JP2021091630A - Liquid crystal compound for high-frequency apparatus and liquid crystal composition - Google Patents

Abstract

To provide a composition that has a liquid crystal phase in a broad temperature range, is excellent in solubility to a liquid crystal composition, and is stable to heat or light, while realizing high Δn, a liquid crystal composition that is excellent in high-frequency control effect by using the same and is excellent in the chemical stability, a liquid crystal display device using the liquid crystal composition and a liquid crystal antenna.SOLUTION: The present invention provides a compound represented by a general formula (1) and also provides a liquid crystal composition containing the compound and a liquid crystal display element and a liquid crystal antenna manufactured using the liquid crystal composition.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal compound, a liquid crystal composition containing the liquid crystal compound, 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, and in display applications such as TVs and window displays. As a new application of this liquid crystal, an antenna using a liquid crystal that transmits and receives radio waves between a mobile body such as a car and a communication satellite is attracting attention.
Conventionally, satellite communication uses a parabolic antenna, but when it is used in a mobile body, the parabolic antenna must be directed toward the satellite at any time, and a large moving part is required. However, in an antenna using a liquid crystal, since the transmission / reception direction of radio waves can be changed by operating the liquid crystal, it is not necessary to move the antenna itself, and the shape of the antenna can be made flat.
Autonomous driving of automobiles requires a large amount of high-precision 3D map information to be downloaded, and by incorporating an antenna using a liquid crystal into the automobile, a large amount of data can be downloaded from a communication satellite even if there is no mechanical moving part. It will be possible. The frequency band used for satellite communications is approximately 13 GHz, which is significantly different from the frequencies used in conventional liquid crystal display applications. Therefore, the required physical characteristics of the liquid crystal are also greatly different, and the refractive index anisotropy (Δn) required for the liquid crystal for the antenna is about 0.4, and the operating temperature range is -40 to 120 ° C or more (nematic phase).
Infrared laser image recognition / ranging devices using liquid crystals are also attracting attention as sensors for automatic driving of automobiles. The required characteristics of the liquid crystal for this application are high Δn (0.2 to 0.3) and high operating temperature range (-40 to 120 ° C or higher).
Conventionally, a method for producing a liquid crystal composition using a compound having a bistran structure or a compound having an NCS structure as described below has been reported in response to such required characteristics regarding a high Δn and an operating temperature range. (Patent Documents 1 and 2). However, Δn in these compounds is not yet sufficient, and other physical properties such as dielectric anisotropy (Δε), solubility in a liquid crystal composition, and viscosity are also values that can be put into practical use. It is extremely difficult to develop a composition.

Special Table 2013-544233 Public Relations Japanese Patent Application Laid-Open No. 2016-37607 Public Relations

The problem to be solved by the present invention is to provide a composition having a liquid crystal phase in a wide temperature range, having good solubility in a liquid crystal composition, and being stable to heat and light while achieving high Δn. Further, it is an object of the present invention to provide a liquid crystal composition having excellent high frequency control effect and excellent chemical stability, a liquid crystal display element using the liquid crystal composition, and a liquid crystal antenna.

In order to solve the above-mentioned problems, the inventors of the present application have conducted synthetic studies on various compounds, and found that the problems can be effectively solved by the compound represented by the general formula (I) containing a phenanthrene structure in the molecule. Heading The invention of the present application has been completed. Further, when the compound represented by the general formula (I) is added to the liquid crystal composition, it dissolves well and can widen the liquid crystal phase temperature range of the liquid crystal composition, and phenanthrene having a higher electron density. It has been found that Δn can be further increased by the effect of the structure and the acetylene structure.

When a liquid crystal composition is produced using the compound represented by the general formula (I) provided by the present invention, physical properties such as low viscosity, solubility, specific resistance, voltage retention, heat resistance, and light resistance are maintained. However, a liquid crystal composition having a wide liquid crystal phase temperature range and a large Δn can be obtained, and such a liquid crystal composition is excellent in electromagnetic wave control effect in a high frequency region. Therefore, the liquid crystal composition can be suitably used for a high frequency element, an antenna, a liquid crystal display element, a liquid crystal lens, a birefringent lens for displaying a stereoscopic image, and the like, but is particularly useful as a liquid crystal composition for a liquid crystal antenna.

Hereinafter, the compound of the present invention, a liquid crystal composition containing the compound, and a liquid crystal display element will be described in detail.
The present invention has the following general formula (I).

（式中、
Ｒ^１及びR²は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルファニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、又は、１個の−ＣＨ_２−又は２個以上の−ＣＨ_２−が各々独立して−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−若しくは−Ｃ≡Ｃ−によって置換されていても良い炭素原子数１から２０の直鎖状アルキル基又は炭素原子数３から２０の分岐状若しくは環状アルキル基を表すが、酸素原子同士が直接結合することはなく、当該アルキル基中の任意の水素原子はフッ素原子に置換されていても良く、
Ａ^１及びＡ^２は各々独立して
（ａ）１，４−シクロへキシレン基（この基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−又は−Ｓ−に置き換えられても良い。）
（ｂ）１，４−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
（ｃ）１，４−シクロヘキセニレン基、ビシクロ［２．２．２］オクタン−１，４−ジイル基、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基、５，６，７，８−テトラヒドロナフタレン−１，４−ジイル基、デカヒドロナフタレン−２，６−ジイル基、アントラセン−２，６−ジイル基、アントラセン−１，４−ジイル基、アントラセン−９，１０−ジイル基、フェナントレン−２，７−ジイル基（これらの基中に存在する水素原子はフッ素原子又は塩素原子に置換されても良く、また、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基、５，６，７，８−テトラヒドロナフタレン−１，４−ジイル基、アントラセン−２，６−ジイル基、アントラセン−１，４−ジイル基、アントラセン−９，１０−ジイル基又はフェナントレン−２，７−ジイル基中に存在する１個の−ＣＨ＝又は２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
（ｄ）チオフェン−２，５−ジイル基、ベンゾチオフェン−２，５−ジイル基、ベンゾチオフェン−２，６−ジイル基、ジベンゾチオフェン−３，７−ジイル基、ジベンゾチオフェン−２，６−ジイル基、チエノ[3,2-b]チオフェン−２，５−ジイル基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基を表し、これらの基は無置換であるか又は１つ以上の置換基Ｌ^２によって置換されていても良く、
Ｌ^１及びＬ^２はフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルファニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、又は、１個の−ＣＨ_２−又は２個以上の−ＣＨ_２−が各々独立して−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−若しくは−Ｃ≡Ｃ−によって置換されていても良い炭素原子数１から２０の直鎖状アルキル基又は炭素原子数３から２０の分岐状若しくは環状アルキル基を表すが、酸素原子同士が直接結合することはなく、当該アルキル基中の任意の水素原子はフッ素原子に置換されていても良く、
Ｚ^１及びＺ^２はそれぞれ独立して単結合、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）ＣＯＯ−、−ＯＣＯＣ（ＣＨ_３）＝ＣＨ−、−ＣＨ_２−ＣＨ（ＣＨ_３）ＣＯＯ−、−ＯＣＯＣＨ（ＣＨ_３）―ＣＨ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−N=N−、−C＝N−N＝C−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−又は炭素原子数２〜２０のアルキレン基を表し、このアルキレン基中の１個又は２個以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−で置換されてもよいが酸素原子同士が直接結合することはなく、
ｎ及びｍは０から４の整数を表し、ｐは０から８の整数を表し、
Ａ^１、Ａ^２、Ｌ^１、Ｌ^２、Ｚ^１又はZ²が複数存在する場合、それらは同一であっても異なっていても良く、ただし、−（Ａ^１−Ｚ^１）ｍ−Ｒ^１で表される構造と、−（Ａ^２−Ｚ^２）ｎ−Ｒ^２で表される構造とは同一の構造ではない。）
で表される化合物、及び当該化合物を含む液晶組成物に関する。

