index anisotropy (Δn, wavelength for measurement: 589 nm) was obtained by using a host liquid crystal N composed of the following compounds and adding in an amount of 5%.

(Host Liquid Crystal N)

(Example 1) Production of a compound represented by the formula (I-1)

[Chemical formula 64]

Under a nitrogen atmosphere, 15 g of the compound represented by the formula (I-1-1) and 40 mL of tetrahydrofuran (THF) were charged into a reaction vessel. With cooling of the reaction vessel to -78℃, 50 ml of n-butyllithium (2.6 mol/l) was slowly added dropwise and the mixture was stirred at -78℃ for 30 minutes. Then, 4 g of sulfur was added little by little and the mixture was stirred at -78℃ for another 1 hour. Further,

1-bromopentane was slowly added dropwise at -78℃ and the mixture was stirred at -30℃ for 1 hour. 2 ml of ethyl acetate was added dropwise to the reaction solution; the reaction solution was returned to 0℃; a saturated aqueous solution of ammonium chloride was poured; ethyl acetate was added; and the mixture was subjected to liquid separation treatment. An organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane/hexane) , and thereby, 20 g of a compound represented by the formula (I-1-2) was obtained.

20 g of the compound represented by the formula (I-1-2) and 99 mL of dichloromethane were charged into a reaction vessel. With ice-cooling, 15 g of N-bromosuccinimide was added little by little and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and subjected to liquid separation treatment. An organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane/hexane) , and thereby, 24 g of a compound represented by the formula (I-1-3) was obtained.

Under a nitrogen atmosphere, 24 g of the compound represented by the formula (I-1-3) , 0.2 g of copper (I) iodide, 1 g of tetrakistriphenylphosphine palladium, 15 mL of triethylamine, and 100 mL of N, N-dimethylformamide (DMF) were charged into a reaction vessel. With heating at 70℃, 9.0 g of trimethylsilyl acetylene was added dropwise, and the mixture was heated and stirred at 70℃ for 4 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and purified by column chromatography (silica gel, toluene/hexane) and activated charcoal treatment. Next, 120 mL of methanol and 4.5 g of potassium carbonate were added, and the mixture was stirred at room temperature for 8 hours. Water was added to the reaction solution, and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then purified by column chromatography (silica gel, toluene/hexane) ; and thereby, 13 g of a compound represented by the formula (I-1-4) was obtained.

Under a nitrogen atmosphere, 9 g of the compound represented by the formula (I-1-5) , 0.15 g of copper (I) iodide, 0.5 g of tetrakistriphenylphosphine palladium, 15 mL of triethylamine, and 60 mL of DMF were charged into a reaction vessel. With heating at 80℃, 30 ml of DMF containing 13 g of the compound represented by the formula (I-1-4) was added dropwise, and the mixture was heated and stirred at 80℃ for 4 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then, subjected to column chromatography (silica gel, toluene/hexane) and activated charcoal treatment; and thereby, 18 g of a compound represented by the formula (I-1-6) was obtained.

Into a reaction vessel, 18 g of the compound represented by the formula (I-1-6) , 3.6 g of sodium acetate, and 74 mL of methanol were charged. 3 g of hydroxylamine hydrochloride was added at room temperature, and the mixture was stirred for 10 hours. The reaction solution was poured into water and extraction was carried out with dichloromethane. An organic layer was washed with water, a saturated aqueous sodium hydrogen carbonate solution and brine, successively, and then, a solvent was distilled off and dried; and thereby, 15 g of a compound represented by the formula (I-1-7) was obtained.

Into a reaction vessel, 15 g of the compound represented by the formula (I-1-7) and 100 mL of DMF were charged. With ice-cooling, 6.7 g of N-chlorosuccinimide was added and the mixture was heated and stirred at 40℃ for 2 hours. The reaction solution was cooled and poured into water, and extraction was carried out with dichloromethane. An organic layer was washed with water and brine, successively, and then, a solvent was distilled off and dried; and thereby, 15 g of a compound represented by the formula (I-1-8) was obtained.

