JP7354777B2 - Liquid crystal compounds for high frequency equipment - Google Patents

Description

The present invention relates to a liquid crystal compound, a liquid crystal composition containing the same, and a high frequency phase conversion technique using the liquid crystal composition.

Liquid crystals are used in mobile terminals such as smartphones and tablet devices, as well as display applications such as TVs and window displays. As a new use for liquid crystals, antennas using liquid crystals that transmit and receive radio waves between mobile objects such as cars and communication satellites are attracting attention.
Conventionally, satellite communications have used parabolic antennas, but when used on a mobile object, the parabolic antenna must be oriented toward the satellite at any time, requiring a large movable part. However, with an antenna using a liquid crystal, the direction of transmitting and receiving radio waves can be changed by operating the liquid crystal, so there is no need to move the antenna itself, and the shape of the antenna can be made flat.
Autonomous driving of automobiles requires the downloading of large amounts of high-precision 3D map information, and by incorporating liquid crystal antennas into automobiles, large amounts of data can be downloaded from communication satellites without the need for mechanical moving parts. It becomes possible. The frequency band used for satellite communications is approximately 13 GHz, which is significantly different from the frequency used for conventional liquid crystal display applications. Therefore, the physical properties required for liquid crystals are also significantly different, with the refractive index anisotropy (Δn) required for liquid crystals for antennas being approximately 0.4, and the operating temperature range being -40 to 120°C or higher (nematic phase).
Infrared laser image recognition and ranging devices using liquid crystals are also attracting attention as sensors for self-driving cars. The required characteristics of a liquid crystal for this purpose are a high Δn (0.2 to 0.3) and a high operating temperature range (-40 to 120°C or higher).
In response to such required characteristics regarding high Δn and operating temperature range, methods for manufacturing liquid crystal compositions using compounds having a bistran structure or a compound having an NCS structure as shown below have been reported. (Patent Documents 1 and 2). However, the Δn of these compounds is still not sufficient, and liquid crystals that exhibit values that can withstand practical use in other physical properties such as dielectric anisotropy (Δε), solubility in liquid crystal compositions, and viscosity are still insufficient. Developing compositions is extremely difficult.

Special table 2013-544233 public information Publication of JP-A-2016-37607

The problems to be solved by the present invention are to have a liquid crystal phase with a wide temperature range, low viscosity, good solubility at low temperatures, high specific resistance and voltage holding rate, and high Δn. Furthermore, by using this composition, we can produce liquid crystal compositions with excellent high frequency control effects and excellent chemical stability, as well as liquid crystal display elements and liquid crystal antennas using the liquid crystal compositions. It is about providing.

In order to solve the above problems, the inventors of the present application conducted synthesis studies of various compounds, and as a result, they found that the problems could be effectively solved by a compound containing an NCSe structure in the molecule, leading to the completion of the present invention. In addition, the compound containing the NCSe structure in the molecule has both a mesogenic structure and an NCSe structure, so that when added to a liquid crystal composition, it dissolves well without reducing liquid crystallinity, while increasing the electron density. It has been found that Δn can be further increased by the effect of a high NCSe structure.

If a liquid crystal composition is manufactured using the compound containing the NCSe structure in the molecule provided by the present invention, it will have a wide liquid crystal phase temperature range, low viscosity, solubility, specific resistance, voltage holding rate, heat resistance, and light resistance. It is possible to obtain a liquid crystal composition having large Δn and Δε while maintaining the physical properties, and such a liquid crystal composition has an excellent electromagnetic wave control effect in a high frequency region. Therefore, the liquid crystal composition can be suitably used for high frequency elements, antennas, liquid crystal display elements, liquid crystal lenses, birefringent lenses for stereoscopic image display, etc., and is particularly useful as a liquid crystal composition for liquid crystal antennas.

Hereinafter, the compound containing the NCSe structure in the molecule of the present invention, the liquid crystal composition containing the same, and the liquid crystal display element will be explained in detail.
The form of the mesogenic structure is represented by the following general formula (I)

(In the formula, A ¹ represents a divalent aromatic group, a divalent cycloaliphatic group, or a divalent heterocyclic compound group, and the hydrogen atom in A ¹ may be substituted with L ¹ , 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, Diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH ₂ - or two or more -CH ₂ - each independently -O-, -S-, -CO-, - COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH= From 1 carbon atom which may be substituted with CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- 20 linear alkyl groups or branched or cyclic alkyl groups having 3 to 20 carbon atoms, but the oxygen atoms do not bond directly to each other, and any hydrogen atoms in the alkyl group are replaced with fluorine atoms. It may be done,
Z ¹ is each independently a single bond, -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 having 2 to 20 carbon atoms Represents an alkylene group, and one or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but oxygen atoms are not directly bonded to each other. ,
n1 represents an integer from 1 to 10,
Here, when a plurality of A ¹ and Z ¹ exist, they may be the same or different. )
It is represented by the substructure represented by .

Furthermore, the present invention provides general formula (i-1)

(In the formula,
R ⁱ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, any hydrogen atom in the alkyl group may be substituted with a halogen atom, and one of the alkyl groups or two or more -CH ₂ - each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- may be substituted, but the oxygen atoms do not bond with each other. ,
A ⁱ¹ and A ⁱ² are each independently (a) a 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group is - (May be replaced with O- or -S-.)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group 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, (the hydrogen atoms present in these groups are replaced with fluorine atoms or chlorine atoms) Also, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydro One group present in naphthalene-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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
represents a group selected from the group consisting of, and these groups may be unsubstituted or substituted with one or more substituents ^Li1 ,
L ⁱ¹ 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 - each 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 optionally substituted with -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 the oxygen atoms do not bond directly to each other, and any hydrogen atom in the alkyl group is substituted with a fluorine atom. You can leave it there,
Z ⁱ¹ is each independently a single bond, -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 having 2 to 20 carbon atoms Represents an alkylene group, and one or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are not directly bonded to each other. ,
n ⁱ¹ represents an integer from 1 to 8,
Here, when a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different. )
The present invention relates to a compound represented by: and a liquid crystal composition containing the compound.

In the compound having the NCSe structure of the present application, the π-conjugated structure can be expanded by the π electrons of the NCSe structure, and therefore, there is an effect of increasing Δn. In particular, by combining the π-conjugated structure in the mesogen structure with the π-conjugated structure in the NCSe structure, the π-conjugated structure spreads throughout the molecule, and Δn can be effectively increased. In particular, when the NCSe structure is bonded in a direction close to parallel to the molecular long axis of the mesogen structure, Δn becomes extremely large because the refractive index anisotropy increases in addition to the refractive index itself.
This is also effective for other physical property values, such as Δε. The NCSe structure strongly attracts electrons when bonded to a ring structure, and the bond angle is close to 180 degrees. Therefore, when the NCSe structure is bonded in a direction close to parallel to the molecular long axis of the mesogen structure, Δε can be effectively increased and a p-type liquid crystal compound can be obtained. On the other hand, when the NCSe structure is bonded in a direction close to perpendicular to the molecular long axis of the mesogen structure, Δε can be effectively reduced and an n-type liquid crystal compound can be obtained.
As the compound represented by general formula (i-1), one type may be used, or two or more types may be used in combination.
In general formula (i-1), R ⁱ¹ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 40 carbon atoms; It is preferably an alkyl group, more preferably a hydrogen atom or a straight chain or branched alkyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom or a straight chain or branched alkyl group having 1 to 6 carbon atoms. A linear alkyl group having 1 to 6 carbon atoms is particularly preferred from the viewpoint of liquid crystallinity and viscosity reduction. Further, any hydrogen atom in the alkyl group may be substituted with a halogen atom, and the halogen atom is preferably a fluorine atom or a chlorine atom, and a fluorine atom is particularly preferred. In addition, when one or more -CH ₂ - in the alkyl group is replaced, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- is preferably substituted with -O-, -S-, -COO-, -OCO-, -CO-S-, -S-CO-, -CH=CH-, -CF=CF- or -C≡C- is preferably substituted with -O-, -S-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C-, From the viewpoint of increasing Δn, substitution with -O-, -S-, -CH=CH-, -CF=CF- or -C≡C- is particularly preferred. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
In general formula (i-1), A ⁱ¹ and A ⁱ² are (a) a 1,4-cyclohexylene group (one -CH ₂ - present in this group or two or more non-adjacent - CH ₂ - may be replaced with -O- or -S-.)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group 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 (the hydrogen atoms present in these groups are replaced with fluorine atoms or chlorine atoms) Also, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydro One group present in naphthalene-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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
It is preferable that it is a group selected from the group consisting of. Here, from the viewpoint of forming a conjugated structure with the π electrons of the NCSe structure and increasing Δn, A ⁱ¹ and A ⁱ² are preferably structures represented by (b), (c), or (d). . On the other hand, from the viewpoint of light resistance and widening the temperature range of the liquid crystal phase, the structure represented by (a) is preferable.

