WO2021079743A1

WO2021079743A1 - Compound, liquid crystal composition and high-frequency phase shifter

Info

Publication number: WO2021079743A1
Application number: PCT/JP2020/038068
Authority: WO
Inventors: 雅弘堀口; 卓央林; 青木　良夫
Original assignee: Dic株式会社
Priority date: 2019-10-21
Filing date: 2020-10-08
Publication date: 2021-04-29
Also published as: JP6977911B2; JPWO2021079743A1; CN114364680A

Abstract

The present invention addresses the problem of providing: a compound which has high refractive index anisotropy Δn, is highly compatible with a liquid crystal composition, and when added to a liquid crystal composition in order to produce an element, is unlikely to cause a decline in the voltage retention rate of said element; a liquid crystal composition containing said compound; and an element which uses said liquid crystal composition. The present invention provides: a compound having a thienothiophene structure and represented by general formula (I); a liquid crystal composition containing said compound; and an element which uses said liquid crystal composition.

Description

Compounds, liquid crystal compositions and high frequency phase shifters

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

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

Conventionally, satellite communication uses a parabolic antenna, but when used in a mobile body, the parabolic antenna must be directed toward the satellite at any time, and a large moving part is required. However, since the antenna using the liquid crystal composition can change the transmission / reception direction of radio waves by operating the liquid crystal, it is not necessary to move the antenna itself, and the shape of the antenna can be made flat.

The refractive index anisotropy Δn of the liquid crystal composition required for these applications is, for example, about 0.4, which is much larger than Δn required for display applications. Therefore, it is required that the compound added to and used in the liquid crystal composition has a large Δn, has high compatibility with the liquid crystal composition, and does not easily decrease the voltage holding ratio when the element is manufactured. Conventionally, a compound having a thienothiophene structure has been reported as a compound having a large Δn. However, these compounds have problems such as low compatibility when added to a liquid crystal composition for an antenna, and lowering the voltage holding ratio of the device when the device is manufactured (non-). Patent Document 1, Patent Documents 1 and 2). Therefore, there has been a demand for the development of a compound having a large Δn, high compatibility with a liquid crystal composition, and a voltage retention rate that does not easily decrease when an element is manufactured.

CN103472116A Gazette CN106518890A Gazette

The problem to be solved by the present invention is that it has a large refractive index anisotropy Δn, has high compatibility with a liquid crystal composition, and when an element is manufactured by adding it to a liquid crystal composition, the voltage retention rate of the element can be determined. It is an object of the present invention to provide a compound which is difficult to lower, a liquid crystal composition containing the compound, and an element using the liquid crystal composition.

As a result of diligent research to solve the above problems, the present inventors have developed a specific compound. That is, the present invention has the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom, and the alkyl One or more of -CH _2- in the group are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-, but the oxygen atoms are Never join,
A ¹ and A ² each represent a hydrocarbon ring or a heterocycle having 3 to 16 carbon atoms which may be independently substituted, ^{but when a plurality of A 1s} are present, they are the same but different. is good, they if a ² there are a plurality may be the same or different and
Z ^1, Z ² and although Z ³ each represent independently a divalent linking group or a single bond, they if Z ¹ there are a plurality may be different even in the same, Z ² is plurality of If they do, they may be the same or different,
m1 and m2 independently represent integers from 0 to 3, while m1 + m2 represent integers from 0 to 3.
A ^x is the following formula (Ax-1) and formula (Ax-2).

(In the formula, the broken line represents the bond position, X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y ¹ , Y ³ , Y ⁴ and Y ⁶ are independent of each other. Represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Y ² and Y ⁵ are independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and an arbitrary hydrogen atom. An alkyl group having 1 to 8 carbon atoms may be present, an alkoxy group having 1 to 7 carbon atoms may be substituted with an arbitrary hydrogen atom, and an arbitrary hydrogen atom may be substituted with a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, wherein one -CH ₂ -or Two or more -CH ₂ -are independent of -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 = It may be replaced by CH-, -CF = CF- or -C≡C-.)
Represents a group selected from. ), Where in the above general formula (I)

The structure represented by and

Provided is a compound whose structure represented by is not the same, and provides a liquid crystal composition containing the compound and an element using the liquid crystal composition.

The compound of the present invention has a large refractive index anisotropy Δn, has high compatibility with the liquid crystal composition, and does not easily lower the voltage retention rate of the element when the element is manufactured by adding it to the liquid crystal composition. Therefore, it is useful as a material for elements such as high-frequency phase shifters, phased array antennas, image recognition devices, ranging devices, liquid crystal display elements, liquid crystal lenses, and birefringent lenses for displaying stereoscopic images.

The present invention provides a compound represented by the general formula (I), a liquid crystal composition containing the compound, and an element using the liquid crystal composition.

In the general formula (I), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom. , One or more of -CH _2- in the alkyl group are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S. It may be replaced by -CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-, but oxygen. Atoms do not bond to each other. From the viewpoint of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis and availability of raw materials, R ¹ is a hydrogen atom, and any hydrogen atom in the group is replaced with a halogen atom. One or more of -CH _2- in the group may be independently set to -O-, -S-, -CH = CH-, -CF = CF- or -C≡C-. It is preferable to represent a linear or branched alkyl group having 1 to 20 carbon atoms which may be replaced, and R ¹ may have any hydrogen atom in the group substituted with a fluorine atom. One or more -CH _2- may be independently replaced with -O-, -CH = CH- or -C≡C- in a linear or branched form having 1 to 12 carbon atoms. It is more preferable to represent an alkyl group, and R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkenyl having 2 to 7 carbon atoms. It is more preferable to represent an oxy group or an alkynyl group having 2 to 8 carbon atoms, and R ¹ is an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkenyl having 2 to 5 carbon atoms. It is particularly preferable to represent a group or an alkynyl group having 3 to 7 carbon atoms.

In the general formula (I), A ¹ and A ² represent hydrocarbon rings or heterocycles having 3 to 16 carbon atoms which may be independently substituted, ^{but when a plurality of A 1s} are present, they are the same. it may be different even if the a ² there are a plurality thereof may be the same or different. From the viewpoint of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis, and availability of raw materials, A ¹ and A ² are independently unsubstituted or one. it may be substituted by or more substituents L ^1,
(A) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- Is also good.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) 1,4-Cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2 , 3,4-Tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6- Diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (even if the hydrogen atom existing in these groups is replaced with a fluorine atom or a chlorine atom Well, also naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene. One in the -1,4-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene-2,7-diyl group -CH = or two or more -CH = may be replaced with -N =.)
(D) Thiophen-2,5-diyl group, benzothiophene-2,5-diyl group, benzothiophene-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6-diyl Group, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = It is preferable to represent a group selected from the group consisting of (may be.), And ^{when a plurality of A 1} and A ² are present, they may be the same or different, and are they independently unsubstituted? or one or more may be substituted by a substituent ^{L 1,} 1,4-phenylene group, naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, phenanthrene-2,7-diyl group , Benzothiophene-2,5-diyl group, benzothiophene-2,6-diyl group, benzothiazole-2,5-diyl group, benzothiophene-2,6-diyl group, dibenzothiophene-3,7-diyl group , Dibenzothiophene-2,6-diyl group or thieno [3,2-b] thiophene-2,5-diyl group is more preferred, and if there are multiple ^{A 1} and A ^{2, they} It may be the same or different, and each of them independently has the following formulas (A-1) to (A-14).

(In the equation, the broken line represents the bonding position, and ^{when a plurality of L 1s} are present, they may be the same or different.) It is more preferable to represent a group selected from the above, and A ¹ and A ² are plural. If present, they may be the same or different, and even more so, each independently represents a group selected from formulas (A-1) to formulas (A-7) and formulas (A-12). Preferably, ^{when there are a plurality of A 1} and A ^2, they may be the same or different, and they are independently from the formula (A-1), the formula (A-3) to the formula (A-7), respectively. It is particularly preferred to represent the group of choice.

L ¹ is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropyl. Amino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or two or more -CH _2- are independently -O-, -S-, -CO-, -COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH 1 to 20 carbon atoms which may be substituted by -OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Represents a linear alkyl group or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but oxygen atoms do not directly bond to each other, and any hydrogen atom in the alkyl group is replaced with a fluorine atom. Represents a group that may be present. From the viewpoint of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis, and availability of raw materials, L ¹ is a fluorine atom, a chlorine atom, or any hydrogen atom in the group is a fluorine atom. One -CH _2- or two or more -CH _{2- in the group} may be independently substituted with -O-, -S-, -CH = CH-, -CF = CF. It is preferable to represent a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, which may be substituted by − or −C≡C−, and L ¹ is fluorine. A linear alkyl group having 1 to 10 carbon atoms, in which any hydrogen atom in the atom or group may be substituted with a fluorine atom, and -CH _{2- in the group may be substituted with -O-.} Alternatively, it is more preferable to represent a branched or cyclic alkyl group having 3 to 10 carbon atoms, and L ¹ is a fluorine atom, a linear alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms. It is more preferable to represent a cyclic alkyl group, and it is particularly preferable that L ¹ represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms.