Into a reaction vessel, 15 g of the compound represented by the formula (I-1-8) , 6.6 g of thiourea, and 110 mL of tetrahydrofuran were charged. With ice-cooling, 15 g of triethylamine was added dropwise, and the mixture was heated and stirred at 40℃ for 5 hours. The reaction solution was cooled and poured into water, and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then, purified by column chromatography (silica gel, toluene/hexane) , activated charcoal treatment and recrystallization (toluene/ethanol) ; and thereby, 12 g of a compound represented by the formula (I-1) was obtained.

MS (EI) : m/z=435

Melting point 113℃

Phase transition temperature Cr113 N 227 Iso (Example 2) Production of a compound represented by the formula (I-2)

[Chemical formula 65]

Into a reaction vessel, 5 g of a compound represented by the formula (I-2-1) , 0.05 g of copper (I) iodide, 0.15 g of tetrakistriphenylphosphine palladium, 7 mL of triethylamine, and 50 mL of N, N-dimethylformamide (DMF) were charged. With heating at 70℃, 10 ml of a DMF solution containing 3.2 g of a compound represented by the formula (I-2-2) was added dropwise, and the mixture was heated and stirred at 70℃ for 4 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then purified by column chromatography (silica gel, toluene/hexane) , and activated charcoal treatment; and thereby, a compound represented by the formula (I-2) was produced.

Properties: oily

MS (EI) : m/z=420

(Example 3) Production of a compound represented by the formula (I-3)

[Chemical formula 66]

A compound represented by the formula (I-3) was produced by the same method as in Example 2 except that the compound represented by the formula (I-2-2) in Example 2 was replaced with a compound represented by the formula (I-3-4) .

MS (EI) : m/z=512

Melting point 65℃

Phase transition temperature Cr65 N 101 Iso (Example 4) Production of a compound represented by the formula (I-4)

[Chemical formula 67]

Under a nitrogen atmosphere, 10 g of a compound represented by the formula (I-4-1) and 15 g of a compound represented by the formula (I-4-2) were reacted with each other in the same manner as in Example 1; then 11 g of N-bromosuccinimide was added little by little in the same manner as in Example 1; and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and subjected to liquid separation treatment. An organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane/hexane) ; and thereby, 19 g of a compound represented by the formula (I-4-4) was obtained.

Under a nitrogen atmosphere, 19 g of the compound represented by the formula (I-4-4) , 14 g of potassium acetate, 14 g of bis (pinacolato) diboron, 90 mL of dimethyl sulfoxide, and 0.4 g of a [1, 1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct were charged into a reaction vessel, and the mixture was heated and stirred at 80℃ for 6 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then, purified by column chromatography (alumina, dichloromethane) ; and thereby, 17 g of a compound represented by the formula (I-4-5) was obtained.

Under a nitrogen atmosphere, 17 g of the compound represented by the formula (I-4-5) , 8 g of potassium carbonate, 8.5 g of 1-bromo-3, 4, 5-trifluorobenzene, 60 mL of toluene, 20 mL of ethanol, 15 mL of water and 0.2 g of bis (triphenylphosphine) palladium (II) dichloride were charged into a reaction vessel, and the mixture was heated and refluxed for 6 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then, purified by column chromatography (silica gel, toluene/hexane) and recrystallization (toluene/ethanol) ; and thereby, 13 g of a compound represented by the formula (I-4) was obtained.

MS (EI) : m/z=440

(Example 5) Production of a compound represented by the formula (I-5)

[Chemical formula 68]

A compound represented by the formula (I-5-2) was produced by the method described in WO2010/115279A1. Under a nitrogen atmosphere, 10 g of a compound represented by the formula (I-5-1) , 9.5 g of the compound represented by formula (I-5-2) , 13.5 g of potassium carbonate, 0.1 g of dichlorobis [di-t-butyl (p-dimethylaminophenyl) phosphino] palladium (II) , 80 mL of toluene, 30 mL of ethanol, and 20 mL of water were charged into a reaction vessel, and the mixture was heated and refluxed for 6 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and then, purified by column chromatography (silica gel, toluene/hexane) and recrystallization (toluene/ethanol) ; and thereby, 10 g of a compound represented by the formula (I-5-3) was obtained.

7 g of a compound represented by the formula (I-5) was produced in the same manner as in Example 1 except that the compound represented by the formula (I-1-6) in Example 1 was replaced with the compound represented by the formula (I-5-3) .