When A ⁱ¹ and A ⁱ² have the structure (b), they are preferably a 1,4-phenylene group, a pyrimidine-2,5-diyl group, or a pyridine-2,5-diyl group, and 1,4-phenylene A group is particularly preferred. In the case of structure (c), naphthalene-2,6-diyl group, naphthalene-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 is preferable, and naphthalene-2,6-diyl group, naphthalene-1,4-diyl group or phenanthrene-2,7-diyl group is particularly preferable. . In the case of structure (d), thiophene-2,5-diyl group, thiazole-2,5-diyl group, benzothiophene-2,5-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-diyl group or thieno[3,2-b]thiophene-2,5 -diyl group is preferred, and from the viewpoint of liquid crystallinity and Δn increase, benzothiophene-2,5-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-diyl group or thieno[3,2-b]thiophene-2,5-diyl group are preferred, and dibenzothiophene-2,6 -diyl group or thieno[3,2-b]thiophene-2,5-diyl group is particularly preferred.

Furthermore, the groups (a) to (d) above may be substituted with one or more substituents L ⁱ¹ . When substituted, L ⁱ¹ 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 group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group or thioisocyano group, and fluorine atom, chlorine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, dimethylamino group, diethylamino group , a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyano group are more preferable, and a fluorine atom, a chlorine atom, a cyano group, an isocyano group, or a thioisocyano group are particularly preferable from the viewpoint of increasing Δn.
L ⁱ¹ is also preferably a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms; or a cyclic alkyl group, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Further, from the viewpoint of solubility, a linear alkyl group having 1 to 3 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms is preferable. Further, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Furthermore, one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and when substituted, -O- , -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, - It is preferable that CH=CH-, -CF=CF- or -C≡C- is substituted, -O-, -S-, -COO-, -OCO-, -CO-S-, -S- It is preferably replaced with CO-, -CH=CH-, -CF=CF- or -C≡C-, -O-, -S-, -COO-, -OCO-, -CH=CH- , -CF=CF- or -C≡C- is more preferable, and from the viewpoint of increasing Δn, -O-, -S-, -CH=CH-, -CF=CF- or -C Particularly preferred is substitution with ≡C-. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
In order for the π electrons of the NCSe structure to be conjugated with the π electrons in the mesogen structure, A ⁱ² is preferably aromatic. In this case, A ⁱ² is (e) a 1,4-phenylene group (even if one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N=) good.)
(f) 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (present in these groups) The hydrogen atom may be substituted with a fluorine atom or a chlorine atom, and 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene- One -CH= or two or more -CH= present in the 2,7-diyl group may be replaced with -N=.)
(g) 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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
A group selected from the group consisting of is preferable, and these groups may be unsubstituted or substituted with one or more substituents L ⁱ¹ .
In general formula (i-1), Z ⁱ¹ is each independently a single bond, -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- or -N=CH - is preferably a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =C(CH ₃ )COO-, -OCOC(CH ₃ )=CH-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- Preferably, a single bond, -CH=CH-, -CF=CF-, -C≡C-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- More preferably, from the viewpoint of increasing Δn, a single bond, -C≡C-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- It is particularly preferred that there be.
Z ⁱ¹ is also preferably an alkylene group having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 12 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. . One or more -CH ₂ - groups in the alkylene group are preferably substituted with -O-, -COO- or -OCO-. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
n ⁱ¹ is preferably an integer from 1 to 8, preferably an integer from 1 to 6, and particularly preferably an integer from 1 to 3. Further, from the viewpoint of increasing solubility and reducing viscosity, it is preferably an integer of 1 to 2, and in order to increase the upper limit of the temperature range of the liquid crystal phase, it is preferably an integer of 2 to 3.

Preferred examples of the compounds represented by formula (i-1) of the present invention are shown below, but the present invention is not limited thereto.

The compound represented by general formula (i-1) is preferably a compound represented by general formula (i-1-1).

In general formula (i-1-1), R ⁱ¹¹ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and when replacing any hydrogen atom in the alkyl group, a fluorine atom or A chlorine atom is preferred, and when one or more -CH ₂ - in the alkyl group is replaced, -O-, -S-, -CH=CH-, -CF=CF- or -C≡C - is preferred, but it is not preferred that oxygen atoms bond to each other.
In the general formula (i-1-1), A ⁱ¹¹ and A ⁱ²¹ are each independently a 1,4-cyclohexylene group, a 1,4-phenylene group, a 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, benzothiazole-2,6 -diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6-diyl group or thieno[3,2-b]thiophene-2,5-diyl group.

Furthermore, A ⁱ¹¹ and A ⁱ²¹ may be substituted with one or more substituents L ⁱ¹¹ . When substituted, L ⁱ¹¹ is preferably a fluorine atom, a chlorine atom, a cyano group, an isocyano group, a thioisocyano group, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Further, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Furthermore, one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently -O-, -S-, -CH=CH-, -CF=CF It is also preferred that it is replaced by - or -C≡C-. However, it is not preferable for oxygen atoms to bond with each other.
In general formula (i-1-1), Z ⁱ¹¹ are each independently a single bond, -CH=CH-, -CF=CF-, -C≡C-, -N=N-, -C=N- Preferably, N=C-, -CH=N- or -N=CH-.
Z ⁱ¹¹ is also preferably an alkylene group having 2 to 6 carbon atoms. It is also preferred that one or more -CH ₂ - in the alkylene group is substituted with -O-, -COO- or -OCO-. However, it is not preferable for oxygen atoms to bond with each other.
Preferably, n ⁱ¹¹ is an integer from 1 to 3.

Further, as the compound represented by the general formula (i-1), compounds represented by the general formulas (i-1-2a) to (i-1-2d) are preferable.

(In the formula, R ⁱ¹² and A ⁱ²² represent the same meanings as R ⁱ¹¹ and A ⁱ²¹ above, and A ⁱ¹² and A ⁱ²⁴ represent the same meanings as A ⁱ¹¹ above.)
As the compound represented by the general formula (i-1), compounds represented by the general formulas (i-1-a1) to (i-1-v3) are particularly preferred.

(In the formula, R ^i1a represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 6 carbon atoms, or a straight chain or branched alkoxy group having 1 to 6 carbon atoms.)
In the present invention, the NCSe structure of a compound containing an NCSe structure in its molecule can be produced by the following method. Of course, the spirit and scope of the present invention are not limited to these manufacturing examples.

A compound having a partial structure (S-2) can be obtained by heating a compound having an amino group together with a formyl group source to cause a dehydration reaction. Examples of the formyl group source include formic acid, methyl formate, ethyl formate, formic acid acetic anhydride, and the like. At this time, an organic solvent may be used, and examples of the organic solvent include toluene, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide. Next, a compound having the partial structure (S-3) can be obtained by subjecting the compound having the partial structure (S-2) to a dehydration reaction using a base and a dehydrating reagent. Examples of the base include triethylamine, N,N-diisopropylethylamine, and 1,8-diazabicyclo[5.4.0]-7-undecene. Examples of the dehydrating reagent include triphosgene, phosgene, and phosphoryl chloride. Finally, a compound having the NCSe structure can be obtained by heating and reacting the compound having the partial structure (S-3) with selenium in an organic solvent. Examples of organic solvents include toluene, tetrahydrofuran, dichloromethane, and the like.
The compound represented by general formula (i-1) can be produced as follows.

A compound represented by general formula (S-6) can be obtained by heating the compound represented by general formula (S-5) together with a formyl radical to cause a dehydration reaction. Examples of the formyl group source include formic acid, methyl formate, ethyl formate, formic acid acetic anhydride, and the like. At this time, an organic solvent may be used, and examples of the organic solvent include toluene, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide. Next, the compound represented by (S-7) can be obtained by subjecting the compound represented by (S-6) to a dehydration reaction using a base and a dehydrating reagent. Examples of the base include triethylamine, N,N-diisopropylethylamine, and 1,8-diazabicyclo[5.4.0]-7-undecene. Examples of the dehydrating reagent include triphosgene, phosgene, and phosphoryl chloride. Finally, the compound represented by formula (i-1) can be obtained by heating and reacting the compound represented by (S-7) with selenium in an organic solvent. Examples of organic solvents include toluene, tetrahydrofuran, dichloromethane, and the like.
Examples of reaction conditions other than those described in each step are those described in Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemis. try(Beilstein) -Institut für Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Those described in the literature such as Organic Synthesis (John Wiley & Sons, Inc.) or SciFinder (Chemical Abstracts Service, Examples include those listed in databases such as American Chemical Society) and Reaxys (Elsevier Ltd.).