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 there are a plurality of Z 1,} they may be the same or different. well, they if Z ² there are a plurality may be the same or different. From the viewpoint of compatibility with liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis and availability of raw materials, Z ¹ , Z ² and Z ³ are independently single-bonded, −CH = CH -, - CF = CF - , - C≡C -, - COO -, - OCO -, - OCOO -, - CF 2 O -, - 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 2 CH 2 O -, -N = N-, -C = N-N = C-, -CH = N-, -N = CH- or an alkylene group having 2 to 20 carbon atoms, and one of the alkylene groups or two or more -CH ₂ - is -O -, - COO- or preferably also represent a substituted group is substituted with ^-OCO-, ^Z ^1, Z ² and ^{Z 3} are identical those when there are a plurality of They may be present or different, and they are independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -N. = N-, -CH = N-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or more preferably represent a single bond, Z ¹ , When ^{there are a plurality of Z 2} and Z ^3, they may be the same or different, and they are independently -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, respectively. -C≡C- or more preferably a single ^bond, Z 1, ^{Z 2} and ^{Z 3} are those when there are a plurality of which may be the same or different and each independently _-CF 2 O- , -OCF _2- , -C ≡ C- or a single bond is even more preferred, ^{and if there are multiple Z 1} , Z ² and Z ^3, they may be the same or different and are independent of each other. It is particularly preferable to represent -C≡C- or a single bond.

In the general formula (I), m1 and m2 independently represent integers from 0 to 3, while m1 + m2 represent integers from 0 to 3. From the viewpoints of compatibility with the liquid crystal composition, refractive index anisotropy, voltage retention, ease of synthesis and availability of raw materials, m1 and m2 independently represent 0, 1 or 2, respectively, and m1 + m2 is 0. It is preferable to represent an integer from 3 to 3, m1 and m2 independently represent 0, 1 or 2, m1 + m2 more preferably represent 0, 1 or 2, and m1 and m2 independently represent 0 or 2, respectively. It is more preferable that m1 + m2 represents 0, 1 or 2, m1 and m2 each independently represent 0 or 1, and m1 + m2 particularly preferably represent 0 or 1.

In the general formula (I), ^{A x} is the following formula (Ax-1) and Formula (Ax-2)

(In the formula, the broken line represents the bond position, X ¹ and X ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y ¹ , Y ³ , Y ⁴ and Y ⁶ are independent of each other. Represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Y ² and Y ⁵ are independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and an arbitrary hydrogen atom. An alkyl group having 1 to 8 carbon atoms may be present, an alkoxy group having 1 to 7 carbon atoms may be substituted with an arbitrary hydrogen atom, and an arbitrary hydrogen atom may be substituted with a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, wherein one -CH ₂ -or Two or more -CH ₂ -are independent of -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 = It represents a group selected from CH-, -CF = CF-or may be substituted with -C≡C-).
From the viewpoint of increasing the voltage holding ratio, ^{it is preferable that Y 2} and Y ⁵ have the above-mentioned structure. On the other hand, when a ^{thioisocyano group (-NCS) is used as Y 2} and Y ⁵ , the voltage retention rate may decrease depending on the electron-conjugated state with the thienothiophene structure.
Compatibility with the liquid crystal composition, the refractive index anisotropy, voltage holding ratio, in terms of ease and the availability of raw materials for synthetic, A ^x following equation (Ax-1-i) and Formula (Ax-2 -I)

(In the formula, the broken line represents the bond position, X ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y ¹¹ , Y ³¹ , Y ⁴¹ and Y ⁶¹ are independent hydrogen atoms and fluorine atoms, respectively. Alternatively, it represents a chlorine atom, and Y ²¹ and Y ⁵¹ are independent fluorine atoms, chlorine atoms, cyano groups, nitro groups, pentafluorosulfanyl groups, and the number of carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. From 1 to 8 alkyl groups, an alkoxy group having 1 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, and 2 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. preferably represents a group selected from.) representing the 8 alkenyl group or an optionally alkenyloxy group 7 good 2 carbon atoms substituted hydrogen atom is a fluorine atom, a ^x is the following formula ( Ax-1-ii)

(In the formula, the broken line represents the bond position, and X ¹² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Y ¹² and Y ³² independently represent a hydrogen atom, a fluorine atom or a chlorine atom, Y ²² is a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is replaced with a fluorine atom. An alkyl group having 1 to 8 carbon atoms which may be used, an alkoxy group having 1 to 7 carbon atoms which may have any hydrogen atom replaced by a fluorine atom, and an arbitrary hydrogen atom which has been replaced by a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. More preferably represents a group selected from), ^{A x} is the following formula (Ax-1-iii)

(In the formula, the broken line represents the bond position, X ¹³ represents a hydrogen atom, a methyl group or an ethyl group, and
Y ¹³ and Y ³³ independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ²³ represents a fluorine atom, a chlorine atom or a cyano group. More preferably represents a group selected from), ^{A x} is the following formula (Ax-1-iv)

(In the formula, the broken line represents the bond position, Y ¹⁴ and Y ³⁴ each independently represent a hydrogen atom or a fluorine atom, and Y ²⁴ represents a fluorine atom or a cyano group). preferable.

The compound represented by the general formula (I) is in the formula.

The structure represented by and

It is preferable that the structures represented by are not the same structure. This is because when the two structures bonded to both ends of the thieno [3,2-b] thiophene-2,5-diyl group are the same, the crystal state of the compound is high because the structure of the compound is highly symmetric. This is because it becomes energetically stable, crystals are likely to precipitate from the liquid crystal composition, and storage stability is likely to be lowered.

The compound represented by the general formula (I) has a wide temperature range indicating a liquid crystal phase, dielectric anisotropy, compatibility with a liquid crystal composition, refractive index anisotropy, voltage retention, and ease of synthesis. And from the viewpoint of availability of raw materials, the following general formula (Ii)

(In the formula, R ¹¹ is a hydrogen atom, any hydrogen atom in the group may be replaced with a halogen atom, and one or two or more -CH _2- in the group are independently -O-. , -S-, -CH = CH-, -CF = CF- or -C≡C- representing a linear or branched alkyl group having 1 to 20 carbon atoms.
A ¹¹ and A ²¹ are independently 1,4-phenylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, phenanthrene-2,7-diyl group, benzothiophene-2,5, respectively. -Diyl group, benzothiophene-2,6-diyl group, benzothiazole-2,5-diyl group, benzothiazole-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6 - represents a diyl group or a thieno [3,2-b] thiophene-2,5-diyl ^{group, if a 11} there are a plurality thereof may be different even in the ^{same, a 21} there are multiple if they may be the same or different and these groups may be substituted by or is one or more substituents L ¹¹ is unsubstituted,
In L ^11, a fluorine atom, a chlorine atom, or any hydrogen atom in the group may be substituted with a fluorine atom, and one -CH _2- or two or more -CH _{2- in the group} are independent of each other. A linear alkyl group having 1 to 20 carbon atoms or 3 carbon atoms which may be substituted by -O-, -S-, -CH = CH-, -CF = CF- or -C≡C-. Represents a branched or cyclic alkyl group from 20 to 20, ^{but if a plurality of L 11s} are present, they may be the same or different.
Z ¹¹ , Z ²¹ and Z ³¹ are independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -N. = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, Z 11} there are a plurality of if they may be the same or different and they if Z ²¹ there are a plurality may be the same or different and
m11 and m21 independently represent 0, 1 or 2, respectively, while m1 + m2 represent an integer from 0 to 3.
A ^x1 is the following formula (Ax-1-i) and formula (Ax-2-i).

(In the formula, the broken line represents the bond position, X ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y ¹¹ , Y ³¹ , Y ⁴¹ and Y ⁶¹ are independent hydrogen atoms and fluorine atoms, respectively. Alternatively, it represents a chlorine atom, and Y ²¹ and Y ⁵¹ are independent fluorine atoms, chlorine atoms, cyano groups, nitro groups, pentafluorosulfanyl groups, and the number of carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. From 1 to 8 alkyl groups, an alkoxy group having 1 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, and 2 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. Represents a group selected from 8 alkenyl groups or alkenyloxy groups having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom). ) Is preferable, and the following general formula (Iii)

(In the formula, in R ¹² , any hydrogen atom in the group may be replaced with a fluorine atom, and one or two or more -CH _2- in the group are independently -O- and -CH, respectively. = Represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be replaced by CH- or -C≡C-.
A ¹² and A ²² are independently expressed from the following equations (A-ii-1) to (A-ii-14).

(In the formula, the broken line represents the bonding position, and ^{when a plurality of L 12s} are present, they may be the same or different.), But when there are a plurality of ^{A 12s, they are the same.} may be be different also, they if a ²² there are a plurality may be the same or different and
In L ^12, a fluorine atom or any hydrogen atom in the group may be substituted with a fluorine atom, and -CH _{2- in} the group may be substituted by -O-, which is a direct number of carbon atoms 1 to 10. Represents a chain alkyl group or a branched or cyclic alkyl group having 3 to 10 carbon atoms.
Z ¹² , Z ²² and Z ³² are independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -N. = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, Z 12} there are a plurality of If they are the same or different, ^{if there are multiple Z 22s} they may be the same or different.
m12 and m22 independently represent 0, 1 or 2, and m12 + m22 represent 0, 1 or 2, respectively.
X ¹² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Y ¹² and Y ³² independently represent a hydrogen atom, a fluorine atom or a chlorine atom, Y ²² is a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is replaced with a fluorine atom. An alkyl group having 1 to 8 carbon atoms which may be used, an alkoxy group having 1 to 7 carbon atoms which may have any hydrogen atom replaced by a fluorine atom, and an arbitrary hydrogen atom which has been replaced by a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. ) Is more preferable, and the following general formula (I-iii)

(In the formula, R ¹³ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, or a carbon atom. Represents the alkynyl group of the numbers 2 to 8
A ¹³ and A ²³ are independently expressed in the following formulas (A-iii-1) to (A-iii-7) and (A-iii-12).