MS(EI) : m/z=423

(Example 6) Production of a compound represented by the formula (I-6)

[Chemical formula 69]

In a reaction vessel, 5 g of a compound represented by the formula (I-6-1) , 0.05 g of copper (I) iodide, 0.25 g of tetrakistriphenylphosphine palladium, 25 mL of triethylamine, and 25 mL of N, N-dimethylformamide (DMF) were charged. The mixture was heated and stirred at 80℃ for 4 hours. The reaction solution was poured into water and extraction was carried out with toluene. An organic layer was washed with water and brine, successively, and purified by column chromatography (silica gel, toluene/hexane) and activated charcoal treatment; and thereby, 2.4 g of a compound represented by the formula (I-6) was produced. Melting point 96℃

MS (EI) : m/z=530

(Examples 7 to 15 and Comparative Examples 1 to 8)

The following abbreviations are used to describe the liquid crystal compounds in the Examples.

(Ring structure)

[Chemical formula 70]

(Side chain structure)

2- CH ₃CH ₂-

3- CH ₃ (CH ₂) ₂-

4- CH ₃ (CH ₂) ₃-

5- CH ₃ (CH ₂) ₄-

-2 -CH ₂CH ₃

-3 - (CH ₂) ₂CH ₃

-4 - (CH ₂) ₃CH ₃

-5 - (CH ₂) ₄CH ₃

-Cl -Cl

(Linking group)

- Single bond

-T- -C≡C-

A host liquid crystal N composed of the following compounds was prepared.

(Host Liquid Crystal N)

Compounds represented by the formula (I-6) from (I-1) synthesized in Examples were added to the host liquid crystal N, to prepare liquid crystal compositions (M-1) to (M-6) for evaluation. In addition, the compound represented by the formula (R-1) described in Non-Patent Literature 1, the compounds represented by the formulas (R-2) and (R-3) described in Patent Literature 1, and the compound represented by the formula (R-4) described in Patent Literature 3 were added to prepare liquid crystal compositions (RM-1) to (RM-4) for comparison.

[Chemical formula 71]

(Liquid crystal composition (M-1) )

Host liquid crystal N 90.0%

Compound represented by formula (I-1) 10.0%

(Liquid crystal composition (M-2) )

Host liquid crystal N 90.0%

Compound represented by formula (I-2) 10.0%

(Liquid crystal composition (M-3) )

Host liquid crystal N 90.0%

Compound represented by formula (I-3) 10.0%

(Liquid crystal composition (M-4) )

Host liquid crystal N 90.0%

Compound represented by formula (I-4) 10.0%

(Liquid crystal composition (M-5) )

Host liquid crystal N 90.0%

Compound represented by formula (I-5) 10.0%

(Liquid crystal composition (M-6) )

Host liquid crystal N 90.0%

Compound represented by formula (I-6) 10.0%

Each compound for evaluation was evaluated in terms of the storage stability. For storage stability, 2 mL of each prepared liquid crystal composition was sealed in a glass vial under an argon atmosphere and stored at 10℃ for 4 weeks, and then, the state thereof was visually evaluated. Evaluation results are shown in tables below.

[Table 1]

From the above results, it is found that the compounds of the present invention are less likely to cause precipitation when added to the liquid crystal composition, and have a high compatibility with the liquid crystal composition.

Next, the characteristics of each compound to be evaluated in a high frequency region were evaluated. For the measurement, a transmission delay-mode cut back type strip-line method and a relative permittivity/dielectric loss tangent measuring device (manufactured by KEYCOM Corporation) were used. The dielectric constant anisotropy of each of the prepared liquid crystal compositions at 13.17 GHz and 20℃ was measured, and the dielectric constant anisotropy Δε (13.17 GHz) of each compound for evaluation was calculated by extrapolation.

Evaluation results are shown in Table 2.

[Table 2]

From the above results, it is found that all of the compounds of the present invention exhibit a large dielectric constant anisotropy in a high frequency region. Since the compounds of the present invention form a broad conjugated system via a ring structure and a linking group, it is considered that the compounds exhibit a large dielectric constant anisotropy in a high frequency region.