Moreover, a reaction solvent can be used as appropriate in each step. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water, and the like. When carrying out the reaction in a two-phase system of organic solvent and water, it is also possible to add a phase transfer catalyst. Specific examples of phase transfer catalysts include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

Further, purification can be performed in each step as necessary. Examples of purification methods include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purifying agent include silica gel, NH ₂ silica gel, alumina, activated carbon, and the like.

The composition containing one or more compounds having an NCSe structure in its molecule preferably exhibits a liquid crystal phase at room temperature. The lower limit of the compound containing the NCSe structure in the molecule is preferably 1% or more, preferably 2% or more, 3% or more, and 5% or more in the composition. It is preferable to contain 10% or more, it is preferable to contain 15% or more, it is preferable to contain 20% or more, it is preferable to contain 25% or more, it is preferable to contain 30% or more, and % or more, preferably 70% or more, and preferably 90% or more. In addition, from the viewpoint that the liquid crystal composition stably maintains a liquid crystal phase in a wide temperature range, it is preferable that 90% or more of the liquid crystal composition be composed of a compound containing an NCSe structure in the molecule. It is preferable to use two or more types of compounds containing the NCSe structure, preferably to use three or more types, preferably to use five or more types, and preferably to use seven or more types. In addition, the upper limit is preferably 90% or less, preferably 80% or less, preferably 70% or less, preferably 60% or less, preferably 50% or less, It is preferably contained at 40% or less, preferably at most 30%, preferably at most 20%, preferably at most 10%, preferably at most 5%, and preferably at most 3%. It is preferable.

More specifically, the content is preferably from 1 to 95% by mass, preferably from 2 to 90% by mass, even more preferably from 5 to 80% by mass, and especially from 10 to 70% by mass. preferable.

A composition containing a compound containing an NCSe structure in its molecule may contain a compound having a liquid crystal phase in addition to the compound containing an NCSe structure in its molecule, or may contain a compound having no liquid crystal phase. It's okay. Examples of the compound having no liquid crystal phase include antioxidants, ultraviolet inhibitors, chiral agents, antistatic agents, dichroic dyes, and the like.

The composition containing a compound containing an NCSe structure in the molecule of the present invention preferably contains a compound represented by the following general formula (II).

(In the formula,
R ⁱⁱ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a halogen atom, and one of the alkyl groups or two or more -CH ₂ - each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- may be substituted, but the oxygen atoms do not bond with each other. ,
A ⁱⁱ¹ and A ⁱⁱ² each independently represent (a) a 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group is - (May be replaced with O- or -S-.)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group 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 (the hydrogen atoms present in these groups are replaced with fluorine atoms or chlorine atoms) Also, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydro One group present in naphthalene-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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
represents a group selected from the group consisting of, and these groups may be unsubstituted or substituted with one or more substituents L ⁱⁱ¹ ,
L ⁱⁱ¹ 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 - each 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 optionally substituted with -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 the oxygen atoms do not bond directly to each other, and any hydrogen atom in the alkyl group is substituted with a fluorine atom. You can leave it there,
Z ⁱⁱ¹ is each independently a single bond, -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 having 2 to 20 carbon atoms Represents an alkylene group, and one or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but oxygen atoms are not directly bonded to each other. ,
X ⁱⁱ¹ is a hydrogen atom, 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 group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH ₂ - or two or more -CH ₂ - each independently -O-, -S-, -CO- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, - Number of carbon atoms optionally substituted by CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- It represents a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but the oxygen atoms do not bond directly to each other, and any hydrogen atom in the alkyl group is a fluorine atom. may be replaced with
n ⁱⁱ¹ represents an integer from 1 to 8,
Here, when a plurality of A ⁱⁱ¹ and Z ⁱⁱ¹ exist, they may be the same or different. )
R ⁱⁱ¹ is preferably a hydrogen atom or a straight chain or branched alkyl group having 1 to 40 carbon atoms, preferably a hydrogen atom or a straight chain or branched alkyl group having 1 to 20 carbon atoms, and It is more preferably a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms. A linear alkyl group having 1 to 6 atoms is particularly preferred from the viewpoint of liquid crystallinity and viscosity reduction. Further, any hydrogen atom in the alkyl group may be substituted with a halogen atom, and the halogen atom is preferably a fluorine atom or a chlorine atom, and a fluorine atom is particularly preferred. In addition, when one or more -CH ₂ - in the alkyl group is replaced, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- is preferably substituted with -O-, -S-, -COO-, -OCO-, -CO-S-, -S-CO-, -CH=CH-, -CF=CF- or -C≡C- is preferably substituted with -O-, -COO-, -OCO-, -CH=CH-, -CF=CF- or -C≡C-, which increases Δn. From this point of view, substitution with -O-, -CH=CH-, -CF=CF- or -C≡C- is particularly preferred. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
In general formula (i-1), A ⁱⁱ¹ and A ⁱⁱ² are (a) a 1,4-cyclohexylene group (one -CH ₂ - present in this group or two or more non-adjacent - CH ₂ - may be replaced with -O- or -S-.)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group 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 (the hydrogen atoms present in these groups are replaced with fluorine atoms or chlorine atoms) Also, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydro One group present in naphthalene-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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
It is preferable that it is a group selected from the group consisting of. Here, from the viewpoint of forming a conjugated structure with the π electrons of the NCSe structure and increasing Δn, A ⁱⁱ¹ and A ⁱⁱ² are preferably structures represented by (b), (c), or (d). . On the other hand, from the viewpoint of light resistance and widening the temperature range of the liquid crystal phase, the structure represented by (a) is preferable.

When A ⁱⁱ¹ and A ⁱⁱ² have the structure (b), they are preferably a 1,4-phenylene group, a pyrimidine-2,5-diyl group, or a pyridine-2,5-diyl group, and 1,4-phenylene A group is particularly preferred. In the case of structure (c), naphthalene-2,6-diyl group, naphthalene-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 is preferable, and naphthalene-2,6-diyl group, naphthalene-1,4-diyl group or phenanthrene-2,7-diyl group is particularly preferable. . In the case of structure (d), thiophene-2,5-diyl group, thiazole-2,5-diyl group, benzothiophene-2,5-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-diyl group or thieno[3,2-b]thiophene-2,5 -diyl group is preferred, and from the viewpoint of liquid crystallinity and Δn increase, benzothiophene-2,5-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-diyl group or thieno[3,2-b]thiophene-2,5-diyl group are preferred, and dibenzothiophene-2,6 -diyl group or thieno[3,2-b]thiophene-2,5-diyl group is particularly preferred.

Further, the groups (a) to (d) above may be substituted with one or more substituents L ⁱⁱ¹ . When substituted, L ⁱⁱ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group , a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyano group, and a fluorine atom, a chlorine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, and a dimethylamino group. , a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyano group, and a fluorine atom, a chlorine atom, a cyano group, an isocyano group, or a thioisocyano group are especially preferable from the viewpoint of increasing Δn. preferable.
L ⁱⁱ¹ is also preferably a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms; or a cyclic alkyl group, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Further, from the viewpoint of solubility, a linear alkyl group having 1 to 3 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms is preferable. Further, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Furthermore, one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and when substituted, -O- , -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, - It is preferable that CH=CH-, -CF=CF- or -C≡C- is substituted, -O-, -S-, -COO-, -OCO-, -CO-S-, -S- It is preferably replaced with CO-, -CH=CH-, -CF=CF- or -C≡C-, -O-, -COO-, -OCO-, -CH=CH-, -CF= More preferably, it is replaced with CF- or -C≡C-, and from the viewpoint of increasing Δn, it is replaced with -O-, -CH=CH-, -CF=CF- or -C≡C-. This is particularly preferred. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
In order to increase Δn of the liquid crystal composition, A ⁱⁱ¹ and A ⁱⁱ² are preferably aromatic. In this case, A ⁱⁱ¹ and A ⁱⁱ² are (d) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= It's okay if you get hurt.)
(e) 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (present in these groups) The hydrogen atom may be substituted with a fluorine atom or a chlorine atom, and 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene- One -CH= or two or more -CH= present in the 2,7-diyl group may be replaced with -N=.)
(g) 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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
A group selected from the group consisting of is preferable, and these groups may be unsubstituted or substituted with one or more substituents L ⁱⁱ¹ .
In general formula (i-1), Z ⁱⁱ¹ each independently represents a single bond, -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- or -N=CH - is preferably a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =C(CH ₃ )COO-, -OCOC(CH ₃ )=CH-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- Preferably, a single bond, -CH=CH-, -CF=CF-, -C≡C-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- More preferably, from the viewpoint of increasing Δn, a single bond, -C≡C-, -N=N-, -C=N-N=C-, -CH=N- or -N=CH- It is particularly preferred that there be.
Z ⁱⁱ¹ is also preferably an alkylene group having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 12 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. . Preferably, one or more -CH ₂ - groups in the alkylene group are substituted with -O-, -COO- or -OCO-. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosive nature, it is not preferable for oxygen atoms to bond with each other.
X ⁱⁱ¹ is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH ₂ - or 2 -CH ₂ - each independently represents -O-, -S-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CH =CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- It is preferably 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 optionally contain a fluorine atom, a chlorine atom, a cyano group, an isocyano group, or a thioisocyano group. , or one -CH ₂ - or two or more -CH ₂ - are each independently substituted with -O-, -CH=CH-, -CF=CF- or -C≡C- A linear alkyl group having 1 to 12 carbon atoms is more preferable, and a fluorine atom, a chlorine atom, a cyano group or a thioisocyano group is particularly preferable, and a fluorine atom, a chlorine atom, a cyano group or a thioisocyano group is preferable. It is particularly preferable that
n ⁱⁱ¹ is preferably an integer from 1 to 8, preferably an integer from 1 to 6, particularly preferably an integer from 1 to 3. Further, from the viewpoint of reducing viscosity, it is preferably an integer of 1 to 2, and in order to increase the upper limit of the temperature range of the liquid crystal phase, it is preferably an integer of 2 to 3.