(Wherein the dashed line represents a bond position, they if L ¹³ there are a plurality may be the same or different.) Represents a group selected from,
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 independently represent -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C ≡ C- or a single bond, respectively.
m13 and m23 independently represent 0 or 1, and m13 + m23 represent 0, 1 or 2, respectively.
X ¹³ represents a hydrogen atom, a methyl group or an ethyl group.
Y ¹³ and Y ³³ independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ²³ represents a fluorine atom, a chlorine atom or a cyano group. ) Is more preferable, and the following general formulas (I-iv-1) to (I-iv-3)

(In the formula, R ¹⁴ represents an alkyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 3 to 7 carbon atoms.
A ¹⁴ and A ²⁴ are the following formulas (A-iv-1), formulas (A-iv-3) to formulas (A-iv-7).

(Wherein the dashed line represents a bond position, they if L ¹⁴ there are a plurality may be the same or different.) Represents a group selected from,
L ¹⁴ represents a fluorine atom or a linear alkyl group having 1 to 8 carbon atoms.
Z ¹⁴ , Z ²⁴ and Z ³⁴ each independently represent -C≡C- or a single bond.
Y ¹⁴ and Y ³⁴ independently represent a hydrogen atom or a fluorine atom, and Y ²⁴ represents a fluorine atom or a cyano group, respectively. ) Is particularly preferable.

Specifically, as the compound represented by the general formula (I), the following formulas (I-1) to (I-29)

Examples thereof include compounds represented by.

The compound of the present invention can be produced by the following production method.
(Manufacturing method 1) Production of a compound represented by the following formula (s-7)

(In the formula, 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, and A. ¹⁴ and A ²⁴ represent groups selected from the above formulas (A-iv-1), formulas (A-iv-3) to formulas (A-iv-7), and Y ¹⁴ and Y ³⁴ are independent of each other. Represents a hydrogen atom or a fluorine atom, and Y ²⁴ represents a fluorine atom or a cyano group.)
By reacting the compound represented by the formula (s-1) with, for example, N-bromosuccinimide, the compound represented by the formula (s-2) can be obtained.

By reacting the compound represented by the formula (s-2) with, for example, N-iodosuccinimide, the compound represented by the formula (s-3) can be obtained.

By reacting the compound represented by the formula (s-3) with the compound represented by the general formula (s-4), the compound represented by the general formula (s-5) can be obtained. 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, and dichlorobis [di-tert-butyl (p-dimethylaminophenyl) phosphino] palladium. (II), tetrakis (triphenylphosphine) palladium (0) and the like can be mentioned. When palladium (II) acetate is used as the metal catalyst, ligands such as triphenylphosphine and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl may be added. Specific examples of the base include potassium carbonate, potassium phosphate, cesium carbonate and the like.

By reacting the compound represented by the general formula (s-5) with the compound represented by the general formula (s-6), the compound represented by the general formula (s-7) can be obtained. Examples of the reaction method include a Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst include the above. Specific examples of the copper catalyst include copper (I) iodide. Specific examples of the base include triethylamine and the like.
(Manufacturing method 2) Production of a compound represented by the following formula (s-14)

(In the formula, Alkyl represents an alkyl group, Y ¹⁴ and Y ³⁴ independently represent a hydrogen atom or a fluorine atom, and Y ²⁴ represents a fluorine atom or a cyano group.)
The compound represented by the formula (s-10) can be obtained by reacting the compound represented by the formula (s-8) with the compound represented by the formula (s-9) in the presence of Lewis acid. Specific examples of Lewis acid include aluminum chloride (III) and the like.

The compound represented by the formula (s-11) can be obtained by reducing the carbonyl group of the compound represented by the formula (s-10). Examples of the reaction method include a method using aluminum chloride (III) and lithium aluminum hydride.

The compound represented by the formula (s-12) can be obtained by reacting the compound represented by the formula (s-11) with, for example, N-bromosuccinimide.

By reacting the compound represented by the formula (s-12) with the compound represented by the general formula (s-13), the compound represented by the general formula (s-14) can be obtained. Examples of the reaction method include a Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst, the copper catalyst and the base include the above.

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

The functional group can be protected as needed in each process. Protecting groups include, for example, GREENE'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE co-authored, A John Wiley, Inc., A John Wiley, Inc., Protecting Group, etc.) The group is mentioned.

In addition, purification can be performed as needed in each process. 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, activated carbon and the like.

The compound represented by the general formula (I) is preferably used by being added to the liquid crystal composition. When the liquid crystal composition contains a compound represented by the general formula (I), it may contain one compound represented by the general formula (I), and a plurality of compounds represented by the general formula (I). May be contained. 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 5% by mass or more. It is more preferably 10% by mass or more and 95% by mass or less, further preferably 15% by mass or more and 90% by mass or less, and 20% by mass or more and 85% by mass or less. Is particularly preferable. Here, the "total content of the compounds represented by the general formula (I)" is expressed in the general formula (I) when the liquid crystal composition contains one compound represented by the general formula (I). It means the content of the compound represented, and when the liquid crystal composition contains a plurality of compounds represented by the general formula (I), the total content of the plurality of compounds represented by the general formula (I) is summed up. means.

The liquid crystal composition containing the compound represented by the general formula (I) preferably has a refractive index anisotropy (Δn) of 0.15 or more and 1.00 or less. From the viewpoint 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 0.20 or more, preferably 0.95 or less, and 0.25 or more. It is more preferably 0.90 or less, more preferably 0.30 or more and 0.85 or less, and particularly preferably 0.35 or more and 0.80 or less.

A liquid crystal composition containing a compound represented by the general formula (I) can be applied to a high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image. When used, the liquid crystal composition containing the compound represented by the general formula (I) preferably has a dielectric anisotropy (Δε) of 2 or more and 60 or less. From the viewpoint of the liquid crystal phase temperature range, storage stability, weather resistance, driving voltage, rotational viscosity and elastic modulus of the liquid crystal composition, the dielectric anisotropy (Δε) is preferably 2.5 or more and preferably 50 or less. It is more preferably 3 or more and 40 or less, and particularly preferably 3.5 or more and 30 or less.

The liquid crystal composition containing the compound represented by the general formula (I) is preferably used for a high frequency device. The frequency range is preferably 1 MHz or more and 1 THz or less, more preferably 1 GHz or more and 500 GHz or less, further preferably 2 GHz or more and 300 GHz or less, and 5 GHz or more and 150 GHz or less. It is particularly preferable to have.

The liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (IV).

(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 is the formula from the following formula (A6-1) (A6-8)

(Wherein the dashed line represents. A binding position) represents a group selected from those if A ³ there are multiple it may have the same or different and
Z ⁴ is -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _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 ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH -OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _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 represents a single bond, even they are the same ^{if Z 4} there are a plurality of May be different
m3 represents an integer from 1 to 4
A ^y is the following formula (Ay-1) and Formula (Ay-2)

(In the formula, the broken line represents the bond position, Y ⁷ , Y ⁹ , Y ¹⁰ and Y ¹² independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸ and Y ¹¹ independently represent a fluorine atom. , Chlorine atom, cyano group, thioisocyano group, nitro group, pentafluorosulfanyl group, alkyl group with 1 to 8 carbon atoms in which any hydrogen atom is replaced with fluorine atom, any hydrogen atom is substituted with fluorine atom. An alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms in which any hydrogen atom is substituted with a fluorine atom, or an alkenyl having 2 to 7 carbon atoms in which any hydrogen atom is substituted with a fluorine atom. Represents an oxy group, where one -CH _2- or two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-,-. CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO- It represents a group selected from CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-). ) Is preferably contained. From the viewpoint of the liquid crystal phase temperature range, refractive index anisotropy, dielectric anisotropy, rotational viscosity and elastic modulus of the liquid crystal composition, the compound represented by the general formula (VI) is represented by the following general formula (VI-i).

(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 each represents a group selected from the formula (A6-6) from the above equation ^(A6-1), they ^{if A 31} there are a plurality may be the same or different and
Z ⁴¹ is -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH = CH-COO-, -OCO -CH = CH-, -CH = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, but they are the same when there are multiple ^{Z 41s.} Can be different
m31 represents an integer from 1 to 3 and represents
^Ay1 is the following formula (Ay-1-i) and formula (Ay-2-i).

(In the formula, the broken line represents the bond position, Y ⁷¹ , Y ⁹¹ , Y ¹⁰¹ and Y ¹²¹ independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸¹ and Y ¹¹¹ independently represent a fluorine atom. , Chlorine atom, cyano group, thioisocyano group, nitro group, pentafluorosulfanyl group, alkyl group having 1 to 8 carbon atoms in which any hydrogen atom may be replaced with fluorine atom, any hydrogen atom becomes fluorine atom An alkoxy group having 1 to 7 carbon atoms which may be substituted, an alkenyl group having 2 to 8 carbon atoms which may have any hydrogen atom substituted with a fluorine atom, or an arbitrary hydrogen atom is substituted with a fluorine atom. Represents an alkenyloxy group having 2 to 7 carbon atoms which may be present.). ) Is preferable, and the compound represented by the general formula (VI) is represented by the following general formula (VI-ii).

(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 formula (A6-5), but when there are a plurality of ^{A 32s, they may be the same or different.}
Z ⁴² represents -CF ₂ O-, -OCF _2- , -CH = CH-, -CF = CF-, -C ≡ C- or a single bond, but they are the same if there are multiple ^{Z 42s.} Can be different
m32 represents 1, 2 or 3
Y ⁷² and Y ⁹² independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸² is a fluorine atom, a chlorine atom, a cyano group, a thioisocyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is fluorine. An alkyl group having 1 to 8 carbon atoms which may be substituted with an atom, an alkoxy group having 1 to 7 carbon atoms which may be substituted with an arbitrary hydrogen atom as a fluorine atom, and an arbitrary hydrogen atom as a fluorine atom. Represents an alkenyl group having 2 to 8 carbon atoms which may be substituted or an alkenyloxy group having 2 to 7 carbon atoms which may have any hydrogen atom substituted with a fluorine atom. ) Is more preferable, and the compound represented by the general formula (VI) is represented by the following general formula (VI-iii).