In addition, it was found that the liquid crystal compositions (M-1) to (M-6) containing the compound of the present invention all exhibited a material characteristic (ηε) of 20 or more. Material characteristic (ηε) is defined as follows.

ε⊥ = (3εaverage-ε∥) /2

tanδ⊥ = (3εaveragetanδaverage-ε∥tanδ∥) /2ε⊥

Modulatability (τ) = (ε∥-ε⊥) /ε ∥

Material characteristic (ηε) = τ/ (max (tanδ∥, tanδ⊥) )

From the above results, the compounds of the present invention have a large refractive index anisotropy Δn and a high compatibility with a liquid crystal composition, and exhibit a large dielectric constant anisotropy in a high frequency region; and therefore, they are useful as a material for devices of a high-frequency phase shifter, a phased array antenna, an image recognition device, distance measuring equipment, a liquid crystal display device, a liquid crystal lens, a birefringent lens for displaying a stereoscopic image or the like.

Claims

A compound represented by the following general formula (I) ,

[Chemical formula 1]

(in the formula, R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein an arbitrary hydrogen atom in the alkyl group may be substituted with a halogen atom, and one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-or -C≡C-with the proviso that oxygen atoms are not bonded to each other;

A ¹ and A ² each independently represent a hydrocarbon ring or a heterocycle having 3 to 16 carbon atoms that are optionally substituted; when multiple A ¹s are present, the A ¹s are optionally the same or different; and when multiple A ²s are present, the A ²s are optionally the same or different;

Z ¹, Z ² and Z ³ each independently represent a divalent linking group or a single bond; when multiple Z ¹s are present, the Z ¹s are optionally the same or different; and when multiple Z ²s are present, the Z ²s are optionally the same or different;

m1 and m2 each independently represent an integer from 0 to 3; and

A ^x represents a hydrogen atom, a fluorine atom, a chlorine atom or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein an arbitrary hydrogen atom in the alkyl group is optionally substituted with a halogen atom; one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF-or -C≡C-with the proviso that oxygen atoms are not bonded to each other; or A ^x represents a structure selected from the group consisting of (Ax-1) to (Ax-5) ,

(in the formulas, the broken line represents a binding position; and Y ¹ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl or alkoxy group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom is optionally substituted with a fluorine atom, and when multiple Y ¹s are present, the Y ¹s are optionally the same or different; Y ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom is optionally substituted with a fluorine atom, and one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, CF=CF-or -C≡C-with the proviso that oxygen atoms are not bonded to each other) , wherein: when A ^x is a structure selected from the group consisting of the formulas (Ax-1) to (Ax-5) , m1+m2 represents an integer from 0 to 3; and when A ^x is not a structure selected from the group consisting of the formulas (Ax-1) to (Ax-5) , m1+m2 represents an integer from 1 to 4) .
The compound according to claim 1, wherein, in general formula (I) , A ¹ and A ² each independently represent a group selected from the group consisting of:

(a) a 1, 4-cyclohexylene group (wherein one -CH ₂-or two or more nonadjacent -CH ₂-’s are optionally substituted with -O-or -S-) ;

(b) a 1, 4-phenylene group (wherein one -CH= or two or more nonadjacent -CH=’s are optionally substituted with -N=) ;

(c) a 1, 4-cyclohexenylene group, a bicyclo [2.2.2] octane-1, 4-diyl group, a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 1, 2, 3, 4-tetrahydronaphthalene-2, 6-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, a decahydronaphthalene-2, 6-diyl group, an anthracene-2, 6-diyl group, an anthracene-1, 4-diyl group, an anthracene-9, 10-diyl group, or a phenanthrene-2, 7-diyl group (wherein a hydrogen atom present in the groups is optionally substituted with a fluorine atom or a chlorine atom, and one -CH= or two or more -CH=’s present in a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 1, 2, 3, 4-tetrahydronaphthalene-2, 6-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, an anthracene-2, 6-diyl group, an anthracene-1, 4-diyl group, an anthracene-9, 10-diyl group or a phenanthrene-2, 7-diyl group are optionally substituted with -N=) ; and