Further, as the compound represented by the general formula (II), compounds represented by the general formulas (II-2a) to (II-2d) are preferable.

(In the formula, R ⁱⁱ¹² , A ⁱⁱ²² and X ⁱⁱ¹² represent the same meanings as R ⁱⁱ¹ , A ⁱⁱ² and X ⁱⁱ¹ above, and A ⁱⁱ¹² and A ⁱⁱ²⁴ represent the same meanings as A ⁱⁱ¹ above.)
As the compound represented by the general formula (II), compounds represented by the general formulas (II-a1) to (II-e8) are particularly preferred.

(In the formula, R ^ii1a represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 6 carbon atoms, or a straight chain or branched alkoxy group having 1 to 6 carbon atoms.)
The lower limit of the preferable total content of compounds represented by general formula (i-1) or general formula (II) with respect to the total amount of the composition of the present invention is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, It is 100%. The preferable upper limit values of the content are 100%, 99%, 98%, and 95%.

The compounds further included in the composition of the present invention are preferably compounds represented by the following general formulas (A1) to (A3).

In the above formula, R ^b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and has a 3- to 6-membered ring structure. Any -CH ₂ - present in the group may be -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF- or -C≡C - may be substituted with, and any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but linear alkyl groups having 1 to 7 carbon atoms, carbon atoms A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and a linear 3-alkenyl group having 1 to 5 carbon atoms whose terminal is substituted with an alkoxyl group having 1 to 3 carbon atoms. Alkyl groups are preferred. Further, when an asymmetric carbon is generated due to branching, the compound may be optically active or racemic.

Ring A, Ring B and Ring C may each be independently substituted with a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. Good 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6- optionally substituted with one or more fluorine atoms Diyl group, 1,4-cyclohexenylene group optionally substituted with fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5 -diyl group, trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted with a fluorine atom, or A 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms is preferred. In particular, when Ring B is a trans-1,4-cyclohexylene group or a trans-decahydronaphthalene-trans-2,6-diyl group, Ring A may be a trans-1,4-cyclohexylene group. Preferably, when Ring C is a trans-1,4-cyclohexylene group or a trans-decahydronaphthalene-trans-2,6-diyl group, Ring B and Ring A are a trans-1,4-cyclohexylene group. It is preferable that there be. Furthermore, in (A3), ring A is preferably a trans-1,4-cyclohexylene group.
L ^a , L ^b and L ^c are linking groups, and each independently represents a single bond, an ethylene group (-CH ₂ CH ₂ -), a 1,2-propylene group (-CH(CH ₃ )CH ₂ - and -CH ₂ CH(CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CH=CF-, - CF=CH-, -CF=CF-, -C≡C- or -CH=NN=CH-, but includes a single bond, ethylene group, 1,4-butylene group, -COO-, -OCF ₂ -, -CF ₂ O-, -CF=CF- or -C≡C- is preferred, and a single bond or ethylene group is particularly preferred. Moreover, it is preferable that at least one of (A2) and at least two of (A3) represent a single bond.

Ring Z is an aromatic ring and can be represented by the following general formulas (La) to (Lc).

In the formula, Y ^a to Y ^j each independently represent a hydrogen atom or a fluorine atom, but in (La), at least one of Y ^a and Y ^b is preferably a fluorine atom, and in (Lb), It is preferable that at least one of Y ^d to Y ^f is a fluorine atom, and it is particularly preferable that Y ^d is a fluorine atom.

The terminal group P ^a is a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group or a difluoromethyl group, or an alkoxyl group having 2 or 3 carbon atoms substituted with two or more fluorine atoms, or an alkyl group. group, alkenyl group or alkenyloxy group, preferably a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group, and particularly preferably a fluorine atom.

In addition, when using compounds represented by general formulas (A1) to (A3) in combination, even if the same options (ring A, L ^a, etc.) in different molecules represent the same substituent, different substituents It may also represent

The lower limits of the preferable content of the compounds represented by formulas (A1) to (A3) with respect to the total amount of the composition of the present invention are 1%, 2%, 5%, and 8%. %, 10%, 13%, 15%, 18%, 20%, 22%, 25%, and 30%. The upper limit values of the preferable content are 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, and 10%. , 8%, and 5%.

Further, in general formulas (A1) to (A3), general formulas (i-1) and (ii) of the present invention are excluded.

When the composition of the present invention needs to have a low viscosity and a fast response speed, it is preferable to set the lower limit value higher and the upper limit value higher. Furthermore, if it is necessary to maintain a high Tni of the composition of the present invention and to obtain a composition that is less likely to cause burn-in, it is preferable to set the lower limit value to a lower value and the upper limit value to a lower value. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to set the lower limit value to a higher value and the upper limit value to a higher value.

More preferable forms of general formulas (A1) to (A3) can be represented by the following general formulas (A1a) to (A3c).

(In the formula, A, B, C, Y ^a and Y ^b represent the same meanings as A, B, C, Y ^a and Y ^b in general formulas (A1) to (A3).)
More preferred are the following compounds.

The compounds further included in the composition of the present invention are preferably compounds represented by the following general formulas (B1) to (B3).

In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and has a 3- to 6-membered ring structure. Any -CH ₂ - present in the group may be -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF- or -C≡C -, any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, a carbon atom A linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and a linear 3-alkenyl group having 1 to 5 carbon atoms whose terminal is substituted with an alkoxyl group having 1 to 3 carbon atoms. Alkyl groups are preferred. Further, when an asymmetric carbon is generated due to branching, the compound may be optically active or racemic.

Ring D, Ring E and Ring F may each be independently substituted with a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6- optionally substituted with one or more fluorine atoms Diyl group, 1,4-cyclohexenylene group optionally substituted with fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5 -diyl group, trans-1,4-cyclohexylene group, trans-decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted with a fluorine atom, or A 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms is preferred. In particular, when Ring E is a trans-1,4-cyclohexylene group or a trans-decahydronaphthalene-trans-2,6-diyl group, Ring D may be a trans-1,4-cyclohexylene group. Preferably, when Ring F is a trans-1,4-cyclohexylene group or a trans-decahydronaphthalene-trans-2,6-diyl group, Ring D and Ring E are a trans-1,4-cyclohexylene group. It is preferable that there be. Further, in (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , L ^e and L ^f are linking groups, and each independently represents a single bond, an ethylene group (-CH ₂ CH ₂ -), a 1,2-propylene group (-CH(CH ₃ )CH ₂ - and )-CH ₂ CH (CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C-, -OCH ₂ -, -CH ₂ O- or -CH=NN=CH-, but does not include a single bond, ethylene group, -COO-, -OCF ₂ -, -CF ₂ O-, -CF=CF- or -C≡C- are preferred, and a single bond, ethylene group or -COO- is particularly preferred. Further, it is preferable that at least one of (B2) and at least two of (B3) represent a single bond.

Ring Y is an aromatic ring and can be represented by the following general formulas (L ^d ) to (L ^f ).

In the formula, Y ^k to Y ^q each independently represent a hydrogen atom or a fluorine atom, and in (Le), Y ^m is preferably a fluorine atom.