(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 formula (A6-5), but when there are a plurality of ^{A 33s, they may be the same or different.}
Z ⁴³ is _{_{-CF 2 O -, - OCF 2}} -, - C≡C- or represents a single ^bond, they ^{if Z 43} there are a plurality may be the same or different and
m33 represents 1, 2 or 3
Y ⁷³ and Y ⁹³ independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y ⁸³ represents a fluorine atom, a chlorine atom, a cyano group or a thioisocyano group. ) Is more preferable, and the compound represented by the general formula (VI) is from the following general formula (VI-iv-1) to the general formula (VI-iv-21).

In particular, R ⁶¹⁴ is a compound represented by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. preferable.

The liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (III).

(In the formula, R ³¹ and R ³² are independently alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, or carbon atoms 2 to 7 respectively. Represents the alkenyloxy group of
A ³¹ and A ³² are independently expressed by the following equations (A3-1) to (A3-8).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A 32s,} they may be the same or different.
m31 represents an integer from 1 to 4. ) May be contained. From the viewpoint of the liquid crystal phase temperature range, refractive index anisotropy, dielectric anisotropy, rotational viscosity and elastic modulus of the liquid crystal composition, the compound represented by the general formula (III) is represented by the following general formula (III-i).

(In the formula, R ³¹¹ and R ³²¹ each independently have an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of
A ³¹¹ and A ³²¹ are independently derived from the following equations (A31-1) to (A31-6).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A 321s,} they may be the same or different.
m311 represents an integer from 1 to 3. ) Is preferable, and the compound represented by the general formula (III) is the following general formula (III-ii).

(In the formula, R ³¹² and R ³²² are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of
A ³¹² and A ³²² are independently derived from the following equations (A32-1) to (A32-4).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A 322s,} they may be the same or different.
m312 represents 1 or 2. ) Is more preferable, and the compound represented by the general formula (III) is the following general formula (III-iii).

(In the formula, R ³¹³ and R ³²³ independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
A ³¹³ and A ³²³ are independently represented by the following equations (A33-1) and (A33-2), respectively.

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A 323s,} they may be the same or different.
m313 represents 1 or 2. ) Is more preferable, and the compound represented by the general formula (III) is from the following general formula (III-iv-1) to the general formula (III-iv-10).

(In the formula, R ³¹⁴ and R ³²⁴ independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms). It is particularly preferable that the compound is a compound.

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

When the dielectric anisotropy (Δε) of the liquid crystal composition containing the compound represented by the general formula (I) is neutral or negative, the liquid crystal composition has the following general formula (IV).

(In the formula, R ⁴¹ and R ⁴² are independently alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, or carbon atoms 2 to 7 respectively. Represents the alkenyloxy group of
A ⁴¹ and A ⁴² are independently expressed by the following equations (A4-1) to (A4-11).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A 41s,} they may be the same or different, and when there are a plurality of ^{A 42s, they are the same.} Can be different
Z ⁴¹ and Z ⁴² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _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 ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH _2- OCO-, -CH = CH-, -N = Represents N-, -CH = N-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, but when there are multiple ^{Z 41s.} They may be the same or different, and ^{if there are multiple Z 42s,} they may be the same or different.
m41 and m42 independently represent integers from 0 to 3, while m41 + m42 represent integers from 1 to 3. ) May be contained. From the viewpoint of the liquid crystal phase temperature range, refractive index anisotropy, dielectric anisotropy, rotational viscosity and elastic modulus of the liquid crystal composition, the compound represented by the general formula (IV) is represented by the following general formula (IV-i).

(In the formula, R ⁴¹¹ and R ⁴²¹ are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of
Although A ⁴¹¹ and ^{A 421} each independently represent a group selected from the formula (A4-9) from the above equation ^(A4-1), they ^{if A 411} there are a plurality optionally be the same or different If there are multiple A ^421s, they may be the same or different.
Z ⁴¹¹ and Z ⁴²¹ are independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, but Z ⁴¹¹ When there are a plurality of them, they may be the same or different, and ^{when there are a plurality of Z 421s,} they may be the same or different.
m411 and m421 independently represent integers from 0 to 3, while m411 + m421 represent integers from 1 to 3. ) Is preferable, and the compound represented by the general formula (IV) is the compound represented by the following general formula (IV-ii).

(In the formula, R ⁴¹² and R ⁴²² are independently alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Represents the alkenyloxy group of
Although A ⁴¹² and ^{A 422} each independently represent a group selected from the formula (A4-7) from the above equation ^(A4-1), they ^{if A 412} there are a plurality optionally be the same or different If there are multiple A ^422s, they may be the same or different.
Z ⁴¹² and Z ⁴²² independently form -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O-, -OCF _2- or single bond. As represented, ^{when there are a plurality of Z 412s,} they may be the same or different, and ^{when there are a plurality of Z 422s,} they may be the same or different.
m412 and m422 independently represent 0, 1 or 2, while m412 + m422 represent 1 or 2. ) Is more preferable, and the compound represented by the general formula (IV) is the following general formula (IV-iii).

(In the formula, R ⁴¹³ and R ⁴²³ independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, respectively.
Although A ⁴¹³ and ^{A 423} each independently represent a group selected from the formula (A4-5) from the above equation ^(A4-1), they ^{if A 413} there are a plurality optionally be the same or different If there are multiple A ^423s, they may be the same or different.
Z ⁴¹³ and Z ⁴²³ independently represent -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- or a single bond, but ^{if there are multiple Z 413s,} they are the same but different. If there are a plurality of Z ^423s, they may be the same or different.
m413 and m423 independently represent 0, 1 or 2, while m413 + m423 represent 1 or 2. ) Is more preferable, and the compound represented by the general formula (IV) is from the following general formula (IV-iv-1) to the general formula (IV-iv-8).

(In the formula, R ⁴¹⁴ and R ⁴²⁴ independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms). It is particularly preferable that the compound is a compound.

A stabilizer may be added to the liquid crystal composition containing the compound represented by the general formula (I) in order to improve its storage stability. Examples of stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. Be done. When a stabilizer is used, the amount added is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. Further, one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. The following general formula (X1) is used as a stabilizer.

(In the formula, Sp ^x1 has one -CH _2- or two or more non-adjacent -CH _2- independently of -O-, -S-, -CO-, -COO-, and -OCO. -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, An alkylene group or single with 1 to 20 carbon atoms that may be substituted by -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-. Representing a bond, A ^x1 is from the following formula (Ax1-1) to formula (Ax1-8).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A x1,} they may be the same or different.
Z ^x1 is -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _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 ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH -OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N -, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, but ^{if there are multiple Z x1,} they may be the same May be different
mx1 represents 0 or 1 and represents
mx2 represents an integer from 0 to 4. ) Is mentioned. From the viewpoint of voltage retention and compatibility with the liquid crystal composition, the compound represented by the general formula (X1) is represented by the following general formula (X1-i).

(In the formula, Sp ^x11 is a _{carbon in which one -CH 2-} or two or more non-adjacent-CH ₂ -s may be independently substituted with -O-, -COO- or -OCO-, respectively. Represents an alkylene group or a single bond having 1 to 20 atoms, and A ^x11 is the following formula (Ax11-1) and formula (Ax11-2).

(In the formula, the broken line represents the bonding position.) However, ^{when there are a plurality of A x11s,} they may be the same or different.
Z ^x11 represents -COO-, -OCO-, -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO- or a single bond, but ^{if there are multiple Z x11s} , they are different even if they are the same. May be
mx11 represents 0 or 1 and represents
mx21 represents 0 or 1. ) Is preferable, and the compound represented by the general formula (X1) is from the following general formula (X1-ii-1) to the general formula (X1-ii-4).

(In the formula, Sp ^x12 represents an alkylene group or a single bond having 1 to 20 carbon atoms.) It is particularly preferable that the compound is represented by.

Further, the liquid crystal composition containing the compound represented by the general formula (I) is described in the following general formula (X2).

(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 ^x22 each independently represent a spacer group or a single bond.
mx21 represents 0 or 1 and represents
mx22 represents 0 or 1,
mx23 represents 0 or 1. ) Is mentioned. From the viewpoint of voltage retention and compatibility with the liquid crystal composition, the compound represented by the general formula (X2) is represented by the following general formula (X2-i).

(In the formula, R ^x211 , ^Rx221 , ^Rx231 and ^Rx241 independently represent a hydrogen atom, an oxygen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, respectively. ,
Sp ^x211 , Sp ^x221 , Sp ^x231 and Sp ^x221 may each independently replace any hydrogen atom in the group with a fluorine atom, and one -CH _2- or two or more non-adjacent hydrogen atoms. -CH _2- independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-,- A linear or branched alkylene group having 1 to 20 carbon atoms which may be replaced with CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-. Represents a single bond
mx211 represents 0 or 1 and represents
mx221 represents 0 or 1
mx231 represents 0 or 1. ) Is preferable, and the compound represented by the general formula (X2) is represented by the following general formula (X2-ii).