(During the ceremony,
R ¹ and R ² are hydrogen atom, 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. A group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanogroup, or one -CH _2- or two or more -CH _2- are independently -O-, -S-, respectively. -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- may be substituted. 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 oxygen atoms do not directly bond to each other and any hydrogen atom in the alkyl group. May be replaced with a fluorine atom,
A ¹ and ^{A 2} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is - It may be replaced with O- or -S-.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) 1,4-Cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2 , 3,4-Tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6- Diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (even if the hydrogen atom existing in these groups is replaced with a fluorine atom or a chlorine atom Well, also naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene. One in the -1,4-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene-2,7-diyl group -CH = or two or more -CH = may be replaced with -N =.)
(D) Thiophene-2,5-diyl group, benzothiophene-2,5-diyl group, benzothiophene-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6-diyl Group, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
Represents a group selected from the group consisting of, these groups may be substituted by or one or more substituents L ² or is unsubstituted,
L ¹ and L ² are 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. A group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH _2- or two or more -CH ₂ --independently each of -O-, -S-, -CO- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- Number of carbon atoms which may be substituted by CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- It represents a linear alkyl group from 1 to 20 or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but the oxygen atoms are not directly bonded to each other, and any hydrogen atom in the alkyl group is a fluorine atom. May be replaced with
Z ¹ and Z ² are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF ₂ O-,- OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -CH = C (CH ₃ ) COO-, -OCOC (CH ₃ ) = CH-, _{-CH 2-} CH (CH ₃ ) COO-,- OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O-, -N = N-, -C = N-N = C-, -CH = N-, -N = CH- or 2 carbon atoms Represents ~ 20 alkylene groups, one or more of the alkylene groups -CH _2- may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are directly bonded to each other. Never
n and m represent integers from 0 to 4, p represent integers from 0 to 8.
If there are multiple A ¹ , A ² , L ¹ , L ² , Z ¹ or Z ² , they may be the same or different, but- ^{(A 1- Z 1} ) m-R ¹ The structure represented by and the structure represented by- ^{(A 2- Z 2} ) n-R ² are not the same structure. )
The present invention relates to a compound represented by, and a liquid crystal composition containing the compound.

In the compound represented by the general formula (I) of the present application, since the π-conjugated structure can be expanded by the phenanthrene skeleton, there is an effect of increasing Δn. Further, since the acetylene structure is effectively bonded to the 2nd and 7th positions in the phenanthrene, the π-conjugated structure is effectively expanded, so that Δn is effectively increased. In particular, since the acetylene structure is bonded to the 2- and 7-positions of phenanthrene, the compound represented by the general formula (I) has a rigid rod-shaped molecular shape and exhibits high liquid crystallinity. Therefore, Δn becomes extremely large and T _ni is increased, which also contributes to enhancing the liquid crystallinity of the compound.
As the compound represented by the compound represented by the general formula (I), one type may be used, or two or more types may be used in combination.
In the general formula (I), R ¹ and R ² are hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group and mercapto group. , Methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group or thioisocyano group, preferably hydrogen atom, fluorine atom, chlorine atom, pentafluorosulfanyl group, nitro group, cyano group. , Isocyano group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group or thioisocyano group, more preferably fluorine atom, chlorine atom, cyano group, isocyano group or thioisocyano group. It is particularly preferable from the viewpoint of increasing Δn and Δε.
R ¹ and R ² are also preferably linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, and linear alkyl groups having 1 to 12 carbon atoms. , A branched or cyclic alkyl group is preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is particularly preferable. Further, from the viewpoint of solubility, a linear alkyl group having 2 to 6 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. Further, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - 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-, It may be replaced by -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, and if so, -O- , -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- It is preferably replaced by CH = CH-, -CF = CF- or -C≡C-, with -O-, -S-, -COO-, -OCO-, -CO-S-, -S- It is preferably replaced by CO−, −CH = CH−, −CF = CF− or −C≡C−, −O−, −COO−, −OCO−, −CH = CH−, −CF = It is more preferably replaced by CF- or -C≡C-, and is replaced by -O-, -CH = CH-, -CF = CF- or -C≡C- from the viewpoint of increasing Δn. Is particularly preferred. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosiveness, it is not preferable that oxygen atoms are bonded to each other.
In the general formula (I), A ¹ and A ² are (a) 1,4-cyclohexylene groups (one -CH _2- existing 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 = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) 1,4-Cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2 , 3,4-Tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6- Diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group, (hydrogen atoms present in these groups are replaced with fluorine atom or chlorine atom. Also good, 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 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, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
It is preferably a group selected from the group consisting of. Here, from the viewpoint of forming a π-electron conjugated structure together with the phenanthrene skeleton and the acetylene structure and increasing Δn, A ¹ and A ² may be structures represented by (b), (c) or (d). preferable. 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 ¹ and A ² have the structure of (b), they are preferably a 1,4-phenylene group, a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, preferably 1,4-phenylene. It is particularly preferable that it is a group. In the case of the 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 the 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 preferable, and from the viewpoint of liquidity and increase in Δn, 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 preferable, and dibenzothiophene-2,6 -Diyl groups or thieno [3,2-b] thiophene-2,5-diyl groups are particularly preferred.