(d) a thiophene-2, 5-diyl group, a benzothiophene-2, 5-diyl group, a benzothiophene-2, 6-diyl group, a dibenzothiophene-3, 7-diyl group, a dibenzothiophene-2, 6-diyl group, or a thieno [3, 2-b] thiophene-2, 5-diyl group (wherein one -CH= or two or more nonadjacent -CH=’s present in the groups are optionally substituted with -N=) ,

wherein the selected group is optionally unsubstituted or substituted with one or more substituents L ¹,

L ¹ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear alkyl group having 1 to 20 carbon atoms or branched or cyclic alkyl group having 3 to 20 carbon atoms wherein one -CH ₂-or two or more -CH ₂-’s are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-or -C≡C-with the proviso that oxygen atoms are not directly bonded to each other, and an arbitrary hydrogen atom in the alkyl group is optionally substituted with a fluorine atom.
The compound according to claim 1 or 2, wherein, in the general formula (I) , Z ¹, Z ² and Z ³ each independently represent a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CH ₂O-, -OCH ₂-, -CF ₂O-, -OCF ₂-, -CH=CHCOO-, -OCOCH=CH-, -CH=C (CH ₃) COO-, -OCOC (CH ₃) =CH-, -CH ₂-CH (CH ₃) COO-, -OCOCH (CH ₃) -CH ₂-, -OCH ₂CH ₂O-, -N=N-, -C=N-N=C-, -CH=N-, -N=CH-, -C≡C-C≡C-or an alkylene group having 2 to 20 carbon atoms wherein one -CH ₂-or two or more -CH ₂-’s in the alkylene group are optionally substituted with -O-, -S-, -COO-or -OCO-with the proviso that oxygen atoms are not directly bonded to each other.
The compound according to any one of claims 1 to 3, wherein the above general formula (I) is represented by the following general formula (I-i) ,

[Chemical formula 2]

(in the formula, R ¹¹ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group is optionally substituted with a halogen atom and one -CH ₂-or two or more -CH ₂-’s in the group are each independently and optionally substituted with -O-, -S-, -CH=CH-, -CF=CF-or -C≡C-;

A ¹¹ and A ²¹ each independently represent a 1, 4-phenylene group, a naphthalene-2, 6-diyl group, a naphthalene-1, 4-diyl group, a 5, 6, 7, 8-tetrahydronaphthalene-1, 4-diyl group, a phenanthrene-2, 7-diyl group, a benzothiophene-2, 5-diyl group, a benzothiophene-2, 6-diyl group, a benzothiazole-2, 5-diyl group, a benzothiazole-2, 6-diyl group, a dibenzothiophene-3, 7-diyl group, a dibenzothiophene-2, 6-diyl group or a thieno [3, 2-b] thiophene-2, 5-diyl group, wherein when multiple A ¹¹s are present, the A ¹¹s are optionally the same or different; when multiple A ²¹s are present, the A ²¹s are optionally the same or different; and these groups are optionally unsubstituted or substituted with one or more substituents L ¹¹; L ¹¹ represents a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 20 carbon atoms, or branched or cyclic alkyl group having 3 to 20 carbon atoms wherein an artibrary hydrogen atom in the group is optionally substituted with a fluorine atom and one -CH ₂-or two or more -CH ₂-’s in the group are each independently and optionally substituted with -O-, -S-, -CH=CH-, -CF=CF-or -C≡C-, wherein when multiple L ¹¹s are present, the L ¹¹s are optionally the same or different;

Z ¹¹, Z ²¹ and Z ³¹ each independently represent -OCH ₂-, -CH ₂O-, -SCH ₂-, -CH ₂S-, -CH ₂CH ₂-, -CF ₂O-, -OCF ₂-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C-or a single bond wherein: when multiple Z ¹¹s are present, the Z ¹¹s are optionally the same or different; and when multiple Z ²¹s are present, the Z ²¹s are optionally the same or different;

m11 and m21 each independently represent 0, 1 or 2;

A ^x1 represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms wherein an arbitrary hydrogen atom in the group is optionally substituted with a halogen atom and one -CH ₂-or two or more -CH ₂-’s in the group are each independently optionally substituted with -O-, -S-, -CH=CH-, -CF=CF-or -C≡C-, or A ^x1 represents a structure selected from the group consisting of the following formulas (Ax-1-i) to (Ax-5-i) ,