(In the formula, R ^x212 and R ^x222 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, respectively.
Sp ^x212 and Sp ^x222 each independently _{replace one -CH 2-} or two or more non-adjacent -CH _2-s with -O-, -COO- or -OCO-, respectively. It represents a linear alkylene group or a single bond having 1 to 10 carbon atoms which may be used.
mx212 represents 0 or 1. ) Is more preferable, and the compound represented by the general formula (X2) is represented by the following general formula (X2-iii).

(In the formula, R ^x213 and ^Rx223 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, respectively.
Sp ^x213 is a linear chain having 1 to 10 carbon atoms in which one -CH _2- or two or more non-adjacent -CH _{2-s may be independently replaced with -COO- or -OCO-.} Represents a alkylene group. ) Is particularly preferable.

In the present invention, the ring structure contained in the 1,4-cyclohexylene group, the decahydronaphthalene-2,6-diyl group and the 1,3-dioxane-2,5-diyl group is either a trans form or a cis form, respectively. However, from the viewpoint of liquid crystallinity, the content of each trans form is preferably higher than that of the cis form, and the content of the trans form in the ring structure is more preferably 80% or more. , The content of the trans body in the ring structure is more preferably 90% or more, the content of the trans body in the ring structure is even more preferably 95% or more, and the content of the trans body in the ring structure is 98. % Or more is particularly preferable. Further, in the present invention, the following notation (CY-1)

(In the formula, the broken line represents the bond position.) Means the trans form and / or the cis form of the 1,4-cyclohexylene group.

Further, in the present invention, each element may be replaced with an isotope of the same element.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "mass%". When handling substances that are unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. The purity of each compound is UPLC (Waters ACQUITY UPLC, BEH C ₁₈ (100 x 2.1 mm x 1.7 μm), acetonitrile / water or acetonitrile / water containing 0.1% formic acid, PDA, column temperature 40 ° C.), GPC ( Shimadzu HPLC Prominence, Shodex KF-801 (300 mm x 8 mm x 6 μm) + KF-802 (300 mm x 8 mm x 6 μm), acetonitrile, RI, UV (254 nm), column temperature 40 ° C.), GC (Agient 6890A, J & W DB- Determined by 1, 30 m x 0.25 mm x 0.25 μm, carrier gas He, FID, 100 ° C (1 minute) → temperature rise 10 ° C / min → 300 ° C (12 minutes)) or ¹ H NMR (JEOL, 400 MHz). did.
(Example 1) Production of a compound represented by the formula (I-1)

Under a nitrogen atmosphere, 12.6 g of aluminum chloride (III) and 38 mL of dichloromethane were added to the reaction vessel. A solution prepared by dissolving 10.0 g of butyryl chloride in 10 mL of dichloromethane was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 2 hours. A solution prepared by dissolving 12.0 g of the compound represented by the formula (I-1-1) in 48 mL of dichloromethane was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water and subjected to liquid separation treatment. The organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 10.0 g of the compound represented by the formula (I-1-2).

Under a nitrogen atmosphere, 7.2 g of lithium aluminum hydride and 58 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 12.7 g of aluminum chloride (III) was added little by little. While cooling with ice, a solution prepared by dissolving 10.0 g of the compound represented by the formula (I-1-2) in 30 mL of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 5 hours. While cooling with ice, 10% hydrochloric acid was added dropwise, and the precipitate was removed by filtration. Purification by column chromatography (silica gel, dichloromethane / hexane) gave 7.0 g of the compound represented by the formula (I-1-3).

7.0 g of the compound represented by the formula (I-1-3) and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 7.6 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. The organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 10.0 g of the compound represented by the formula (I-1-4).

Under a nitrogen atmosphere, 9.9 g of the compound represented by the formula (I-1-4), 0.3 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.3 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 79 mL of diisopropylamine, and 158 mL of N, N-dimethylformamide were added. While heating at 90 ° C., 5.9 g of the compound represented by the formula (I-1-5) was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is washed successively with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane), activated carbon treatment and recrystallization (acetone / methanol) to obtain the formula (I-1). 2.8 g of the represented compound was obtained.
Phase transition temperature: C 68 I
1H-NMR (400MHz, CHLOROFORM-D) δ 7.34-7.29 (m, 2H), 7.26-7.22 (m, 1H), 7.12 (td, J = 9.4,7) 0.8Hz, 1H), 6.90 (d, J = 0.9Hz, 1H), 2.90-2.87 (m, 2H), 1.74-1.66 (m, 2H), 1.42 (Td, J = 14.9, 7.3Hz, 2H), 0.94 (t, J = 7.3Hz, 3H)
MS (EI): m / z = 332
(Example 2) Production of a compound represented by the formula (I-2)

7.0 g of the compound represented by the formula (I-2-1) and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 9.3 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. The organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 8.8 g of the compound represented by the formula (I-2-2).

Under a nitrogen atmosphere, 8.8 g of the compound represented by the formula (I-2-2), 0.3 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.3 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 141 mL of N, N-dimethylformamide were added. While heating at 90 ° C., 4.0 g of 1-hexyne was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The compound represented by the formula (I-2-3) is obtained by sequentially washing the organic layer with 5% hydrochloric acid and a saline solution, and then purifying the organic layer by column chromatography (silica gel, dichloromethane / hexane) and activated carbon treatment. 0 g was obtained.

7.0 g of the compound represented by the formula (I-2-3) and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 6.9 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. The organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 7.7 g of the compound represented by the formula (I-2-4).

Under a nitrogen atmosphere, 7.7 g of the compound represented by the formula (I-2-4), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 141 mL of N, N-dimethylformamide were added. While heating at 90 ° C., 4.0 g of the compound represented by the formula (I-2-5) was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is washed successively with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane), activated carbon treatment and recrystallization (acetone / methanol) to obtain the formula (I-2). 5.5 g of the represented compound was obtained.
MS (EI): m / z = 356
(Example 3) Production of a compound represented by the formula (I-3)

By the same method except that butyryl chloride was replaced with valeryl chloride and the compound represented by the formula (I-1-5) was replaced with the compound represented by the formula (I-3-5) in Example 1. A compound represented by the formula (I-3) was produced.
MS (EI): m / z = 364
(Example 4) Production of a compound represented by the formula (I-4)

By the same method except that 1-hexyne was replaced with 1-heptin and the compound represented by the formula (I-2-5) was replaced with the compound represented by the formula (I-4-5) in Example 2. A compound represented by the formula (I-4) was produced.
MS (EI): m / z = 388
(Example 5) Production of a compound represented by the formula (I-5)

It is represented by the formula (I-5) by the same method except that the compound represented by the formula (I-1-5) is replaced with the compound represented by the formula (I-5-2) in Example 1. The compound was produced.
MS (EI): m / z = 400
(Example 6) Production of a compound represented by the formula (I-6)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-6-1), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 141 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 3.7 g of the compound represented by the formula (I-6-2) in 11 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane), activated carbon treatment and recrystallization (acetone / methanol) to formula (I-6-3). ) Was obtained.

Under a nitrogen atmosphere, 5.9 g of the compound represented by the formula (I-6-3) and 59 mL of tetrahydrofuran were added to the reaction vessel. 13 mL of a butyllithium / hexane solution (1.61 mol / L) was added dropwise at −50 ° C., and the mixture was stirred at −50 ° C. for 1 hour. Carbon dioxide gas was introduced into the reaction solution until no exotherm occurred. The temperature was raised to room temperature, the reaction mixture was poured into 5% hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer is sequentially washed with water and brine, and then purified by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallized (ethyl acetate / hexane), thereby represented by the formula (I-6-4). 5.3 g of the compound to be obtained was obtained.

Under a nitrogen atmosphere, 5.3 g of the compound represented by the formula (I-6-4), 53 mL of 1,2-dichloroethane and 0.5 mL of pyridine were added to the reaction vessel. At room temperature, 2.4 g of thionyl chloride was added dropwise, and the mixture was heated under reflux for 6 hours. Dichloroethane and excess thionyl chloride were distilled off under reduced pressure. 53 mL of 1,2-dichloroethane was added. While cooling with ice, ammonia gas was introduced into the reaction solution until no heat was generated. The temperature was raised to room temperature, the reaction mixture was poured into 5% hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and brine, and the solvent was distilled off under reduced pressure. 53 mL of N, N-dimethylformamide was added. While cooling with ice, 2.5 g of phosphorus oxychloride was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with toluene. The organic layer is washed successively with water and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane) and recrystallized (dichloromethane / methanol). Compound 3 represented by the formula (I-6). 5.5 g was obtained.
MS (EI): m / z = 371
(Example 7) Production of a compound represented by the formula (I-7)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-7-1), 3.2 g of pyridine, and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 10.5 g of trifluoromethanesulfonic anhydride was added dropwise, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into a 5% aqueous sodium hydrogen carbonate solution for liquid separation treatment. The organic layer was washed successively with 5% hydrochloric acid, water and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane). As a result, 9.2 g of the compound represented by the formula (I-7-2) was obtained. Got

Under a nitrogen atmosphere, 9.2 g of the compound represented by the formula (I-7-2), 8.0 g of potassium acetate, 8.3 g of bis (pinacolato) diboron, 74 mL of dimethyl sulfoxide, [1,1'-bis] were placed in the reaction vessel. (Diphenylphosphino) ferrocene] Palladium (II) dichloride, 0.4 g of a dichloromethane adduct was added, and the mixture was heated and stirred at 80 ° C. for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (alumina, dichloromethane) to obtain 6.9 g of the compound represented by the formula (I-7-3).

7.0 g of the compound represented by the formula (I-7-4) and 70 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 7.9 g of N-iodosuccinimide 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. The organic layer was washed with brine and purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 8.8 g of the compound represented by the formula (I-7-5).