Also, the (a) group ~ (d) may be substituted by one or more substituents L ^2.
L ¹ and L ² are 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. The group is preferably a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group or a thioisocyano group, and is preferably a fluorine atom, a chlorine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, a dimethylamino group, a diethylamino group or a diisopropylamino. A group, a trimethylsilyl group, a dimethylsilyl group or a thioisocyano group is more preferable, and a fluorine atom, a chlorine atom, a cyano group, an isocyano group or a thioisocyano group is particularly preferable from the viewpoint of increasing Δn.
L ¹ and L ² are also preferably linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, and linear alkyl groups having 1 to 12 carbon atoms. , A branched or cyclic alkyl group is preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is particularly preferable. Further, from the viewpoint of solubility, a linear alkyl group having 2 to 6 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. Further, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - 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-, It may be replaced by -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, and if so, -O- , -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- It is preferably replaced by CH = CH-, -CF = CF- or -C≡C-, with -O-, -S-, -COO-, -OCO-, -CO-S-, -S- It is preferably replaced by CO−, −CH = CH−, −CF = CF− or −C≡C−, −O−, −COO−, −OCO−, −CH = CH−, −CF = It is more preferably replaced by CF- or -C≡C-, and is replaced by -O-, -CH = CH-, -CF = CF- or -C≡C- from the viewpoint of increasing Δn. Is particularly preferred. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosiveness, it is not preferable that oxygen atoms are bonded to each other.
In order to expand the conjugated structure via the π electron and acetylene structure of the phenanthrene skeleton, it is preferable that ^{A 1} and A ^{2 are aromatic.} In this case, as A ¹ and A ² , (d) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
(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 (existing in these groups) The hydrogen atom may be replaced with a fluorine atom or a chlorine atom, and a naphthalene-2,6-diyl group, a 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 = existing 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, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
Is preferably a group selected from the group consisting of, these groups may be substituted by or one or more substituents L ² or unsubstituted.
In general formula (I), Z ¹ and Z ² are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, respectively. -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 = It is preferably CH-, 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- Is preferable, single bond, -CH = CH-, -CF = CF-, -C≡C-, -N = N-, -C = N-N = C-, -CH = N- or -N = CH. It is more preferably −, and from the viewpoint of increasing Δn, single bond, −C≡C−, −N = N−, −C = N−N = C−, −CH = N− or −N = CH−. Is particularly preferable.
Z ¹ and Z ² are also preferably alkylene groups having 2 to 20 carbon atoms, preferably alkylene groups having 2 to 12 carbon atoms, and are alkylene groups having 2 to 6 carbon atoms. Is particularly preferable. It is preferable that one or more -CH _2- in the alkylene group is substituted with -O-, -COO- or -OCO-. However, since peroxide is not suitable for use as a liquid crystal composition due to its explosiveness, it is not preferable that oxygen atoms are bonded to each other.
n and m are preferably integers of 0 to 4, preferably integers of 0 to 3, particularly preferably integers of 0 to 2, and particularly preferably 0 to 1. Further, it is preferably 0 or 1 from the viewpoint of reducing the viscosity, and is preferably 2 in order to increase the upper limit of the temperature range of the liquid crystal phase. Further, the total value of n + m is preferably an integer of 0 to 4, preferably an integer of 1 to 3, and particularly preferably 1 or 2.
p is preferably an integer of 0 to 8, preferably an integer of 0 to 6, particularly preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.
When ^{there are a plurality of A 1} , A ² , L ¹ , L ² , Z ¹ or Z ² , they may be the same or different. However, in the general formula (I), the structure represented by- ^{(A 1- Z 1} ) m-R ¹ and the structure represented by- ^{(A 2- Z 2} ) n-R ² are the same structure. It is preferable that it is not. This is because the symmetry of the compound represented by the general formula (I) is lowered to lower the crystallinity and improve the solubility, and it is possible to prevent precipitation when added to the liquid crystal composition. Is. By adding a larger amount of the compound to the liquid crystal composition, it is possible to increase Δn of the liquid crystal composition and widen the temperature range showing the liquid crystal phase.

Specific examples of preferable compounds of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

The compound represented by the general formula (I) is preferably a compound represented by the general formula (i-1a), the general formula (i-1b) and the general formula (i-1c).

In the general formula (i-1a), the general formula (i-1b) and the general formula (i-1c), R ⁱ¹ and R ⁱ² are hydrogen atoms, fluorine atoms, chlorine atoms, cyano groups, isocyano groups, thioisocyano groups or carbons. It is preferably a linear, branched or cyclic alkyl group having 1 to 6 atoms, and preferably a fluorine atom, a cyano group, an isocyano group, a thioisocyano group or a linear alkyl group having 1 to 6 carbon atoms. Especially preferable. Further, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Further, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - CH = CH - , - CF = CF- or -C It is also preferable that it is replaced by ≡ C−. However, it is not preferable that the oxygen atoms are bonded to each other.
In the general formula (i-1a), the general formula (i-1b) and the general formula (i-1c), A ⁱ¹ and A ⁱ² are independently 1,4-cyclohexylene groups and 1,4-phenylene groups, respectively. , Naphthalene-2,6-diyl group, 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, It is preferably a 5-diyl group.

Further, A ⁱ¹ and A ⁱ² may be substituted with one or more substituents L ^i2.
L ⁱ¹ and L ⁱ² are 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. Further, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - CH = CH - , - CF = CF- or -C It is also preferable that it is replaced by ≡ C−. However, it is not preferable that the oxygen atoms are bonded to each other.
In the general formula (i-1a), the general formula (i-1b) and the general formula (i-1c), Z ⁱ¹ and Z ⁱ² are independently single-bonded, −CH = CH−, −CF = CF−, respectively. It is preferable that −C≡C−, −N = N−, −C = N−N = C−, −CH = N− or −N = CH−.
Z ⁱ¹ and Z ⁱ² are also preferably alkylene groups having 2 to 6 carbon atoms. It is also preferable that one or more -CH _2- in the alkylene group is substituted with -O-, -COO- or -OCO-. However, it is not preferable that the oxygen atoms are bonded to each other.
p is preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

The compounds represented by the general formula (I) include the general formula (i-1b-1), the general formula (i-1b-2), the general formula (i-1c-1) and the general formula (i-). The compound represented by 1c-2) is preferable.

^{(Wherein, R i1, R i2, L} i1, L i2 and p the above general formula (i-1a), formula (i-1b) and the general formula (R ⁱ¹ of i-1c) in, R ^i2, It has the ^{same meaning as L i1} , L ^{i 2} and p, and q1 and q2 independently represent 1 or 2 respectively.)
As the compound represented by the general formula (I), the compounds represented by the formulas (i-1-a1) to (i-1-e8) are particularly preferable.

In the present invention, the bisacetylene phenanthrene structure can be produced by the following method. Of course, the gist and scope of the present invention are not limited by these production examples.

The compound represented by the general formula (I) can be produced as follows.

(Formula (S-1) in the ^{L 1} and p, and ^{R 2, A 2, L 1} , Z 2 and p in the formula (S-2) is, ^R 2 in the general formula (I), respectively, ^{A 2} , L ¹ , Z ² and p have the same meaning.)
The general formula (S-) is obtained by selectively performing a sonogashira coupling reaction with the corresponding acetylene compound on the compound represented by the formula (S-1) (X ^{1 is a chlorine atom or a bromine atom).} The compound represented by 2) can be obtained. In the Sonogashira coupling reaction, a palladium catalyst, a copper catalyst, a base or the like is used. Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium.
Examples of the copper catalyst include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper triflate (I) and the like. Examples of the base include triethylamine, N, N-diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. At this time, an organic solvent may be used, and examples of the organic solvent include tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Next, the compound represented by the general formula (I) can be obtained by performing a Sonogashira coupling reaction with the corresponding acetylene compound on the compound represented by the formula (S-2). Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium. Examples of the copper catalyst include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper triflate (I) and the like. Examples of the base include triethylamine, N, N-diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. At this time, an organic solvent may be used, and examples of the organic solvent include tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.

Further, the compound represented by the general formula (I) can be produced as follows.

^{(L 1} and p in the formula (S-3) have the same meaning as ^{L 1} and p in the general formula (I), respectively.)
For the compound represented by the formula (S-3) (X ² is a chlorine atom, a bromine atom, and an iodine atom, and the two X ^2s may be the same or different), the corresponding acetylene compound and Sonogashira By carrying out the coupling reaction, the compound represented by the general formula (I) can be obtained. In the Sonogashira coupling reaction, a palladium catalyst, a copper catalyst, an amine, an organic solvent and the like are used. Examples of the palladium catalyst include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium. Examples of the copper catalyst include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper triflate (I) and the like. Examples of the base include triethylamine, N, N-diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
At this time, an organic solvent may be used, and examples of the organic solvent include tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.