The terminal group P ^b represents a cyano group (-CN), a cyanato group (-OCN), -C≡CCN or an isothiocyano group (-NCS), and preferably a cyano group or an isothiocyano group.

In addition, when using compounds represented by general formulas (B1) to (B3) in combination, even if the same options (ring D, L ^d, etc.) in different molecules represent the same substituent, they may be different substituents. It may also represent

Further, general formulas (B1) to (B3) exclude general formulas (i-1) and (ii) of the present invention.

The lower limits of the preferable content of the compounds represented by formulas (B1) to (B3) with respect to the total amount of the composition of the present invention are 1%, 2%, 5%, and 8%. %, 10%, 13%, 15%, 18%, 20%, 22%, 25%, and 30%. The upper limit values of the preferable content are 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, and 10%. , 8%, and 5%.

When the composition of the present invention needs to have a low viscosity and a fast response speed, it is preferable to set the lower limit value to a lower value and the upper limit value to a higher value. Furthermore, if it is necessary to maintain a high Tni of the composition of the present invention and to obtain a composition that is less likely to cause burn-in, it is preferable to set the lower limit value to a lower value and the upper limit value to a higher value. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to set the lower limit value to a higher value and the upper limit value to a higher value.

More preferable forms of general formulas (B1) to (B3) can be represented by the following general formulas (B1a) to (B2c).

(In the formula, A, B, Y ^k and Y ^l represent the same meanings as A, B, Y ^k and Y ^l in general formulas (B1) to (B3).)
More preferred are the following compounds.

It is preferable that compounds represented by the following general formulas (C1) to (C3) are further included in the composition of the present invention.

In the above formula, R ^d and P ^e each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and may have 3 to 6 carbon atoms. It may have a cyclic structure of membered rings, and any -CH ₂ - present in the group is -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF= It may be replaced by CF- or -C≡C-, and any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but it may be replaced by a straight carbon atom having 1 to 7 carbon atoms. A linear alkyl group, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxyl group having 1 to 3 carbon atoms, or A linear alkyl group having 1 to 5 carbon atoms substituted with an alkoxyl group having 1 to 3 carbon atoms is preferred, and at least one is a linear alkyl group having 1 to 7 carbon atoms, and at least one is a linear alkyl group having 2 to 7 carbon atoms. A linear 1-alkenyl group or a linear 3-alkenyl group having 4 to 7 carbon atoms is particularly preferred. Further, when an asymmetric carbon is generated due to branching, the compound may be optically active or racemic.

Ring G, Ring H, Ring I and Ring J each independently represent a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms, or 1,4-phenylene group optionally substituted with a methyl group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, a naphthalene-2,6-diyl group optionally substituted with 1 to 2 fluorine atoms a tetrahydronaphthalene-2,6-diyl group, a 1,4-cyclohexenylene group optionally substituted with 1 to 2 fluorine atoms, a 1,3-dioxane-trans-2,5-diyl group, Represents a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, which is substituted with a transdecahydronaphthalene-trans-2,6-diyl group or one or more fluorine atoms in each compound. Naphthalene-2,6-diyl group which may be substituted with 1 to 2 fluorine atoms, tetrahydronaphthalene-2,6-diyl group which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenyl group which may be substituted with fluorine atoms It is preferable that the number of lene groups, 1,3-dioxane-trans-2,5-diyl groups, pyrimidine-2,5-diyl groups, or pyridine-2,5-diyl groups is one or less, and the other rings are trans -1,4-cyclohexylene group or 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms or methyl groups is preferred.

L ^g , L ^h and L ⁱ are linking groups, and each independently represents a single bond, an ethylene group (-CH ₂ CH ₂ -), a 1,2-propylene group (-CH(CH ₃ )CH ₂ - and )-CH ₂ CH (CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C- or -CH=NN=CH-, but does not include a single bond, ethylene group, 1,4-butylene group, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CF=CF-, -C≡C- or -CH=NN=CH-, and at least one of them is preferred in (C2) and at least one of them is in (C3). Preferably, at least two represent single bonds.

In addition, when using compounds represented by general formulas (C1) to (C3) in combination, even if the same options (ring G, L ^g, etc.) in different molecules represent the same substituent, they may be different substituents. It may also represent

Further, in general formulas (C1) to (C3), general formulas (A1) to (A3), (B1) to (B3), (i-1) and (ii) of the present invention are excluded.

The lower limits of the preferable content of the compounds represented by formulas (C1) to (C3) with respect to the total amount of the composition of the present invention are 1%, 2%, 5%, and 8%. %, 10%, 13%, 15%, 18%, 20%, 22%, 25%, and 30%. The upper limit values of the preferable content are 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, and 10%. , 8%, and 5%.

When the composition of the present invention needs to have a low viscosity and a fast response speed, it is preferable to set the lower limit value to a lower value and the upper limit value to a higher value. Further, if it is necessary to maintain a high Tni of the composition of the present invention and to obtain a composition that is less likely to cause burn-in, it is preferable to set the lower limit value to a higher value and the upper limit value to a higher value. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to set the lower limit value to a lower value and the upper limit value to a lower value.

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, preferably 0 or 1, and preferably 1 when compatibility with other liquid crystal molecules is important.

More preferable forms of (C1) can be represented by the following general formulas (C1a) to (C1h).

In each of the above formulas, R ^f and R ^g each independently represent a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 1-alkenyl group having 4 to 7 carbon atoms. Represents a linear 3-alkenyl group, a linear alkoxyl group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms whose terminal is substituted with an alkoxyl group having 1 to 3 carbon atoms. However, at least one of them represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms. However, when rings G1 to G8 are aromatic rings, the corresponding R ^f excludes 1-alkenyl groups and alkoxyl groups, and when rings H1 to H8 are aromatic rings, the corresponding R ^g refers to 1-alkenyl groups and alkoxyl groups. Exclude groups.

Ring G1 and ring H1 are each independently substituted with a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group; 1,4-phenylene group which may be substituted with one or more fluorine atoms, naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2 which may be substituted with 1 to 2 fluorine atoms, 6-diyl group, 1,4-cyclohexenylene group optionally substituted with 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group, but in each compound, trans decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6 which may be substituted with one or more fluorine atoms. -diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted with fluorine atoms, 1,3- The number of dioxane-trans-2,5-diyl groups, pyrimidine-2,5-diyl groups, or pyridine-2,5-diyl groups is preferably one or less, in which case the other ring is trans-1,4 - A cyclohexylene group or a 1,4-phenylene group optionally substituted with 1 to 2 fluorine atoms or methyl groups. Ring G2 and Ring H2 are each independently substituted with a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group. 1,4-phenylene group which may be substituted with one or more fluorine atoms, naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2 which may be substituted with 1 to 2 fluorine atoms, 6-diyl group, but in each compound, trans decahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, 1- The number of tetrahydronaphthalene-2,6-diyl groups optionally substituted with two fluorine atoms is preferably one or less, and in that case, the other ring is a trans-1,4-cyclohexylene group or a A 1,4-phenylene group optionally substituted with ~2 fluorine atoms or methyl groups. Ring G3 and ring H3 are each independently a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group, and naphthalene-2 which may be substituted with one or more fluorine atoms. ,6-diyl group, represents a tetrahydronaphthalene-2,6-diyl group optionally substituted with 1 to 2 fluorine atoms, but naphthalene optionally substituted with one or more fluorine atoms in each compound The number of -2,6-diyl groups and tetrahydronaphthalene-2,6-diyl groups optionally substituted with 1 to 2 fluorine atoms is preferably one or less.

More preferred are the following compounds.

More preferable forms of (C2) can be represented by the following general formulas (C2a) to (C2m).

In the above formula, ring G1, ring G2, ring G3, ring H1, ring H2 and ring H3 represent the above-mentioned meanings, ring I1 is the same as ring G1, ring I2 is the same as ring G2, and ring I3 is the same as ring G3. express meaning. In addition, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, 1 to 2 fluorine atoms a tetrahydronaphthalene-2,6-diyl group which may be substituted with, a 1,4-cyclohexenylene group which may be substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, The number of pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably one or less, and in that case, the other ring is a trans-1,4-cyclohexylene group or one to two pyridine-2,5-diyl groups. It is a 1,4-phenylene group which may be substituted with a fluorine atom or a methyl group.

More preferred are the following compounds.

Next, more preferable forms of (C3) can be represented by the following general formulas (C3a) to (C3f).