Under a nitrogen atmosphere, 8.8 g of the compound represented by the formula (I-7-5) and 5.3 g of potassium carbonate, 8.1 g of the compound represented by the formula (I-7-3), 45 mL of toluene were placed in the reaction vessel. 27 mL of ethanol, 27 mL of water, and 0.4 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-7-6) by sequentially washing with water and brine, and then purifying by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol). 7.3 g of compound was obtained.

Under a nitrogen atmosphere, 5.4 g of lithium aluminum hydride and 54 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 4.8 g of aluminum chloride (III) was added little by little. While cooling with ice, a solution prepared by dissolving 7.3 g of the compound represented by the formula (I-7-6) in 15 mL of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 5 hours. While cooling with ice, 10% hydrochloric acid was added dropwise, and the precipitate was removed by filtration. Purification by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol) gave 4.9 g of the compound represented by the formula (I-7-7).

In Example 1, the compound represented by the formula (I-1-4) is the compound represented by the formula (I-7-7), and the compound represented by the formula (I-1-5) is represented by the formula (I-1-5). A compound represented by the formula (I-7) was produced by the same method except that the compound represented by -7-8) was replaced.
MS (EI): m / z = 468
(Example 8) Production of a compound represented by the formula (I-8)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-8-1), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 141 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 4.0 g of the compound represented by the formula (I-8-2) in 8 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with 5% hydrochloric acid and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane), activated carbon treatment and recrystallization (acetone / methanol) to formula (I-8-3). ) Was obtained.

Under a nitrogen atmosphere, 5.6 g of the compound represented by the formula (I-8-3), 2.8 g of potassium acetate, 4.0 g of bis (pinacolato) diboron, 56 mL of dimethyl sulfoxide, [1,1'-bis] were placed in the reaction vessel in a reaction vessel. (Diphenylphosphino) ferrocene] Palladium (II) dichloride 0.1 g of a dichloromethane adduct was added, and the mixture was heated and stirred at 80 ° C. for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (alumina, dichloromethane) to obtain 5.0 g of the compound represented by the formula (I-8-4).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-4), 2.4 g of potassium carbonate, 2.7 g of the compound represented by the formula (I-8-5), and 40 mL of toluene were placed in the reaction vessel. 20 mL of ethanol, 20 mL of water, and 0.2 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is washed successively with water and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane) and recrystallized (dichloromethane / hexane). Compound 3 represented by the formula (I-8). 8.8 g was obtained.
MS (EI): m / z = 476
(Example 9) Production of a compound represented by the formula (I-9)

In Example 1, the compound represented by the formula (I-1-4) is the compound represented by the formula (I-9-1), and the compound represented by the formula (I-1-5) is represented by the formula (I-1-5). A compound represented by the formula (I-9) was produced by the same method except that it was replaced with the compound represented by -9-2).
MS (EI): m / z = 472
(Example 10) Production of a compound represented by the formula (I-10)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-10-1) and 4.2 g of potassium carbonate, 4.1 g of the compound represented by the formula (I-10-2), 56 mL of toluene were placed in the reaction vessel. 28 mL of ethanol, 28 mL of water, and 0.4 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-10-3) by sequentially washing with water and a saline solution and then purifying by column chromatography (silica gel, dichloromethane / hexane) and recrystallization (dichloromethane / methanol). 5.0 g of the compound was obtained.

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-3), 2.9 g of potassium carbonate, 2.7 g of the compound represented by the formula (I-10-4), and 40 mL of toluene were placed in the reaction vessel. 20 mL of ethanol, 20 mL of water, and 0.3 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The compound 4 represented by the formula (I-10) is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / hexane) after sequentially washing the organic layer with water and saline. 0.0 g was obtained.
MS (EI): m / z = 406
(Example 11) Production of a compound represented by the formula (I-11)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-11-1), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 140 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 3.4 g of the compound represented by the formula (I-11-2) in 7 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with 5% hydrochloric acid, water and saline, and then purified by column chromatography (silica gel, toluene / hexane), activated carbon treatment and recrystallization (acetone / ethanol) to formula (I-11). 5.6 g of the compound represented by -3) was obtained.

Under a nitrogen atmosphere, 5.6 g of the compound represented by the formula (I-11-3) and 56 mL of tetrahydrofuran were added to the reaction vessel. 20 mL of sec-butyllithium / cyclohexane and hexane solution (1.0 mol / L) were added dropwise at −60 ° C., and the mixture was stirred at −60 ° C. for 1 hour. 4.0 g of triisopropyl borate was added dropwise at −60 ° C., and the temperature was raised to 0 ° C. While cooling with ice, 20 mL of 10% hydrochloric acid was added dropwise, and the mixture was stirred at room temperature for 1 hour. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and brine, and then purified by column chromatography (alumina, ethyl acetate) to obtain 5.1 g of the compound represented by the formula (I-11-4).

Under a nitrogen atmosphere, 5.1 g of the compound represented by the formula (I-11-4), 2.7 g of the compound represented by the formula (I-11-5), 3.0 g of potassium carbonate, and dichlorobis [dichlorobis [di] were placed in the reaction vessel in a reaction vessel. -T-butyl (p-dimethylaminophenyl) phosphino] Palladium (II) 0.2 g, toluene 40 mL, ethanol 20 mL, water 20 mL were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-11-6) by sequentially washing with water and a saline solution and then purifying by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol). 4.9 g of compound was obtained.

It is represented by the formula (I-11) by the same method except that the compound represented by the formula (I-6-3) is replaced with the compound represented by the formula (I-11-6) in Example 6. The compound was produced.
MS (EI): m / z = 451
(Example 12) Production of a compound represented by the formula (I-12)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-12-1), 8.6 g of potassium acetate, 8.2 g of bis (pinacolato) diboron, 70 mL of dimethyl sulfoxide, [1,1'-bis] were placed in the reaction vessel. (Diphenylphosphino) ferrocene] Palladium (II) dichloride, 0.4 g of a dichloromethane adduct was added, and the mixture was heated and stirred at 80 ° C. for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (alumina, dichloromethane) to obtain 6.7 g of the compound represented by the formula (I-12-2).

Under a nitrogen atmosphere, 6.7 g of the compound represented by the formula (I-12-2) and 4.9 g of potassium carbonate, 6.6 g of the compound represented by the formula (I-12-3), 54 mL of toluene were placed in the reaction vessel. 27 mL of ethanol, 27 mL of water, and 0.2 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (silica gel, dichloromethane / hexane) to obtain 5.9 g of the compound represented by the formula (I-12-4).

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-12-5), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 141 mL of N, N-dimethylformamide were added. While heating at 90 ° C., 3.1 g of trimethylsilylacetylene was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (silica gel, toluene / hexane) and activated charcoal treatment to obtain 5.9 g of the compound represented by the formula (I-12-6). Obtained.

5.9 g of the compound represented by the formula (I-12-6), 118 mL of methanol and 5.4 g of potassium carbonate were added to the reaction vessel, and the mixture was stirred at room temperature for 8 hours. Water was added to the reaction mixture, and the mixture was extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (silica gel, toluene / hexane) to obtain 3.6 g of the compound represented by the formula (I-12-7).

In a nitrogen atmosphere, 4.6 g of the compound represented by the formula (I-12-4), 0.1 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.1 g of isopropylbiphenyl [XPhos], 0.1 g of palladium (II) acetate, 37 mL of diisopropylamine, and 74 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 3.6 g of the compound represented by the formula (I-12-7) in 7 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-12) by sequentially washing with water and brine, and then purifying by column chromatography (silica gel, toluene / hexane), activated charcoal treatment, and recrystallization (toluene / ethanol). 4.8 g of the compound was obtained.
MS (EI): m / z = 468
(Example 13) Production of a compound represented by the formula (I-13)

By the same method except that the compound represented by the formula (I-7-1) was replaced with the compound represented by the formula (I-13-1) in Example 7, the formula (I-13-3) was used. The compound represented was produced.

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-13-4), 7.0 g of the compound represented by the formula (I-13-3), 5.3 g of potassium carbonate, and dichlorobis [dichlorobis [di] were placed in the reaction vessel in a reaction vessel. -T-Butyl (p-dimethylaminophenyl) phosphino] Palladium (II) 0.2 g, toluene 56 mL, ethanol 28 mL, water 28 mL were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The compound represented by the formula (I-13) 6 is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) after sequentially washing the organic layer with water and saline. .1 g was obtained.
MS (EI): m / z = 342
(Example 14) Production of a compound represented by the formula (I-14)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-14-1), 0.2 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.2 g of isopropylbiphenyl [XPhos], 0.2 g of palladium (II) acetate, 70 mL of diisopropylamine, and 140 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 4.0 g of the compound represented by the formula (I-14-2) in 8 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-14) by sequentially washing with water and brine, and then purifying by column chromatography (silica gel, toluene / hexane), activated charcoal treatment, and recrystallization (toluene / hexane). 6.0 g of the compound was obtained.
MS (EI): m / z = 338
(Example 15) Production of a compound represented by the formula (I-15)

In Example 8, the compound represented by the formula (I-8-1) is the compound represented by the formula (I-15-1), and the compound represented by the formula (I-8-2) is the compound represented by the formula (I-8-2). A compound represented by the formula (I-15-3) was produced by the same method except that the compound represented by -15-2) was replaced.

In Example 14, the compound represented by the formula (I-14-1) is the compound represented by the formula (I-15-3), and the compound represented by the formula (I-14-2) is represented by the formula (I-14-2). A compound represented by the formula (I-15) was produced by the same method except that the compound represented by -15-4) was replaced.
MS (EI): m / z = 410
(Example 16) Production of a compound represented by the formula (I-16)

By the same method except that the compound represented by the formula (I-7-1) was replaced with the compound represented by the formula (I-16-1) in Example 7, the formula (I-16-5) was used. The compound represented was produced.