The composition containing one or more compounds represented by the general formula (I) preferably has a liquid crystal phase at room temperature. The compound represented by the general formula (I) is preferably contained in the composition as a lower limit value of 1% or more, preferably 2% or more, preferably 3% or more, and 5% or more. It is preferably contained, preferably 10% or more, preferably 15% or more, preferably 20% or more, preferably 25% or more, and preferably 30% or more. , 50% or more, preferably 70% or more, and preferably 90% or more. Further, from the viewpoint that the liquid crystal composition maintains a stable liquid crystal phase in a wide temperature range, it is preferable that 90% or more of the liquid crystal composition is composed of a compound represented by the general formula (I). It is preferable to use two or more kinds of compounds represented by the formula (I), preferably three or more kinds, preferably five or more kinds, and preferably seven or more kinds. Further, as an upper limit value, it is preferably contained in an amount of 90% or less, preferably 80% or less, preferably 70% or less, preferably 60% or less, and preferably 50% or less. It is preferably contained in an amount of 40% or less, preferably 30% or less, preferably 20% or less, preferably 10% or less, preferably 5% or less, and 3% or less. Is preferable.

More specifically, it is preferably contained in an amount of 1 to 95% by mass, preferably 2 to 90% by mass, further preferably 5 to 80% by mass, and particularly preferably 10 to 70% by mass. preferable.

The composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. May be contained. Examples of the compound having no liquid crystal phase include an antioxidant, an ultraviolet inhibitor, a chiral agent, an antistatic agent, a dichroic dye, and the like.

The composition containing the compound represented by the general formula (I) of the present invention preferably contains the compounds represented by the following general formulas (A1) to (A3).

The compounds represented by the general formulas (A1) to (A3) are so-called fluorine-based (halogen-based) p-type compounds.

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 have a cyclic structure of a 3- to 6-membered ring. _{Any −CH 2} − present in the group may be −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF = CF− or −C≡C. It may be substituted with −, and any hydrogen atom existing in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but it may be a linear alkyl group having 1 to 7 carbon atoms or a carbon atom. A linear 1-alkenyl group having a number of 2 to 7, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkoxyl group having 1 to 5 carbon atoms at the end of which have 1 to 5 carbon atoms. Alkyl groups are preferred. When asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring A, Ring B and Ring C can be independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms, respectively. A good 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-2,6- 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 Representing a −diyl group, but a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted with a fluorine atom or A 1,4-phenylene group which may be substituted with 1 or 2 fluorine atoms is preferable. Ring A may be a trans-1,4-cyclohexylene group, especially if ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group. Preferably, ring B and ring A are trans-1,4-cyclohexylene groups when ring C is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group. It is preferable to have. Further, in (A3), the ring A is preferably a trans-1,4-cyclohexylene group.
L ^a, is ^{L b} and ^{L c} a linking group, are independently a single bond, an ethylene group _{(-CH 2 CH 2 -),} 1,2- propylene group _{(-CH (CH 3) CH 2} - and -CH ₂ CH (CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C- or -CH = NN = CH-, but single bond, ethylene group, 1,4-butylene Groups, -COO-, -OCF _2- , -CF ₂ O-, -CF = CF- or -C≡C- are preferred, and single bonds or ethylene groups are particularly preferred. Further, it is preferable that at least one of them represents a single bond in (A2) and at least two of them represent a single bond in (A3).

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 (L b), it is preferable. At least one of ^{Y d to Y f} is preferably a fluorine atom, and more preferably ^{Y d is a fluorine atom.}

Terminal group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or 2 or more carbon atoms substituted by fluorine atoms 2 or 3 of the alkoxyl group, an alkyl Although it represents a group, an alkenyl group or an alkenyloxy group, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.

In the case of using a combination of the compound represented by the general formulas (A1) (A3), even the same choices in different molecules (rings A and L ^a, etc.) represent the same substituent, different substituents May be represented.

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

When a composition having a low viscosity and a fast response rate is required, it is preferable to raise the above lower limit value and raise the upper limit value. Further, when a composition in which the Tni of the composition of the present invention is kept high and seizure is less likely to occur is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

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

(. Representing ^{wherein, A, B, C, Y} a and ^{Y b} are A in the general formulas (A1) (A3), B , C, the same meaning as ^{Y a} and ^{Y b)}
More preferably, it is the following compound.

The composition containing the compound represented by the general formula (I) of the present invention preferably contains the compounds represented by the following general formulas (B1) to (B3).

The compounds represented by the general formulas (B1) to (B3) are so-called cyano-based p-type compounds.

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 have a cyclic structure of a 3- to 6-membered ring. _{Any −CH 2} − present in the group may be −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF = CF− or −C≡C. It may be exchanged by −, and any hydrogen atom existing in the group may be replaced by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms or a carbon atom. A linear 1-alkenyl group having a number of 2 to 7, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkoxyl group having 1 to 5 carbon atoms at the end of which have 1 to 5 carbon atoms. Alkyl groups are preferred. When asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring D, Ring E and Ring F can be independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms, respectively. A good 1,4-phenylene group, optionally substituted with one or more fluorine atoms, naphthalene-2,6-diyl group, optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6- 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 Representing a −diyl group, but a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted with a fluorine atom or A 1,4-phenylene group which may be substituted with 1 or 2 fluorine atoms is preferable. Ring D may be a trans-1,4-cyclohexylene group, especially if ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group. Preferably, ring D and ring E are trans-1,4-cyclohexylene groups when ring F is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group. It is preferable to have. Further, in (B3), the ring D is preferably a trans-1,4-cyclohexylene group.

L ^d, the ^{L e} and ^{L f} a linking group, are independently a single bond, an ethylene group _{(-CH 2 CH 2 -),} 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 single bond, ethylene group, -COO-, -OCF _2- , -CF ₂ O-, -CF = CF- or -C≡C- are preferable, and a single bond, an ethylene group or -COO- is particularly preferable. Further, it is preferable that at least one of them represents a single bond in (B2) and at least two of them represent a single bond in (B3).

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, but in (Le), Y ^m is preferably a fluorine atom.

The terminal group P ^b represents a cyano group (-CN), a cyanato group (-OCN) or -C≡CCN, with a cyano group being preferred.

When compounds represented by the general formulas (B1) to (B3) are used in combination, the same alternatives (rings D, L ^d, etc.) in different molecules may represent the same substituent but different substituents. May be represented.

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

When a composition having a low viscosity and a high response rate is required, it is preferable to lower the lower limit value and raise the upper limit value. Further, when a composition in which the Tni of the composition of the present invention is kept high and seizure is unlikely to occur is required, it is preferable to lower the lower limit value and raise the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

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

(. Representing wherein, A, B, ^{Y k} and ^{Y l} A in general formulas (B1) (B3), B , the same meaning as ^{Y k} and ^{Y l)}
More preferably, it is the following compound.

The composition containing the compound represented by the general formula (I) of the present invention preferably contains the compounds represented by the following general formulas (C1) to (C3).

The compounds represented by the general formulas (C1) to (C3) are so-called non-polar compounds having a dielectric anisotropy of about 0.