In the above formula, ring G1, ring G2, ring H1, ring H2, ring I1 and ring I2 represent the above-mentioned meanings, and ring J1 represents the same meaning as ring G1 and ring J2 represents the same meaning as ring G2. In addition, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, 1 to 2 fluorine atoms a tetrahydronaphthalene-2,6-diyl group which may be substituted with, a 1,4-cyclohexenylene group which may be substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, The number of pyrimidine-2,5-diyl groups or pyridine-2,5-diyl groups is preferably one or less, and in that case, the other ring is a trans-1,4-cyclohexylene group or one to two pyridine-2,5-diyl groups. It is a 1,4-phenylene group which may be substituted with a fluorine atom or a methyl group.

More preferred are the following compounds.

Expressed by general formula (i-1), general formulas (A1) to (A3), general formulas (B1) to (B3), and general formulas (C1) to (C3) with respect to the total amount of the composition of the present invention. The lower limits of the total preferred content of the compounds are 80%, 85%, 88%, 90%, 92%, 93%, 94%, and 95%. %, 96%, 97%, 98%, 99%, and 100%. The preferable upper limit values of the content are 100%, 99%, 98%, and 95%.

Expressed by general formula (i-1), general formulas (A1a) to (A3c), general formulas (B1a) to (B2c), and general formulas (C1a) to (C3f) with respect to the total amount of the composition of the present invention. The lower limits of the total preferred content of the compounds are 80%, 85%, 88%, 90%, 92%, 93%, 94%, and 95%. %, 96%, 97%, 98%, 99%, and 100%. The preferable upper limit values of the content are 100%, 99%, 98%, and 95%.

The composition of the present invention preferably does not contain a compound having a structure in which heteroatoms such as oxygen atoms are bonded to each other, such as a peracid (-CO-OO-) structure, in the molecule.

When the reliability and long-term stability of the composition are important, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less based on the total mass of the composition. It is preferably contained in an amount of 1% or less, more preferably 1% or less, and most preferably substantially free.

When placing emphasis on stability by UV irradiation, the content of the compound in which chlorine atoms are substituted is preferably 15% or less, preferably 10% or less, based on the total mass of the composition. % or less, more preferably 5% or less, preferably 3% or less, and even more preferably substantially no content.

It is preferable to increase the content of the compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80% relative to the total mass of the composition. % or more, more preferably 90% or more, even more preferably 95% or more, and the composition is composed only of compounds in which substantially all the ring structures in the molecule are 6-membered rings. Most preferably.

In order to suppress deterioration of the composition due to oxidation, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group should be reduced to the total mass of the composition. It is preferably 10% or less, more preferably 8% or less, more preferably 5% or less, preferably 3% or less, and even more preferably substantially free.

When emphasizing the improvement of viscosity and Tni, it is possible to reduce the content of a compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which the hydrogen atom may be substituted with a halogen. Preferably, the content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, more preferably 8% or less, based on the total mass of the composition. , more preferably 5% or less, preferably 3% or less, and even more preferably substantially no content.

In the present application, "substantially not contained" means not contained except for unintentionally contained substances.

When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, and when the alkenyl group is bonded to cyclohexane, the alkenyl group has 2 to 5 carbon atoms. Preferably, when the alkenyl group is bonded to benzene, the number of carbon atoms in the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are not directly bonded. Preferably not.

In order to improve the stability of the liquid crystal composition in the present invention, it is preferable to add an antioxidant. Examples of antioxidants include hydroquinone derivatives, nitrosamine-based polymerization inhibitors, hindered phenol-based antioxidants, and more specifically, tert-butylhydroquinone, methylhydroquinone, and " Q-1300, Q-1301, BASF's IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1425, "IRGANOX1520", "IRGANOX1726", Examples include "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565", and the like.

The amount of the antioxidant added is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, based on the polymerizable liquid crystal composition.

In order to improve the stability of the liquid crystal composition in the present invention, it is preferable to add a UV absorber. The UV absorber is preferably one that has an excellent ability to absorb ultraviolet rays with a wavelength of 370 nm or less and, from the viewpoint of good liquid crystal display properties, has little absorption of visible light with a wavelength of 400 nm or more. More specifically, examples include hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and triazine compounds. Examples of dophenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N, N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl- Examples include 4-hydroxybenzyl)benzene and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate. Examples of benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H -benzotriazol-2-yl)phenol), (2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, Triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy- hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-(2'-hydroxy-3',5'- di-tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2,6-di-tert -butyl-p-cresol, pentaerythrityl-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], including TINUVIN109, TINUVIN171, TINUVIN326, manufactured by BASF Japan Ltd. TINUVIN327, TINUVIN328, TINUVIN770, TINUVIN900, TINUVIN928, and KEMISORB 71, KEMISORB 73, and KEMISORB 74 manufactured by ChemiPro Kasei Co., Ltd. can also be preferably used.

It is preferable that the composition containing the compound containing the NCSe structure in the molecule of the present invention has a refractive index anisotropy (Δn) of 0.15 or more at 25°C. In particular, when used for high frequency applications, Δn is preferably 0.20 or more, preferably 0.25 or more, preferably 0.30 or more, particularly 0.35 or more. preferable.
The composition containing the compound containing the NCSe structure in the molecule of the present invention preferably has an absolute value of dielectric anisotropy (|Δε|) of 10 or more, preferably 10 to 40 at 25°C. Preferably, 20 to 40 is more preferable. Both positive and negative dielectric anisotropy values are preferred.
Further, η at 20° C. is preferably 5 to 45 mPa·s, more preferably 5 to 25 mPa·s, and particularly preferably 10 to 20 mPa·s. Further, T _ni is preferably 60°C to 200°C, more preferably 70°C to 190°C, and particularly preferably 80°C to 180°C.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. "%" in the compositions of the following Examples and Comparative Examples means "% by mass" unless otherwise specified.
Hereinafter, the following abbreviations will be used.
Me: Methyl group Et: Ethyl group Tol: Toluene DBU: 1,8-diazabicyclo[5.4.0]-7-undecene DMF: N,N-dimethylformamide THF: Tetrahydrofuran DMAP: N,N-dimethyl-4- Aminopyridine DIC: N,N-diisopropylcarbodiimide MEHQ: 4-methoxyphenol p-TsOH: p-toluenesulfonic acid Cr: Crystal
N: Nematic phase Sm: Smectic phase Iso: Isotropic liquid (Example 1)

Under nitrogen atmosphere, 4-iodoaniline (18.3 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis To a mixture of (triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) was added 1-butyl-4-ethynyl at room temperature. A solution of benzene (14.6 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((4-butylphenyl)ethynyl)aniline (19.8 g, yield 95%).

Under a nitrogen atmosphere, a mixture of 4-((4-butylphenyl)ethynyl)aniline (18.8 g, 76 mmol), formic acid (10.4 g, 227 mmol), and toluene (200 mL) was heated to 80° C. and stirred for 2 hours. . After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After the solvent was distilled off under reduced pressure, N-(4-((4-butylphenyl)ethynyl)phenyl)formamide (9.0 g, yield 43%) was obtained by recrystallizing from toluene/hexane.

Under a nitrogen atmosphere, triphosgene was added to a dichloromethane (100 mL) solution of N-(4-((4-butylphenyl)ethynyl)phenyl)formamide (9.0 g, 32 mmol) and triethylamine (14.4 g, 143 mmol) under ice cooling. (5.8 g, 19 mmol) in dichloromethane (40 mL) was added dropwise, and the mixture was stirred for 4 hours while heating under reflux. Next, selenium (5.1 g, 65 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while being heated under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization from hexane yielded 1-butyl-4-((4-isoselenocyanatophenyl)ethynyl)benzene (P-1) (3.5 g, yield 33%, Cr 91 Iso) was obtained.
(Example 2)

Under nitrogen atmosphere, 2-chloro-4-iodoaniline (21.3 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis(triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) at room temperature. A solution of -4-ethynylbenzene (14.6 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((4-butylphenyl)ethynyl)-2-chloroaniline (22.6 g, yield 95%).

Under a nitrogen atmosphere, a mixture of 4-((4-butylphenyl)ethynyl)-2-chloroaniline (22.6 g, 80 mmol), formic acid (11.0 g, 239 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(4-((4-butylphenyl)ethynyl)-2-chlorophenyl)formamide (12.0 g, yield 48%) was obtained by recrystallizing with toluene/hexane. .

Under a nitrogen atmosphere, N-(4-((4-butylphenyl)ethynyl)-2-chlorophenyl)formamide (12.0 g, 38 mmol) and triethylamine (17.1 g, 169 mmol) were added to a dichloromethane (100 mL) solution under ice cooling. A solution of triphosgene (6.9 g, 23 mmol) in dichloromethane (40 mL) was added dropwise, and the mixture was stirred for 4 hours while heating under reflux. Selenium (6.1 g, 77 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. Water was added and the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization with hexane yielded 4-((4-butylphenyl)ethynyl)-2-chloro-1-isoselenocyanatobenzene (P-2) (4.2 g, yield 29%).
(Example 3)

Under nitrogen atmosphere, 4-iodoaniline (18.3 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis 4-ethynyl-2-fluoro A solution of -1-propoxybenzene (16.4 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((3-fluoro-4-propoxyphenyl)ethynyl)aniline (19.4 g, yield 86%).