In Example 7, the compound represented by the formula (I-7-7) is the compound represented by the formula (I-16-5), and the compound represented by the formula (I-7-8) is the compound represented by the formula (I-7-8). A compound represented by the formula (I-16) was produced by the same method except that the compound represented by -16-6) was replaced.
MS (EI): m / z = 502
(Example 17) Production of a compound represented by the formula (I-17)

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-17-1), 2.5 g of the compound represented by the formula (I-17-2), 2.6 g of potassium carbonate, and dichlorobis [dichlorobis [di] were placed in the reaction vessel in a reaction vessel. -T-Butyl (p-dimethylaminophenyl) phosphino] 0.2 g of palladium (II), 50 mL of toluene, 25 mL of ethanol, and 25 mL of water were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The compound 4 represented by the formula (I-17) is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) after sequentially washing the organic layer with water and saline. .2 g was obtained.
MS (EI): m / z = 474
(Example 18) Production of a compound represented by the formula (I-18)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-18-1), 4.2 g of the compound represented by the formula (I-18-2), 5.1 g of potassium carbonate, N, N were placed in the reaction vessel. -70 mL of dimethylacetamide and 0.1 g of palladium (II) acetate were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed successively with water and brine, and then purified by column chromatography (silica gel, toluene / hexane) to obtain 6.1 g of the compound represented by the formula (I-18-3).

In a nitrogen atmosphere, 6.1 g of the compound represented by the formula (I-18-3), 4.2 g of potassium carbonate, 6.8 g of the compound represented by the formula (I-18-4), 68 mL of toluene, were placed in the reaction vessel. 34 mL of ethanol, 34 mL of water, and 0.4 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-18-5) by sequentially washing with water and saline and then purifying by column chromatography (silica gel, toluene / heptane) and recrystallization (toluene / ethanol). 6.3 g of compound was obtained.

In Example 6, the compound represented by the formula (I-6-1) is the compound represented by the formula (I-18-5), and the compound represented by the formula (I-6-2) is the compound represented by the formula (I-6-2). A compound represented by the formula (I-18) was produced by the same method except that the compound represented by -18-6) was replaced.
MS (EI): m / z = 481
(Example 19) Production of a compound represented by the formula (I-19)

By the same method except that the compound represented by the formula (I-12-5) was replaced with the compound represented by the formula (I-19-1) in Example 12, the formula (I-19-3) was used. The compound represented was produced.

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-19-4), 4.2 g of potassium carbonate, 5.2 g of the compound represented by the formula (I-19-5), 56 mL of toluene, were placed in the reaction vessel. 28 mL of ethanol, 28 mL of water, and 0.2 g of bis (triphenylphosphine) palladium (II) dichloride were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-19-6) by sequentially washing with water and saline and then purifying by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol). 7.0 g of the compound was obtained.

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-19-6), 0.1 g of copper (I) iodide, 2-dicyclohexylphosphino-2', 4', 6'-tri 0.1 g of isopropylbiphenyl [XPhos], 0.1 g of palladium (II) acetate, 37 mL of diisopropylamine, and 74 mL of N, N-dimethylformamide were added. While heating at 90 ° C., a solution prepared by dissolving 3.3 g of the compound represented by the formula (I-19-3) in 7 mL of N, N-dimethylformamide was added dropwise, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer is represented by the formula (I-19) by sequentially washing with water and brine, and then purifying by column chromatography (silica gel, toluene / hexane), activated charcoal treatment, and recrystallization (toluene / ethanol). 6.1 g of the compound was obtained.
MS (EI): m / z = 534
(Example 20) Production of a compound represented by the formula (I-20)

Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (I-20-1), 7.0 g of the compound represented by the formula (I-20-2), 4.1 g of potassium carbonate, and dichlorobis [dichlorobis [di] were placed in the reaction vessel in a reaction vessel. -T-Butyl (p-dimethylaminophenyl) phosphino] Palladium (II) 0.2 g, toluene 56 mL, ethanol 28 mL, water 28 mL were added, and the mixture was heated under reflux for 6 hours. The reaction mixture was poured into water and extracted with toluene. The compound represented by the formula (I-20) 8 is purified by column chromatography (silica gel, toluene / hexane) and recrystallization (toluene / ethanol) after sequentially washing the organic layer with water and saline. .1 g was obtained.
MS (EI): m / z = 584
(Example 21 and Comparative Example 1)
In the examples, the following abbreviations are used for the description of the liquid crystal compound.
(Ring structure)

(Side chain structure)
2- CH ₃ CH ₂ -
3-CH ₃ (CH ₂ ) _2-
4-CH ₃ (CH ₂ ) _3-
_{_{_{5- CH 3 (CH 2) 4}}} -
-2 -CH ₂ CH ₃
-3- (CH ₂ ) ₂ CH ₃
-4- (CH ₂ ) ₃ CH ₃
-5- (CH ₂ ) ₄ CH ₃
-Cl-Cl
(Connecting group)
-Single bond-T--C≡C-
A maternal liquid crystal N composed of the following compounds was prepared.
(Mother liquid crystal N)
2-Ph3-T-PhPh-3 20.0%
4-Ph3-T-PhPh-3 36.0%
3-Ph1Ph1Ph-Cl 10.0%
5-Ph1Ph1Ph-Cl 20.0%
5-CyPhPh1Ph-2 7.0%
5-CyPhPh1Ph-3 7.0%
Compounds represented by formulas (I-1) to (I-20) described in Examples 1 to 20 are added to the mother liquid crystal N, and the liquid crystal composition (M-1) to be evaluated is used. A liquid crystal composition (M-20) was prepared. Further, the compound represented by the formula (R-1) described in Non-Patent Document 1, the compound represented by the formula (R-2) described in Patent Document 1, and the formula (R-3) represented by the formula (R-3) described in Patent Document 2. ) And the compound represented by the formula (R-4) were added to prepare a liquid crystal composition (RM-4) from the liquid crystal composition (RM-1) to be compared.

(Liquid crystal composition (M-1))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-1) 10.0%
(Liquid crystal composition (M-2))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-2) 10.0%
(Liquid crystal composition (M-3))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-3) 10.0%
(Liquid crystal composition (M-4))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-4) 10.0%
(Liquid crystal composition (M-5))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-5) 10.0%
(Liquid crystal composition (M-6))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-6) 10.0%
(Liquid crystal composition (M-7))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-7) 10.0%
(Liquid crystal composition (M-8))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-8) 10.0%
(Liquid crystal composition (M-9))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-9) 10.0%
(Liquid crystal composition (M-10))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-10) 10.0%
(Liquid crystal composition (M-11))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-11) 10.0%
(Liquid crystal composition (M-12))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-12) 10.0%
(Liquid crystal composition (M-13))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-13) 10.0%
(Liquid crystal composition (M-14))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-14) 10.0%
(Liquid crystal composition (M-15))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-15) 10.0%
(Liquid crystal composition (M-16))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-16) 10.0%
(Liquid crystal composition (M-17))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-17) 10.0%
(Liquid crystal composition (M-18))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-18) 10.0%
(Liquid crystal composition (M-19))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-19) 10.0%
(Liquid crystal composition (M-20))
Maternal liquid crystal N 90.0%
Compound represented by formula (I-20) 10.0%
(Liquid crystal composition (RM-1))
Maternal liquid crystal N 90.0%
Compound represented by formula (R-1) 10.0%
(Liquid crystal composition (RM-2))
Maternal liquid crystal N 90.0%
Compound represented by formula (R-2) 10.0%
(Liquid crystal composition (RM-3))
Maternal liquid crystal N 90.0%
Compound represented by formula (R-3) 10.0%
(Liquid crystal composition (RM-4))
Maternal liquid crystal N 90.0%
Compound represented by formula (R-4) 10.0%
The dielectric anisotropy Δε and the refractive index anisotropy Δn of the obtained liquid crystal composition are shown in the table below. In addition, the storage stability of each compound to be evaluated was evaluated. For storage stability, 2 mL of each obtained liquid crystal composition was sealed in a glass vial under an argon atmosphere, and the state after storage at 10 ° C. for 4 weeks was visually evaluated. The evaluation results are shown in the table below.

From the above results, it can be seen that the compound of the present invention is less likely to precipitate when added to the liquid crystal composition and has high compatibility with the liquid crystal composition.

Each liquid crystal composition to be evaluated was enclosed in a TN cell having a thickness of 8.5 μm. A rectangular voltage of 30 V at a frequency of 100 Hz was applied to each of the obtained liquid crystal cells at 50 ° C. for 50 hours. The voltage holding ratio was measured for each liquid crystal cell, and the difference (ΔV _HR ) in the voltage holding ratio before and after the voltage was applied was calculated. As the value of [Delta] V _HR is small, it means that reduction of the voltage holding ratio of the liquid crystal cell is small. The voltage holding ratio was measured at a frequency of 60 Hz and an applied voltage of 1 V and 333 K. The results are shown in the table below.

From the above results, it can be seen that the device using the liquid crystal composition to which the compound of the present invention is added is less likely to cause a decrease in the voltage retention rate.

Next, the characteristics of each obtained liquid crystal composition in the high frequency region were evaluated. For the measurement, a transmission delay method Cut back type stripline method relative permittivity / dielectric loss tangent measuring device (manufactured by KEYCOM) was used. Here, each physical property value is defined as follows.