In the above formula, R ^d and ^Re 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 branches. It may have a cyclic structure of a member ring, and any −CH ₂ − present in the group is −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF =. It may be exchanged by CF- or -C≡C-, and any hydrogen atom existing in the group may be replaced by a fluorine atom or a trifluoromethoxy group, but directly having 1 to 7 carbon atoms. A chain 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 terminal thereof. A linear alkyl group having 1 to 5 carbon atoms substituted with an alkoxyl group having 1 to 3 carbon atoms is preferable, and at least one of them is a linear alkyl group having 1 to 7 carbon atoms and 2 to 7 carbon atoms. Is particularly preferably a linear 1-alkenyl group or a linear 3-alkenyl group having 4 to 7 carbon atoms. When asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring G, ring H, ring I and ring J are independently trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1-2 fluorine atoms or It is substituted with a 1,4-phenylene group, which may be substituted with a methyl group, a naphthalene-2,6-diyl group, which may be substituted with one or more fluorine atoms, and one or two fluorine atoms. May be tetrahydronaphthalene-2,6-diyl group, 1,4-cyclohexenylene group optionally substituted with 1-2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, Represents a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, in which each compound is substituted with a transdecahydronaphthalene-trans-2,6-diyl group, one or more fluorine atoms. May be naphthalene-2,6-diyl group, may be substituted with 1-2 fluorine atoms tetrahydronaphthalene-2,6-diyl group may be substituted with 1,4-cyclohexeni The number of rene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidin-2,5-diyl group or pyridine-2,5-diyl group is preferably 1 or less, and the other rings are trans. It is preferably a 1,4-phenylene group that may be substituted with a -1,4-cyclohexylene group or one or two fluorine atoms or a methyl group.

L ^g , L ^h and ^Li are linking groups, which are independently single bonds, ethylene groups (-CH ₂ CH _2- ), 1,2-propylene groups (-CH (CH ₃ ) CH _2- and, respectively. ) -CH ₂ CH (CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O-,- Represents CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C- or -CH = NN = CH-, but single bond, ethylene group, 1,4- Butylene groups, -COO-, -OCO-, -OCF _2- , -CF ₂ O-, -CF = CF-, -C≡C- or -CH = NN = CH- are preferable, and in (C2), It is preferred that at least one, in (C3), at least two of them represent a single bond.

When compounds represented by the general formulas (C1) to (C3) are used in combination, the same alternatives (ring G, ^Lg, etc.) in different molecules may represent the same substituent but different substituents. May be represented.

Further, in the general formulas (C1) to (C3), the general formulas (A1) to (A3) of the present invention are excluded.

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

When a composition having a low viscosity and a high response rate is required, it is preferable to lower the lower limit value and raise the upper limit value. Further, when a composition that keeps the Tni of the composition of the present invention high and is less likely to cause seizure is required, it is preferable to raise the above lower limit value and raise the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to lower the lower limit value and lower the upper limit 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.

A more preferable form in (C1) can be represented by the following general formulas (C1a) to (C1h).

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

Ring G1 and ring H1 are independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or two fluorine atoms or a methyl group, respectively. May be 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2, optionally substituted with one or two fluorine atoms, 6-Diyl group, 1,4-cyclohexenylene group optionally substituted with 1-2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidin-2,5-diyl It represents a group or a pyridine-2,5-diyl group, but in each compound, a transdecahydronaphthalene-trans-2,6-diyl group may be substituted with one or more fluorine atoms. -Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted with 1-2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted with fluorine atom, 1,3- The number of dioxane-trans-2,5-diyl groups, pyrimidin-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 1,4-phenylene group that may be substituted with a cyclohexylene group or one or two fluorine atoms or a methyl group. Rings G2 and H2 are independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or two fluorine atoms or a methyl group, respectively. May be 1,4-phenylene group, naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, tetrahydronaphthalene-2, optionally substituted with one or two fluorine atoms, Representing a 6-diyl group, in each compound a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group optionally substituted with one or more fluorine atoms, 1- The number of tetrahydronaphthalene-2,6-diyl groups that may be substituted by two fluorine atoms is preferably one or less, in which case the other ring is a trans-1,4-cyclohexylene group or one. It is a 1,4-phenylene group which may be substituted with ~ 2 fluorine atoms or a methyl group. Ring G3 and ring H3 may be independently substituted with 1 or 2 fluorine atoms or methyl groups, respectively. 1,4-Phenylene group may be substituted with 1 or more fluorine atoms. Naphthalene-2. , 6-Diyl group, tetrahydronaphthalene which may be substituted with 1 or 2 fluorine atoms-2,6-diyl group, but may be substituted with 1 or more fluorine atoms in each compound. The number of the −2,6-diyl group and the tetrahydronaphthalene-2,6-diyl group which may be substituted with 1 or 2 fluorine atoms is preferably 1 or less.

More preferably, it is the following compound.

A more preferable form in (C2) can be represented by the following general formulas (C2a) to (C2m).

In the above equation, ring G1, ring G2, ring G3, ring H1, ring H2 and ring H3 have the same meanings as described above, ring I1 is ring G1, ring I2 is ring G2, and ring I3 is ring G3, respectively. Represents meaning. Further, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, and one or two fluorine atoms. Tetrahydronaphthalene-2,6-diyl group optionally substituted with 1,4-cyclohexenylene group optionally substituted with fluorine atom, 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, in which case the other ring is a trans-1,4-cyclohexylene group or one or two. It is a 1,4-phenylene group that may be substituted with a fluorine atom or a methyl group.

More preferably, it is the following compound.

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

In the above equation, ring G1, ring G2, ring H1, ring H2, ring I1 and ring I2 have the same meanings as those described above, ring J1 has the same meaning as ring G1 and ring J2 has the same meaning as ring G2. Further, in each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, and one or two fluorine atoms. Tetrahydronaphthalene-2,6-diyl group optionally substituted with, 1,4-cyclohexenylene group optionally substituted with fluorine atom, 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, in which case the other ring is a trans-1,4-cyclohexylene group or one or two. It is a 1,4-phenylene group that may be substituted with a fluorine atom or a methyl group.

More preferably, it is the following compound.

It is represented by the general formulas (I), the general formulas (A1) to (A3), the general formulas (B1) to (B3), and the general formulas (C1) to (C3) with respect to the total amount of the composition of the present invention. The lower limit of the preferred total content of the compounds is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%. Yes, 96%, 97%, 98%, 99%, 100%. The preferred upper limit of the content is 100%, 99%, 98% and 95%.

It is represented by the general formulas (I), the general formulas (A1a) to (A3c), the general formulas (B1a) to (B2c), and the general formulas (C1a) to (C3f) with respect to the total amount of the composition of the present invention. The lower limit of the preferred total content of the compounds is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%. Yes, 96%, 97%, 98%, 99%, 100%. The preferred upper limit of the content is 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 such as a peracid (-CO-OO-) structure are bonded to each other in the molecule.

When the reliability and long-term stability of the composition are emphasized, 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 1% or less, and most preferably not substantially contained.

When the stability by UV irradiation is emphasized, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, and 8% or less, based on the total mass of the composition. % Or less, more preferably 5% or less, more preferably 3% or less, and even more preferably substantially no content.