(in the formulas, the broken line represents a binding position, Y ¹¹ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group or alkoxy group having 1 to 8 carbon atoms wherein when multiple Y ¹¹s are present, the Y ¹¹s are optionally the same or different; Y ²¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an isothiocyano group, or an alkyl group having 1 to 8 carbon atoms wherein an arbitrary hydrogen atom is optionally substituted with a fluorine atom, wherein one -CH ₂-or two or more -CH ₂-’s in the alkyl group are each independently and optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CH=CH-, -CF=CF-or -C≡C-with the proviso that oxygen atoms are not bonded to each other) , wherein: when A ^x1 is a structure selected from the group consisting of the formulas (Ax-1-i) to (Ax-5-i) , m11+m21 represents an integer from 0 to 2; and when A ^x1 is not a structure selected from the group consisting of the formulas (Ax-1-i) to (Ax-5-i) , m11+m21 represents an integer from 1 to 3) .
The compound according to any one of claims 1 to 4, wherein the above general formula (I) is represented by the following general formula (I-ii) ,

[Chemical formula 3]

(in the formula, R ¹² represents a linear or branched alkyl group having 1 to 12 carbon atoms wherein an arbitrary hydrogen atom in the group is optionally substituted with a fluorine atom, and one -CH ₂-or two or more -CH ₂-’s in the group are each independently and optionally substituted with -O-, -CH=CH-or -C≡C-;

A ¹² and A ²² each independently represent a group selected from the following formulas (A-ii-1) to (A-ii-17) ,

[Chemical formula 4]

(in the formulas, the broken line represents a binding position, and when multiple L ¹²s are present, the L ¹²s are optionally the same or different) wherein: when multiple A ¹²s are present, the A ¹²s are optionally the same or different; and when multiple A ²²s are present, the A ²²s are optionally the same or different;

L ¹² 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 wherein an arbitrary hydrogen atom in the group is optionally substituted with a fluorine atom and -CH ₂-in the group is optionally substituted with -O-;

Z ¹², Z ²² and Z ³² each independently represent -OCH ₂-, -CH ₂O-, -SCH ₂-, -CH ₂S-, -CH ₂CH ₂-, -CF ₂O-, -OCF ₂-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C-or a single bond wherein: when multiple Z ¹²s are present, the Z ¹²s are optionally the same or different; and when multiple Z ²²s are present, the Z ²²s are optionally the same or different;

m12 and m22 each independently represent 0, 1 or 2, and m12+m22 represents an integer from 0 to 2;

A ^x2 represents a structure selected from either of the formulas (Ax-1-i) and (Ax-2-i) ) .
The compound according to any one of claims 1 to 5, wherein the above general formula (I) is represented by the following general formula (I-iii) ,

[Chemical formula 5]

(in the formula, R ¹³ 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, an alkenyloxy group having 2 to 7 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms;

A ¹³ and A ²³ each independently represent a group selected from the following formulas (A-iii-1) to (A-iii-7) , (A-iii-12) , (A-iii-15) and (A-iii-17) ;

[Chemical formula 6]

(in the formulas, the broken line represents a binding position, and when multiple L ¹³s are present, the L ¹³s are optionally the same or different) ;

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;

Z ¹³, Z ²³ and Z ³³ each independently represent -CF ₂O-, -OCF ₂-, -N=N-, -CH=CH-, -CF=CF-, -C≡C-, -C≡C-C≡C-or a single bond;

m13 and m23 each independently represent 0 or 1;

Y ¹³ each independently represents a hydrogen atom, a fluorine atom or a chlorine atom) .
A composition comprising the compound according to any one of claims 1 to 6.
A liquid crystal composition comprising the compound according to any one of claims 1 to 6.
The liquid crystal composition according to claim 8, wherein the refractive index anisotropy is 0.15 or more.
The liquid crystal composition according to claim 8, wherein the dielectric constant anisotropy is 2 or more.
The liquid crystal composition according to claim 8, wherein the dielectric constant anisotropy is 2 or less.
A high-frequency phase shifter, a phased array antenna, an image recognition device, distance measuring equipment, a liquid crystal display device, a liquid crystal lens, or a birefringent lens for stereoscopic image display using the liquid crystal composition according to claims 8 to 11.