Under a nitrogen atmosphere, a mixture of 4-((3-fluoro-4-propoxyphenyl)ethynyl)aniline (19.4 g, 72 mmol), formic acid (10.0 g, 216 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(4-((3-fluoro-4-propoxyphenyl)ethynyl)phenyl)formamide (10.2 g, yield 48%) was obtained by recrystallizing with toluene/hexane. Ta.

Under a nitrogen atmosphere, a solution of N-(4-((3-fluoro-4-propoxyphenyl)ethynyl)phenyl)formamide (10.2 g, 34 mmol) and triethylamine (15.3 g, 151 mmol) in dichloromethane (100 mL) was cooled with ice. A solution of triphosgene (6.1 g, 21 mmol) in dichloromethane (40 mL) was added dropwise thereto, and the mixture was stirred for 4 hours while heating under reflux. Selenium (5.4 g, 69 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. Water was added and the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization with hexane yielded 2-fluoro-4-((4-isoselenocyanatophenyl)ethynyl)-1-propoxybenzene (P-3) (5.6 g, yield 46%).
(Example 4)

Under nitrogen atmosphere, 2-fluoro-4-iodoaniline (19.8 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis(triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) at room temperature. A solution of -4-ethynylbenzene (14.6 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((4-butylphenyl)ethynyl)-2-fluoroaniline (20.1 g, yield 90%).

Under a nitrogen atmosphere, a mixture of 4-((4-butylphenyl)ethynyl)-2-fluoroaniline (20.1 g, 75 mmol), formic acid (10.4 g, 226 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(4-((4-butylphenyl)ethynyl)-2-fluorophenyl)formamide (12.0 g, yield 54%) was obtained by recrystallizing with toluene/hexane. Ta.

Under a nitrogen atmosphere, a solution of N-(4-((4-butylphenyl)ethynyl)-2-fluorophenyl)formamide (12.0 g, 41 mmol) and triethylamine (18.1 g, 179 mmol) in dichloromethane (100 mL) was cooled with ice. A solution of triphosgene (7.2 g, 24 mmol) in dichloromethane (40 mL) was added dropwise thereto, and the mixture was stirred for 4 hours while heating under reflux. Selenium (6.4 g, 81 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization with hexane yielded 4-((4-butylphenyl)ethynyl)-2-fluoro-1-isoselenocyanatobenzene (P-4) (5.6 g, yield 39%).
(Example 5)

Under nitrogen atmosphere, 2-fluoro-4-iodoaniline (19.8 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis(triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) at room temperature. A solution of -4-(4-hexylcyclohexyl)benzene (24.7 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 2-fluoro-4-((4-(4-hexylcyclohexyl)phenyl)ethynyl)aniline (30.8 g, yield 97%).

Under a nitrogen atmosphere, a mixture of 2-fluoro-4-((4-(4-hexylcyclohexyl)phenyl)ethynyl)aniline (30.8 g, 82 mmol), formic acid (11.2 g, 245 mmol), and toluene (200 mL) was mixed with 80 The mixture was heated to ℃ and stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, recrystallization from toluene/hexane yielded N-(2-fluoro-4-((4-(4-hexylcyclohexyl)phenyl)ethynyl)phenyl)formamide (18.6 g, yield 56%).

Under a nitrogen atmosphere, N-(2-fluoro-4-((4-(4-hexylcyclohexyl)phenyl)ethynyl)phenyl)formamide (18.6 g, 46 mmol), triethylamine (20.4 g, 202 mmol) in dichloromethane (100 mL) ) A solution of triphosgene (8.2 g, 28 mmol) in dichloromethane (40 mL) was added dropwise to the solution under ice cooling, and the mixture was stirred for 4 hours while heating under reflux. Selenium (7.2 g, 92 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization from hexane yielded 2-fluoro-4-((4-(4-hexylcyclohexyl)phenyl)ethynyl)-1-isoselenocyanatobenzene (P-5) (6 .2 g, yield 29%) was obtained.
(Example 6)

Under nitrogen atmosphere, 4-iodoaniline (18.3 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis To a mixture of (triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) was added 2-ethynyl-6-hexyl at room temperature. A solution of naphthalene (21.7 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((6-hexylnaphthalen-2-yl)ethynyl)aniline (26.7 g, yield 98%).

Under a nitrogen atmosphere, a mixture of 4-((6-hexylnaphthalen-2-yl)ethynyl)aniline (26.7 g, 82 mmol), formic acid (11.3 g, 245 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(4-((6-hexylnaphthalen-2-yl)ethynyl)phenyl)formamide (18.4 g, yield 64%) was obtained by recrystallizing with toluene/hexane. Ta.

Under a nitrogen atmosphere, a solution of N-(4-((6-hexylnaphthalen-2-yl)ethynyl)phenyl)formamide (18.4 g, 52 mmol) and triethylamine (23.1 g, 228 mmol) in dichloromethane (100 mL) was cooled with ice. A solution of triphosgene (9.2 g, 31 mmol) in dichloromethane (40 mL) was added dropwise thereto, and the mixture was stirred for 4 hours while heating under reflux. Selenium (8.2 g, 104 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, 2-hexyl-6-((4-isoselenocyanatophenyl)ethynyl)naphthalene (P-6) (4.8 g, yield 22%) was obtained by recrystallizing with hexane. Obtained.
(Example 7)

Under nitrogen atmosphere, 2-fluoro-5-iodoaniline (19.8 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis(triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) at room temperature. A solution of -4-ethynylbenzene (14.6 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 5-((4-butylphenyl)ethynyl)-2-fluoroaniline (16.3 g, yield 73%).

Under a nitrogen atmosphere, a mixture of 5-((4-butylphenyl)ethynyl)-2-fluoroaniline (16.3 g, 61 mmol), formic acid (8.4 g, 183 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(5-((4-butylphenyl)ethynyl)-2-fluorophenyl)formamide (8.8 g, yield 49%) was obtained by recrystallizing with toluene/hexane. Ta.

Under a nitrogen atmosphere, a solution of N-(5-((4-butylphenyl)ethynyl)-2-fluorophenyl)formamide (8.8 g, 30 mmol) and triethylamine (13.3 g, 131 mmol) in dichloromethane (100 mL) was cooled with ice. A solution of triphosgene (5.3 g, 18 mmol) in dichloromethane (40 mL) was added dropwise thereto, and the mixture was stirred for 4 hours while heating under reflux. Selenium (4.7 g, 60 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization with hexane yielded 4-((4-butylphenyl)ethynyl)-1-fluoro-2-isoselenocyanatobenzene (P-7) (2.5 g, yield 24%).
(Example 8)

Under nitrogen atmosphere, 4-iodoaniline (18.3 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (12.7 g, 84 mmol), tetrakis To a mixture of (triphenylphosphine)palladium (0.6 g, 0.5 mmol), copper(I) iodide (0.1 g, 0.5 mmol), and THF (100 mL) was added 3-ethynyldibenzo[b, d] A solution of thiophene (19.1 g, 92 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-(dibenzo[b,d]thiophen-3-ylethynyl)aniline (24.0 g, yield 96%).

Under a nitrogen atmosphere, a mixture of 4-(dibenzo[b,d]thiophen-3-ylethynyl)aniline (24.0 g, 80 mmol), formic acid (11.1 g, 240 mmol), and toluene (200 mL) was heated to 80 °C. Stirred for 2 hours. After adding water to the reaction solution, the aqueous layer was extracted twice with toluene, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (20 g) were added, and the mixture was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, N-(4-(dibenzo[b,d]thiophen-3-ylethynyl)phenyl)formamide (18.2 g, yield 69%) was obtained by recrystallizing with toluene/hexane. Ta.