It is preferable to increase the content of the compound having all 6-membered ring structures in the molecule, and the content of the compound having all 6-membered ring structures in the molecule is 80 with respect to the total mass of the composition. % Or more, more preferably 90% or more, further preferably 95% or more, and the composition is composed only of a compound in which substantially all the ring structures in the molecule are 6-membered rings. It is most preferable to do so.

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 is added to the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained.

When the improvement of viscosity and the improvement of Tni are emphasized, the content of the compound having a 2-methylbenzene-1,4-diyl group in which the hydrogen atom may be substituted with halogen may be reduced. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, preferably 8% or less, based on the total mass of the composition. It is more preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

In the present application, substantially not contained means that it is not contained except for an unintentionally contained substance.

When the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, and the alkenyl group is bonded to cyclohexane, the number of carbon atoms of the alkenyl group is 2 to 5. When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are directly bonded. It is preferable that there is no such thing.

In order to enhance the stability of the liquid crystal composition in the present invention, it is preferable to add an antioxidant. Examples of the antioxidant include hydroquinone derivatives, nitrosoamine-based polymerization inhibitors, hindered phenol-based antioxidants, and more specifically, tert-butylhydroquinone, methylhydroquinone, and Wako Pure Chemical Industries, Ltd. Q-1300, "Q-1301", BASF's "IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1425", "IRGANOX1520", "IRGANOX1726" Examples thereof 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 enhance the stability of the liquid crystal composition in the present invention, it is preferable to add a UV absorber. As the UV absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferable from the viewpoint of good liquid crystal display. More specifically, for example, hindered phenol-based compounds, hydroxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex salt-based compounds, and triazine-based compounds can be mentioned. 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- 4-Hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate can be mentioned. Examples of the benzotriazole-based compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H). -Benzotriazole-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], TINUVIN109, TINUVIN171, TINUVIN326, manufactured by BASF Japan Co., 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.

The composition containing the compound represented by the general formula (I) of the present invention preferably 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, and particularly preferably 0.35 or more. preferable.
The composition containing the compound represented by the general formula (I) of the present invention preferably has a dielectric anisotropy (Δε) at 25 ° C. of +2.0 or more, preferably +2.0 to +4.0. It is preferably present, and more preferably +2.0 to +5.0. For the purpose of low voltage drive, +8.0 to +18.0 is preferable, and +10.0 to +15.0 is more preferable.
Further, the 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 180 ° C., more preferably 70 ° C. to 160 ° C., and particularly preferably 80 ° C. to 150 ° C.

Hereinafter, the present invention will be described 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 "mass%" unless otherwise specified.
Hereinafter, the following abbreviations will be used.
Me: Methyl group Et: Ethyl group iPr: Isopropyl group Ph: Phenyl group DMF: N, N-dimethylformamide THF: tetrahydrofuran AIBN: 2,2'-azobis (isobutyronitrile)
NBS: N-Bromosuccinimide DBU: 1,8-diazabicyclo [5.4.0] -7-Undecene

Cr: Crystal
N: Nematic phase Sm: Smectic phase Iso: Isotropic liquid

(Example 1)

A mixture of 9,10-dihydrophenanthrene (60 g, 333 mmol), acetic acid (340 mL), concentrated sulfuric acid (5 mL) and water (66 mL) was stirred at 80 ° C. and periodic acid (15.2 g, 66 mmol) was added to water (50 mL). ) Was added, followed by iodine (33.8 g, 133 mmol), and the mixture was stirred at 80 ° C. for 12 hours. The ice-cooled reaction solution was added to a saturated aqueous sodium sulfite solution, the aqueous layer was extracted three times with dichloromethane, the organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene, hexane and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: toluene / hexane). The solvent was distilled off under reduced pressure, and then 9,10-dihydrophenanthrene was distilled off under reduced pressure to obtain 2-iodo-9,10-dihydrophenanthrene (46.0 g, yield 45%).

A solution of 2-iodo-9,10-dihydrophenanthrene (45.0 g, 147 mmol) and chloroform (300 mL) was stirred, shaded, ice-cooled, iron (III) chloride (0.4 g, 2 mmol), bromine (47 g, 294 mmol). ) Was added, and the mixture was stirred at room temperature for 12 hours. The ice-cooled reaction solution was added to a saturated aqueous sodium sulfite solution, the aqueous layer was extracted twice with dichloromethane, the organic layers were combined, washed with a saturated aqueous sodium sulfite solution and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, dichloromethane and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: dichloromethane). The solvent was distilled off under reduced pressure and then recrystallized from toluene / hexane / ethanol to obtain 2-bromo-7-iodo-9,10-dihydrophenanthrene (43.6 g, yield 77%).

2-Bromo-7-iodo-9,10-dihydrophenanthrene (43.6 g, 113 mmol), AIBN (0.4 g, 2 mmol), NBS (24.2 g, 136 mmol), carbon tetrachloride (500 mL) under a nitrogen atmosphere. The mixture was stirred and heated to reflux for 5 hours. Water was added to the reaction solution, and the precipitated solid was obtained by filtration and washed with water, water at 60 ° C., and methanol. The obtained solid was washed with toluene / hexane / ethanol and further recrystallized from THF / hexane to obtain 2-bromo-7-iodophenanthrene (27.8 g, yield 64%).

2-Bromo-7-iodophenanthrene (10.0 g, 26 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper (I) iodide (0.2 g, 1 mmol) under a nitrogen atmosphere. , Triethylamine (30 mL), DMF (50 mL) mixed with DMF (40 mL) solution of 4-ethynyl-1,2-difluorobenzene (3.6 g, 26 mmol) at 75 ° C. and heated at 75 ° C. While stirring for 3 hours. Water was poured into the reaction solution, the aqueous layer was extracted 3 times 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, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was recrystallized from acetone / methanol and toluene / ethanol to give 2-bromo-7-((3,4-difluorophenyl) ethynyl) phenanthrene (6.4 g, yield 64%). Obtained.

2-Bromo-7-((3,4-difluorophenyl) ethynyl) phenanthrene (6.4 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper iodide under a nitrogen atmosphere. (I) To a mixture of (0.3 g, 1.5 mmol), triethylamine (120 mL), and THF (180 mL), 1-hexine (4.6 g, 48 mmol) was added dropwise at 60 ° C., and the mixture was heated and refluxed for 5 hours. Stirred. Water was poured into the reaction solution, the aqueous layer was extracted 3 times 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, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was recrystallized from ethyl acetate / methanol and toluene / hexane to form 2-((3,4-difluorophenyl) ethynyl) -7- (1-hexin-1-yl) phenanthrene (1). .2 g, yield 19%) was obtained.
Cr 217 SmA 231 Iso
(Example 2)

2-Bromo-7-iodophenanthrene (20.0 g, 52 mmol), tetrakis (triphenylphosphine) palladium (1.2 g, 1.0 mmol), copper (I) iodide (0.4 g, 2 mmol) under a nitrogen atmosphere. A solution of 1-butyl-4-ethynylbenzene (8.2 g, 52 mmol) in DMF (80 mL) was added dropwise to a mixture of triethylamine (60 mL) and DMF (100 mL) at 75 ° C., while heating at 75 ° C. 3 Stirred for hours. Water was poured into the reaction solution, the aqueous layer was extracted 3 times 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, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 60 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was recrystallized from acetone / methanol and toluene / ethanol to obtain 2-bromo-7-((4-butylphenyl) ethynyl) phenanthrene (15.0 g, yield 64%). ..