ε _⊥ = (3ε _average －ε _∥ ) / 2
tanδ _⊥ = (3ε _average tanδ _average －ε _∥ tanδ _∥ ) / 2ε _⊥
Modulation ability (τ) = (ε _∥ －ε _⊥ ) / ε _∥
Material properties (ηε) = τ / (max (tanδ _∥ , tanδ _⊥ ))
The physical characteristic values of the mother liquid crystal N at 19 GHz and 20 ° C. were as follows.

tan δ _⊥ = 0.014
tanδ _∥ = 0.003
Modulation ability (τ) = 0.25
Material properties (ηε) = 17.5
The physical characteristic values of each of the obtained liquid crystal compositions at 19 GHz and 20 ° C. were similarly measured. As a result, from the liquid crystal composition (M-1) containing the compounds represented by the formulas (I-1) to (I-12) and the formulas (I-16) to (I-20) of the present invention. Regarding (M-20), it was found that the material properties (ηε) were all 25 or more.

From the above results, the compound of the present invention has a large refractive index anisotropy Δn, has high compatibility with the liquid crystal composition, and has a voltage retention rate of the element when the element is manufactured by adding it to the liquid crystal composition. It is useful as a material for elements such as a high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image.

Claims

The following general formula (I)

(In the formula, R 1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom, and the alkyl One or more of -CH 2- in the group are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-, but the oxygen atoms are Never join,
A 1 and A 2 each represent a hydrocarbon ring or a heterocycle having 3 to 16 carbon atoms which may be independently substituted, but when a plurality of A 1s are present, they are the same but different. is good, they if a 2 there are a plurality may be the same or different and
Z 1, Z 2 and although Z 3 each represent independently a divalent linking group or a single bond, they if Z 1 there are a plurality may be different even in the same, Z 2 is plurality of If they do, they may be the same or different,
m1 and m2 independently represent integers from 0 to 3, while m1 + m2 represent integers from 0 to 3.
A x is the following formula (Ax-1) and formula (Ax-2).

(In the formula, the broken line represents the bond position, X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y 1 , Y 3 , Y 4 and Y 6 are independent of each other. Represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Y 2 and Y 5 are independently substituted with a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and an arbitrary hydrogen atom. An alkyl group having 1 to 8 carbon atoms may be present, an alkoxy group having 1 to 7 carbon atoms may be substituted with an arbitrary hydrogen atom, and an arbitrary hydrogen atom may be substituted with a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, wherein one -CH 2 -or Two or more -CH 2 -are independent of -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 = It may be replaced by CH-, -CF = CF- or -C≡C-.)
Represents a group selected from. ), Where in the above general formula (I)

The structure represented by and

A compound whose structure represented by is not the same.
In the general formula (I), A 1 and A 2 are independent of each other.
(A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - is replaced by -O- or -S- Is also good.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) 1,4-Cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2 , 3,4-Tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6- Diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (even if the hydrogen atom existing in these groups is replaced with a fluorine atom or a chlorine atom Well, also naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene. One in the -1,4-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene-2,7-diyl group -CH = or two or more -CH = may be replaced with -N =.)
(D) Thiophene-2,5-diyl group, benzothiophene-2,5-diyl group, benzothiophene-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6-diyl Group, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
Represents a group selected from the group consisting of, these groups may be substituted by or is one or more substituents L 1 is unsubstituted,
L 1 is 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 and a diisopropyl. Amino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH 2- or two or more -CH 2- are independently -O-, -S-, -CO-, -COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH 1 to 20 carbon atoms which may be substituted by -OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Represents a linear alkyl group or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but oxygen atoms do not directly bond to each other, and any hydrogen atom in the alkyl group is replaced with a fluorine atom. The compound according to claim 1, which may be present.
In the general formula (I), Z 1 , Z 2 and Z 3 are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-,-. OCOO -, - CF 2 O - , - 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 2 CH 2 O-, -N = N-, -C = N-N = C-, -CH = N-, -N = CH- or an alkylene group having 2 to 20 carbon atoms, and one or more -CH 2- in the alkylene group is substituted with -O-, -COO- or -OCO-. The compound according to claim 1 or 2, wherein the oxygen atoms do not directly bond with each other.
The above general formula (I) is replaced by the following general formula (Ii).

(In the formula, R 11 is a hydrogen atom, any hydrogen atom in the group may be replaced with a halogen atom, and one or two or more -CH 2- in the group are independently -O-. , -S-, -CH = CH-, -CF = CF- or -C≡C- representing a linear or branched alkyl group having 1 to 20 carbon atoms.
A 11 and A 21 are independently 1,4-phenylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, phenanthrene-2,7-diyl group, benzothiophene-2,5, respectively. -Diyl group, benzothiophene-2,6-diyl group, benzothiazole-2,5-diyl group, benzothiazole-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6 - represents a diyl group or a thieno [3,2-b] thiophene-2,5-diyl group, if a 11 there are a plurality thereof may be different even in the same, a 21 there are multiple if they may be the same or different and these groups may be substituted by or is one or more substituents L 11 is unsubstituted,
In L 11, a fluorine atom, a chlorine atom, or any hydrogen atom in the group may be substituted with a fluorine atom, and one -CH 2- or two or more -CH 2- in the group are independent of each other. A linear alkyl group having 1 to 20 carbon atoms or 3 carbon atoms which may be substituted by -O-, -S-, -CH = CH-, -CF = CF- or -C≡C-. Represents a branched or cyclic alkyl group from 20 to 20, but if a plurality of L 11s are present, they may be the same or different.
Z 11 , Z 21 and Z 31 are independently -OCH 2- , -CH 2 O-, -CH 2 CH 2- , -CF 2 O-, -OCF 2- , -CH = CH-, -N. = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, Z 11 there are a plurality of if they may be the same or different and they if Z 21 there are a plurality may be the same or different and
m11 and m21 independently represent 0, 1 or 2, respectively, while m1 + m2 represent an integer from 0 to 3.
A x1 is the following formula (Ax-1-i) and formula (Ax-2-i).

(In the formula, the broken line represents the bond position, X 11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Y 11 , Y 31 , Y 41 and Y 61 are independent hydrogen atoms and fluorine atoms, respectively. Alternatively, it represents a chlorine atom, and Y 21 and Y 51 are independent fluorine atoms, chlorine atoms, cyano groups, nitro groups, pentafluorosulfanyl groups, and the number of carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. From 1 to 8 alkyl groups, an alkoxy group having 1 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom, and 2 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. Represents a group selected from 8 alkenyl groups or alkenyloxy groups having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom). ), The compound according to any one of claims 1 to 3.
The above general formula (I) is replaced by the following general formula (I-ii).

(In the formula, in R 12 , any hydrogen atom in the group may be replaced with a fluorine atom, and one or two or more -CH 2- in the group are independently -O- and -CH, respectively. = Represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be replaced by CH- or -C≡C-.
A 12 and A 22 are independently expressed from the following equations (A-ii-1) to (A-ii-14).

(In the formula, the broken line represents the bonding position, and when a plurality of L 12s are present, they may be the same or different.), But when there are a plurality of A 12s, they are the same. may be be different also, they if a 22 there are a plurality may be the same or different and
In L 12, a fluorine atom or any hydrogen atom in the group may be substituted with a fluorine atom, and -CH 2- in the group may be substituted by -O-, which is a direct number of carbon atoms 1 to 10. Represents a chain alkyl group or a branched or cyclic alkyl group having 3 to 10 carbon atoms.
Z 12 , Z 22 and Z 32 are independently -OCH 2- , -CH 2 O-, -CH 2 CH 2- , -CF 2 O-, -OCF 2- , -CH = CH-, -N. = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, Z 12 there are a plurality of If they are the same or different, if there are multiple Z 22s they may be the same or different.
m12 and m22 independently represent 0, 1 or 2, but m12 + m22 represent 0, 1 or 2, respectively.
X 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Y 12 and Y 32 independently represent a hydrogen atom, a fluorine atom or a chlorine atom, Y 22 is a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, and any hydrogen atom is replaced with a fluorine atom. An alkyl group having 1 to 8 carbon atoms which may be used, an alkoxy group having 1 to 7 carbon atoms which may have any hydrogen atom replaced by a fluorine atom, and an arbitrary hydrogen atom which has been replaced by a fluorine atom. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms in which any hydrogen atom may be substituted with a fluorine atom. ), The compound according to any one of claims 1 to 4.
The above general formula (I) is replaced by the following general formula (I-iii).

(In the formula, R 13 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, or a carbon atom. Represents the alkynyl group of the numbers 2 to 8
A 13 and A 23 are independently expressed in the following formulas (A-iii-1) to (A-iii-7) and (A-iii-12).

(Wherein the dashed line represents a bond position, they if L 13 there are a plurality may be the same or different.) Represents a group selected from,
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 independently represent -CF 2 O-, -OCF 2- , -CH = CH-, -CF = CF-, -C ≡ C- or a single bond, respectively.
m13 and m23 independently represent 0 or 1, while m13 + m23 represent 0, 1 or 2, respectively.
X 13 represents a hydrogen atom, a methyl group or an ethyl group.
Y 13 and Y 33 independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Y 23 represents a fluorine atom, a chlorine atom and a cyano group, respectively. ), The compound according to any one of claims 1 to 5.
A composition containing the compound according to any one of claims 1 to 6.
A liquid crystal composition containing 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 anisotropy is 2 or more.
The liquid crystal composition according to claim 8, wherein the dielectric anisotropy is 2 or less.
A high-frequency phase shifter, a phased array antenna, an image recognition device, a distance measuring device, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for displaying a stereoscopic image using the liquid crystal composition according to claims 8 to 11.