Under a nitrogen atmosphere, a solution of N-(4-(dibenzo[b,d]thiophen-3-ylethynyl)phenyl)formamide (18.2 g, 56 mmol) and triethylamine (24.8 g, 245 mmol) in dichloromethane (200 mL) was cooled with ice. A solution of triphosgene (9.9 g, 33 mmol) in dichloromethane (80 mL) was added dropwise thereto, and the mixture was stirred for 4 hours while heating under reflux. Selenium (8.8 g, 111 mmol) was added to the reaction solution, and the mixture was stirred for 10 hours while heating under reflux. After adding water to the reaction solution, the aqueous layer was extracted twice with dichloromethane, and the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel (30 g) were added, and the mixture was purified by silica gel column chromatography (30 g of silica gel, mobile phase: toluene, hexane). After distilling off the solvent under reduced pressure, recrystallization from hexane yielded 3-((4-isoselenocyanatophenyl)ethynyl)dibenzo[b,d]thiophene (P-8) (5.3 g, yield 25%). ) was obtained.
(Comparative example 1)

Under a nitrogen atmosphere, 4-iodo-1-isothiocyanatobenzene (8.9 g, 34 mmol), triethylamine (4.1 g, 41 mmol), 1,8-diazabicyclo[5.4.0]-7-undecene (5. 2 g, 34 mmol), tetrakis(triphenylphosphine)palladium (0.2 g, 0.2 mmol), copper(I) iodide (0.04 g, 0.2 mmol), and THF (50 mL) at room temperature. A solution of -butyl-4-ethynylbenzene (5.9 g, 37 mmol) in THF (20 mL) was added dropwise, and the mixture was stirred for 3 hours while heating under reflux. The reaction solution was poured into water, the aqueous layer was extracted twice with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was recrystallized from hexane to obtain 4-((4-butylphenyl)ethynyl)-1-isothiocyanatobenzene (3.1 g, yield 31%).

A parent liquid crystal (LC-1) exhibiting the following physical property values was prepared. All values are actually measured values.

T _n-i (nematic phase-isotropic liquid phase transition temperature): 73.8°C
Δε (dielectric constant anisotropy at 25°C): -2.79
Δn (refractive index anisotropy at 25°C): 0.101
γ ₁ (rotational viscosity coefficient at 25°C): 118
To this base liquid crystal (LC-1), (P-1) to (P-8) obtained in Examples 1 to 8 and Comparative Example 1 and compound (C-1) were added at 0%, 5%, and 10%. % liquid crystal composition was prepared. Extrapolated values at 100% using the least squares method are shown below. By comparing Examples 9 to 16 and Comparative Example 2, it was found that the compound of the present invention effectively increases Δn and Δε.

Claims (11)

General formula (i-1) below

(In the formula,
R ⁱ¹ represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 12 carbon atoms,
Any hydrogen atom in the alkyl group may be substituted with a halogen atom,
One or more -CH ₂ - in the alkyl group may each be independently replaced with -O- ,
Oxygen atoms do not bond with each other,
A ⁱ¹ is
(a) 1,4-cyclohexylene group
(b) 1,4-phenylene group
(c) 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group
(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 group, thieno[3,2-b]thiophene-2,5-diyl group
represents a group selected from the group consisting of,
Ai2 is ^_
(b) 1,4-phenylene group
(c) Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, anthracene-2,6-diyl group, anthracene- 1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group
(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 group, thieno[3,2-b]thiophene-2,5-diyl group
represents a group selected from the group consisting of,
A ⁱ¹ or A ⁱ² may be unsubstituted or substituted with one or more substituents L ⁱ¹ ,
L ⁱ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a carbon atom in which one -CH ₂ - or two or more -CH ₂ - may each be independently substituted with -O- . Represents a linear alkyl group having numbers 1 to 6 or a branched or cyclic alkyl group having 3 to 6 carbon atoms,
Oxygen atoms do not bond directly to each other,
Any hydrogen atom in the alkyl group may be substituted with a fluorine atom,
Z ⁱ¹ each independently represents a single bond, -CH=CH-, -CF=CF-, -C≡C- , or an alkylene group having 2 to 6 carbon atoms,
One or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are not directly bonded to each other,
n ⁱ¹ represents an integer from 1 to 3 ,
Here, when a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different. )
A liquid crystal composition containing a compound represented by: The following formula (P-7)

A liquid crystal composition containing a compound represented by: Furthermore, general formula (II)

(In the formula,
R ⁱⁱ¹ represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 40 carbon atoms,
Any hydrogen atom in the alkyl group may be substituted with a halogen atom, and one or more -CH ₂ - in the alkyl group are each independently -O-, -S-, - CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, - CF=CF- or -C≡C- may be replaced, but
Oxygen atoms do not bond with each other,
A ⁱⁱ¹ and A ⁱⁱ² each independently represent (a) a 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group is - (May be replaced with O- or -S-.)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group 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 (the hydrogen atoms present in these groups are replaced with fluorine atoms or chlorine atoms) Also, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydro One group present in naphthalene-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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
represents a group selected from the group consisting of,
These groups may be unsubstituted or substituted with one or more substituents L ⁱⁱ¹ ,
L ⁱⁱ¹ 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 - each 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 optionally substituted with -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,
Oxygen atoms do not bond directly to each other,
Any hydrogen atom in the alkyl group may be substituted with a fluorine atom,
Z ⁱⁱ¹ is each independently a single bond, -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 having 2 to 20 carbon atoms represents an alkylene group,
One or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are not directly bonded to each other,
X ⁱⁱ¹ is a hydrogen atom, 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 group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH ₂ - or two or more -CH ₂ - each independently -O-, -S-, -CO- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, - Number of carbon atoms optionally substituted by CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- Represents a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms,
Oxygen atoms do not bond directly to each other,
Any hydrogen atom in the alkyl group may be substituted with a fluorine atom,
n ⁱⁱ¹ represents an integer from 1 to 8,
Here, when a plurality of A ⁱⁱ¹ and Z ⁱⁱ¹ exist, they may be the same or different. )
The liquid crystal composition according to claim 1 or 2 , containing one or more compounds represented by the following. In the compound represented by the general formula (II), A ⁱⁱ¹ and A ⁱⁱ² are (e) a 1,4-phenylene group (one -CH= present in this group or two or more non-adjacent -CH= may be replaced with -N=.)
(f) 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (present in these groups) The hydrogen atom may be substituted with a fluorine atom or a chlorine atom, and 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene- One -CH= or two or more -CH= present in the 2,7-diyl group may be replaced with -N=.)
(g) 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 group, thieno[3,2-b]thiophene-2,5-diyl group (one -CH= or two or more non-adjacent -CH= present in this group is replaced with -N= )
represents a group selected from the group consisting of,
The liquid crystal composition according to claim 3 , wherein these groups may be unsubstituted or substituted with one or more substituents L ⁱⁱ¹ . In the compound represented by the general formula (II), one or more Z ⁱⁱ¹ present is -CH=CH-, -CF=CF-, -C≡C-, -N=N- or -C=N The liquid crystal composition according to claim 3 or 4 , wherein -N=C-. The liquid crystal composition according to any one of claims 1 to 5 , having a refractive index anisotropy of 0.15 or more. The liquid crystal composition according to any one of claims 1 to 6 , having a dielectric anisotropy of 2 or more. The liquid crystal composition according to any one of claims 1 to 7 , containing one or more of at least one of an antioxidant, an ultraviolet inhibitor, a chiral agent, an antistatic agent, and a dichroic dye. . A high frequency element, an antenna, a liquid crystal display element, a liquid crystal lens, or a birefringent lens for stereoscopic image display, using the liquid crystal composition according to any one of claims 1 to 8 . General formula (i-1) below

(In the formula,
R ⁱ¹ represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 12 carbon atoms,
Any hydrogen atom in the alkyl group may be substituted with a halogen atom,
One or more -CH ₂ - in the alkyl group may each be independently replaced with -O- ,
Oxygen atoms do not bond with each other,
A ⁱ¹ is
(a) 1,4-cyclohexylene group
(b) 1,4-phenylene group
(c) 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, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group
(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 group, thieno[3,2-b]thiophene-2,5-diyl group
represents a group selected from the group consisting of,
A ⁱ² is
(b) 1,4-phenylene group
(c) Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, anthracene-2,6-diyl group, anthracene- 1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group
(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 group, thieno[3,2-b]thiophene-2,5-diyl group
represents a group selected from the group consisting of,
A ⁱ¹ or A ⁱ² may be unsubstituted or substituted with one or more substituents L ⁱ¹ ,
L ⁱ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a carbon atom in which one -CH ₂ - or two or more -CH ₂ - may each be independently substituted with -O- . Represents a linear alkyl group having numbers 1 to 6 or a branched or cyclic alkyl group having 3 to 6 carbon atoms,
Oxygen atoms do not bond directly to each other,
Any hydrogen atom in the alkyl group may be substituted with a fluorine atom,
Z ⁱ¹ each independently represents a single bond, -CH=CH-, -CF=CF-, -C≡C- , or an alkylene group having 2 to 6 carbon atoms,
One or more -CH ₂ - in this alkylene group may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are not directly bonded to each other,
n ⁱ¹ represents an integer from 1 to 3 ,
Here, when a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different. )
A compound represented by The following formula (P-7)

A compound represented by