2-Bromo-7-((4-butylphenyl) ethynyl) phenanthrene (7.5 g, 18 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper iodide (I) under a nitrogen atmosphere. ) (0.3 g, 1.5 mmol), triethylamine (120 mL), THF (180 mL), 1-pentyl-4-ethynylbenzene (9.3 g, 54 mmol) was added dropwise at 60 ° C., and the mixture was heated to reflux. While stirring for 5 hours. Water was poured into the reaction solution, the aqueous layer was extracted 3 times with toluene, the organic layers were combined, washed with water, 10% hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 50 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was washed with toluene / ethanol, toluene / hexane, and ethyl acetate. It was dissolved in dichloromethane, washed with aqueous ammonia, QuadraSilMP (manufactured by Johnson Matthey) and activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 40 ° C. for 1 hour. Purification by silica gel column chromatography (silica gel 15 g, mobile phase: dichloromethane), distilling off the solvent under reduced pressure, and washing with dichloromethane and ethyl acetate, 2-((4-butylphenyl) ethynyl) -7-(( 4-Pentylphenyl) ethynyl) phenanthrene (3.4 g, yield 37%) was obtained.
Cr 238 N> 350 Iso
(Example 3)

2-Bromo-7-((4-butylphenyl) ethynyl) phenanthrene (7.5 g, 18 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper iodide (I) under a nitrogen atmosphere. ) (0.3 g, 1.5 mmol), triethylamine (120 mL), THF (180 mL), 6-ethynyl-1,2,3,-trifluoronaphthalene (11.1 g, 54 mmol) at 60 ° C. The mixture was added dropwise, heated and refluxed, and stirred for 7 hours. Water was poured into the reaction solution, the aqueous layer was extracted 3 times with toluene, the organic layers were combined, washed with water, 10% hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was washed with toluene / ethanol, toluene / hexane, and ethyl acetate. It was dissolved in dichloromethane, washed with aqueous ammonia, QuadraSilMP (manufactured by Johnson Matthey) and activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 40 ° C. for 1 hour. Purification by silica gel column chromatography (silica gel 10 g, mobile phase: dichloromethane), distilling off the solvent under reduced pressure, and washing with dichloromethane and ethyl acetate, 2-((4-butylphenyl) ethynyl) -7-(( 5,6,7, -trifluoronaphthalene-2-yl) ethynyl) phenanthrene (2.4 g, yield 25%) was obtained.
(Example 4)

2-Bromo-7-iodophenanthrene (10.0 g, 26 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper (I) iodide (0.2 g, 1 mmol) under a nitrogen atmosphere. , DMF (40 mL) solution of 2-chloro-4-ethynyl-1-isothiocyanatobenzene (3.6 g, 26 mmol) at 75 ° C. to a mixture of triethylamine (30 mL) and DMF (50 mL) was added dropwise at 75 ° C. The mixture was stirred for 5 hours while being heated at ° C. Water was poured into the reaction solution, the aqueous layer was extracted 3 times 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, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 30 g, mobile phase: toluene). The solvent was distilled off under reduced pressure and then recrystallized from acetone / methanol to obtain 2-bromo-7- ((3-chloro-4-isothiocianatophenyl) ethynyl) phenanthrene (6.5 g, yield 58%). Obtained.

2-Bromo-7-((3-chloro-4-isothiocyanatophenyl) ethynyl) phenanthrene (6.5 g, 15 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol) under a nitrogen atmosphere. , 1-hexine (4.6 g, 48 mmol) was added dropwise at 60 ° C. to a mixture of copper (I) iodide (0.3 g, 1.5 mmol), triethylamine (120 mL), and THF (180 mL), and heated to reflux. The mixture was stirred for 8 hours. Water was poured into the reaction solution, the aqueous layer was extracted three times with toluene, the organic layers were combined, washed with water and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 20 g, mobile phase: toluene). After distilling off the solvent under reduced pressure, the solvent was recrystallized from toluene / hexane and ethyl acetate / ethanol to give 2-((3-chloro-4-isothiocianatophenyl) ethynyl) -7- (1-hexin-1-yl). ) Phenanthrene (1.0 g, yield 15%) was obtained.
(Comparative Example 1)

2-Ethyl-1,4-diiodobenzene (30.0 g, 84 mmol), triethylamine (10.2 g, 100 mmol), 1,8-diazabicyclo [5.4.0] -7-undecene (12) under a nitrogen atmosphere. .7 g, 84 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), copper (I) iodide (0.1 g, 0.5 mmol), THF (100 mL) at room temperature. A solution of 1-butyl-4-ethynylbenzene (29.2 g, 184 mmol) in THF (40 mL) was added dropwise, and the mixture was stirred with heating and reflux for 3 hours. The reaction mixture 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, toluene and silica gel were added, and the residue was purified by silica gel column chromatography (silica gel 50 g, mobile phase: toluene). The solvent was distilled off under reduced pressure and then recrystallized from toluene / hexane to obtain 1,4-bis ((4-butylphenyl) ethynyl) -2-ethylbenzene (28.8 g, yield 82%).
(Preparation and evaluation of liquid crystal composition)
A maternal liquid crystal (LC-1) showing the following physical property values was prepared. All values are actually measured values.

T _n-i (nematic phase - isotropic liquid phase transition temperature): 74.0 ° C.
Δε (dielectric constant anisotropy at 25 ° C): 5.13
Δn (refractive index anisotropy at 25 ° C): 0.141
γ ₁ (rotational viscosity coefficient at 25 ° C): 98
(P-1), (P-2), (P-3), (P-4) obtained in Examples 1, 2, 3, 4 and Comparative Example 1 with respect to this parent liquid crystal (LC-1). ) And compound (C-1) were added in an amount of 0%, 1% and 3% to prepare a liquid crystal composition. The extrapolated values at 100% using the least squares method are shown below. By comparing Examples 1, 2, 3, 4 and Comparative Example 1, since the compound of the present application shows high Δn and high Tni, it is necessary to effectively increase Δn and Tni when added to the liquid crystal composition. There was found.

Claims (12)

The following general formula (I)

(During the ceremony,
R ¹ and R ² are hydrogen atom, 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. A group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanogroup, or one -CH _2- or two or more -CH _2- are independently -O-, -S-, respectively. -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- may be substituted. 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 oxygen atoms do not directly bond to each other and any hydrogen atom in the alkyl group. May be replaced with a fluorine atom,
A ¹ and ^{A 2} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is - It may be replaced with O- or -S-.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) 1,4-Cyclohexenylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2 , 3,4-Tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, anthracene-2,6- Diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group, phenanthrene-2,7-diyl group (even if the hydrogen atom existing in these groups is replaced with a fluorine atom or a chlorine atom Well, also naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 5,6,7,8-tetrahydronaphthalene. One in the -1,4-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, anthracene-9,10-diyl group or phenanthrene-2,7-diyl group -CH = or two or more -CH = may be replaced with -N =.)
(D) Thiophene-2,5-diyl group, benzothiophene-2,5-diyl group, benzothiophene-2,6-diyl group, dibenzothiophene-3,7-diyl group, dibenzothiophene-2,6-diyl Group, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
Represents a group selected from the group consisting of, these groups may be substituted by or one or more substituents L ² or is unsubstituted,
L ¹ and L ² are 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. A group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH _2- or two or more -CH ₂ --independently each of -O-, -S-, -CO- , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- Number of carbon atoms which may be substituted by CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- It represents a linear alkyl group from 1 to 20 or a branched or cyclic alkyl group having 3 to 20 carbon atoms, but the oxygen atoms are not directly bonded to each other, and any hydrogen atom in the alkyl group is a fluorine atom. May be replaced with
Z ¹ and Z ² are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF ₂ O-,- OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -CH = C (CH ₃ ) COO-, -OCOC (CH ₃ ) = CH-, _{-CH 2-} CH (CH ₃ ) COO-,- OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O-, -N = N-, -C = N-N = C-, -CH = N-, -N = CH- or 2 carbon atoms Represents ~ 20 alkylene groups, one or more of the alkylene groups -CH _2- may be substituted with -O-, -COO- or -OCO-, but the oxygen atoms are directly bonded to each other. Never
n and m represent integers from 0 to 4, p represent integers from 0 to 8.
If there are multiple A ¹ , A ² , L ¹ , L ² , Z ¹ or Z ² , they may be the same or different, but- ^{(A 1- Z 1} ) m-R ¹ The structure represented by and the structure represented by- ^{(A 2- Z 2} ) n-R ² are not the same structure. )
The compound represented by. In the general formula (I) according to claim 1, A ¹ and A ² are (d) 1,4-phenylene groups (one −CH = or two or more non-adjacent groups present in the group). -CH = may be replaced with -N =.)
(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 (existing in these groups) The hydrogen atom may be replaced with a fluorine atom or a chlorine atom, and a naphthalene-2,6-diyl group, a 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 = existing 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, thieno [3,2-b] thiophene-2,5-diyl group (one -CH = present in this group or two or more non-adjacent -CH = are replaced by -N = May be.)
Represents a group selected from the group consisting of, these groups may be substituted by or one or more substituents L ² or is unsubstituted, A compound according to claim 1. The compound according to claim 1 or 2, wherein in the general formula (I) according to claim 1, the total value of n and m represents an integer of 1 to 2. According to claim 1, in the general formula (I), A ¹ and A ² are 1,4-phenylene groups that are unsubstituted or optionally substituted with one or more substituents L ^2. Item 2. The compound according to any one of Items 1 to 3. A liquid crystal composition containing the compound according to any one of claims 1 to 4. General formulas (A1) to (A3)

(In the 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 have a cyclic structure of a 3- to 6-membered ring. _{Any −CH 2} − present in the group may be −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF = CF− or −C≡C. It may be substituted with −, and any hydrogen atom existing in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but when asymmetric carbon is generated by branching, it is optically active as a compound. It may be a racem body,
Even if ring A, ring B and ring C are independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms, respectively. A good 1,4-phenylene group, which may be substituted with one or more fluorine atoms, a naphthalene-2,6-diyl group, which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6- 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 -Represents a diyl group
L ^a , L ^b and L ^c are independently single-bonded, ethylene group (-CH ₂ CH _2- ), 1,2-propylene group (-CH (CH ₃ ) CH _2- and -CH ₂ CH (CH), respectively. ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C-, -N = N-, -C = N-N = C-, -CH = N- or -N = CH- Represent,
Ring Z represents a substituent represented by the general formulas (La) to (Lc).

(In the formula, Y ^{a to Y j} independently represent a hydrogen atom or a fluorine atom, respectively.
Pa ^{is an alkoxyl group or alkyl group having 2 or 3 carbon atoms substituted with a} fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group or a difluoromethyl group or two or more fluorine atoms. Represents an alkenyl group or an alkenyloxy group
When used in combination from the general formula (A1) a compound represented by (A3), even the same choices in different molecules (rings A and L ^a, etc.) represent the same substituent, different substituents It may be represented. )
The liquid crystal composition according to claim 5, which contains one or more compounds represented by. General formulas (B1) to (B3)

(In the 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 have a cyclic structure of a 3- to 6-membered ring. _{Any −CH 2} − present in the group may be −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF = CF− or −C≡C. It may be exchanged by −, and any hydrogen atom existing in the group may be replaced by a fluorine atom or a trifluoromethoxy group, but when asymmetric carbon is generated by branching, it is optically active as a compound. It may be a racem body,
Ring D, Ring E and Ring F can be independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms, respectively. A good 1,4-phenylene group, which may be substituted with one or more fluorine atoms, a naphthalene-2,6-diyl group, which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6- 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 -Represents a diyl group
L ^d , ^Le and L ^f are independently single-bonded, ethylene group (-CH ₂ CH _2- ), 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-, -N = N-, -C = N-N = C-, -CH = N- or -N = CH- Represents
Ring Y represents a substituent represented by the following general formulas (L ^d ) to (L ^f).

(In the formula, Y ^{k to Y q} independently represent a hydrogen atom or a fluorine atom.)
The terminal group P ^b represents a cyano group (-CN), a cyanato group (-OCN) or -C≡CCN.
When compounds represented by the general formulas (B1) to (B3) are used in combination, the same alternatives (rings D, L ^d, etc.) in different molecules represent the same substituents, but different substituents are used. It may be represented. )
The liquid crystal composition according to any one of claims 5 to 6, which contains one or more compounds represented by. General formulas (C1) to (C3)

(In the formula, R ^d and ^Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, and 3 to 6 thereof. It may have a cyclic structure of a member ring, and any −CH ₂ − present in the group is −O−, −CH = CH−, −CH = CF−, −CF = CH−, −CF =. It may be exchanged by CF- or -C≡C-, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group.
Ring G, ring H, ring I and ring J are independently trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1-2 fluorine atoms or It is substituted with a 1,4-phenylene group, which may be substituted with a methyl group, a naphthalene-2,6-diyl group, which may be substituted with one or more fluorine atoms, and one or two fluorine atoms. May be tetrahydronaphthalene-2,6-diyl group, 1,4-cyclohexenylene group optionally substituted with 1-2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, Represents a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group,
L ^{g, L h} and ^{L i} are each independently a single bond, an ethylene group _{(-CH 2 CH 2 -),} 1,2- propylene group _{(-CH (CH 3) CH 2} - and) _-CH 2 CH ( CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O-, -CH = CH-,- CH = CF-, -CF = CH-, -CF = CF-, -C≡C-, -N = N-, -C = N-N = C-, -CH = N- or -N = CH- Represents
When compounds represented by the general formulas (C1) to (C3) are used in combination, the same alternatives (ring G, ^Lg, etc.) in different molecules may represent the same substituent but different substituents. May represent,
In the general formulas (C1) to (C3), the general formulas (A1) to (A3) of the present invention are excluded. )
The liquid crystal composition according to any one of claims 5 to 7, which contains one or more compounds represented by. The liquid crystal composition according to any one of claims 5 to 8, wherein the refractive index anisotropy is 0.15 or more. The liquid crystal composition according to any one of claims 5 to 8, wherein the dielectric anisotropy is 2 or more. The liquid crystal composition according to any one of claims 5 to 10, which contains at least one or more 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 displaying a stereoscopic image using the liquid crystal composition according to any one of claims 5 to 11.