JP2005314385A - Benzene derivative, liquid crystal composition, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal compound having an excellent balance of physical properties such as exhibiting a negative dielectric constant anisotropy together with having comparatively high clear point or a small viscosity, a proper optical anisotropy and compatibility with other liquid crystal compounds, etc., by solving problems that conventional compounds exhibiting a negative dielectric constant anisotropy although exhibiting a negative dielectric constant anisotropy of relatively large numeric value are not appropriate in the balance of properties as a liquid crystal material because having a low clear point or a large viscosity. <P>SOLUTION: The invention relates to a compound represented by formula (1) or (2). In the formula, each of R<SB>a</SB>and R<SB>b</SB>is a hydrogen atom or 1-20C alkyl; each of A<SP>1</SP>, A<SP>11</SP>, A<SP>12</SP>, A<SP>2</SP>, A<SP>21</SP>and A<SP>22</SP>is a cyclic group; each of Y, W, Z<SP>11</SP>, Z<SP>12</SP>, Z<SP>2</SP>, Z<SP>21</SP>and Z<SP>22</SP>is a bond group; and each of j, k, m, n, p and q is 0 or 1 with the proviso that the sum thereof is 1 to 3. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. More specifically, the present invention relates to a benzene derivative, a liquid crystal composition containing the benzene derivative and having a nematic phase, and a liquid crystal display device containing the composition.

  The liquid crystal display element is based on the operation mode of the liquid crystal, such as PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (Bistable twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated). bend), IPS (in-plane switching), VA (vertical alignment), and the like. This element is classified into a PM (passive matrix) and an AM (active matrix) based on the driving method. PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal).

These liquid crystal display elements contain a liquid crystal composition. In the following description, the liquid crystal display element may be simply referred to as an element. A liquid crystal composition may be simply referred to as a composition. A liquid crystal compound may be simply referred to as a compound. In order to improve the characteristics of the device, the composition preferably has appropriate physical properties. The general physical properties necessary for the compound that is a component of the composition are as follows.
(1) Chemical stability and physical stability.
(2) High clearing point.
(3) Low minimum temperature of the liquid crystal phase.
(4) Small viscosity.
(5) Appropriate optical anisotropy.
(6) Appropriate dielectric anisotropy.
(7) Large specific resistance.
The clearing point is a liquid crystal phase-isotropic phase transition temperature. The liquid crystal phase means a nematic phase, a smectic phase, or the like. A compound having a large dielectric anisotropy often has a high viscosity.

  The composition is prepared by mixing many compounds. Therefore, these compounds are preferably miscible with other compounds. Since the device may be used at a temperature below freezing point, a compound having good compatibility at a low temperature is preferable. A compound having a high clearing point or a low minimum temperature of the liquid crystal phase contributes to a wide temperature range of the nematic phase in the composition. Preferred compositions have low viscosity and optical anisotropy suitable for the device mode. The large dielectric anisotropy of the compound contributes to the low threshold voltage of the composition. With such a composition, an element having characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a small driving voltage, a small power consumption, and a large voltage holding ratio can be obtained. .

As a compound exhibiting negative dielectric anisotropy, a compound (i) having 2,3-difluoro1,4-phenylene in a partial structure is generally known (see Non-Patent Document 2). As a compound for improving the dielectric anisotropy, compound (ii) in which trifluoromethyl is bonded to the side orientation of the compound molecule and difluoromethyl are bonded in order to make negative dielectric anisotropy even larger. Compound (iii) and compound (iv), which have been reported, have been reported (see Patent Document 1, Non-patent Document 1, Non-patent Document 2 and Patent Document 2). However, these compounds exhibit a relatively large numerical negative dielectric anisotropy, but have a poor balance of physical properties as a liquid crystal material, such as a low clearing point and a large viscosity. Further preferred liquid crystalline compounds, liquid crystal compositions and liquid crystal display elements are desired.

JP-A-8-040953 WO2000 / 03963 pamphlet Synlett. 1999, No. 4, 389-396 Angew. Chem. Int. Ed. 2000, 39, 4216-4235

  The first object of the present invention is to exhibit a negative dielectric anisotropy and to have a relatively high clearing point, a relatively small viscosity, a suitable optical anisotropy, and excellent compatibility with other liquid crystal compounds. It is to provide a liquid crystal compound having an excellent balance of physical properties. The second object is to provide a liquid crystal composition containing this compound and having a wide temperature range of a nematic phase, a small viscosity, a suitable optical anisotropy, and a low threshold voltage. A third object is to provide a liquid crystal display element containing this composition and having a short response time, a small power consumption, a large contrast, and a high voltage holding ratio.

First, terms used in this specification will be described. A liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase, and may simply be abbreviated as the upper limit temperature. The lower limit temperature of the nematic phase may simply be abbreviated as the lower limit temperature. A compound represented by the formula (1) may be referred to as a compound (1). This notation may be applied to a compound represented by formula (2) or the like. “Arbitrary” indicates that not only the position but also the number is arbitrary. The expression that any A may be replaced with B, C, or D means that one A may be replaced with B, C, or D, and any of a plurality of A is B, C, or In addition to the meaning that it may be replaced by any one of A and D, it means that at least two of A replaced by B, A replaced by C, and A replaced by D may be mixed. Have. For example, n-butyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes CH ₃ (CH ₂ ) ₃ — as well as CH ₃ (CH ₂ ) ₂ O—. _{, CH 3 -O- (CH 2)} 2 -, CH 3 -O-CH 2 -O-, CH 2 = CH- (CH 2) 3 -, CH 3 -CH = CH- (CH 2) 2 -, CH ₃ —CH═CH—CH ₂ —O— and the like are included. In such a case, considering the stability of the compound, it is preferable that a plurality of consecutive —CH ₂ — is not replaced by —O—. Both alkyl and alkylene may be a linear group or a branched group. The same applies to the case where any —CH ₂ — in these groups is replaced by —O— or —CH═CH—. And the quantity of the compound represented by the percentage shown in a composition is a weight percentage (weight%) based on the total weight of a composition.

ここに、ＲａおよびＲｂは独立して水素または炭素数１〜２０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−または−ＳｉＨ_２−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；
Ａ^１、Ａ^１１、Ａ^１２、Ａ^２、Ａ^２１およびＡ^２２は独立して１，４−シクロヘキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり；これらの環において、１つのまたは隣り合わない２つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−または−ＳｉＨ_２−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられもよく；
Ｙは単結合、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−ＣＨ_２ＳｉＨ_２−、−ＳｉＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
Ｗは−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−ＣＨ_２ＳｉＨ_２−、−ＳｉＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３−Ｏ−、−Ｏ−（ＣＨ_２）_３−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
Ｚ^１１、Ｚ^１２、Ｚ^２、Ｚ^２１およびＺ^２２は、独立して単結合、−（ＣＨ_２）_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３−Ｏ−、−Ｏ−（ＣＨ_２）_３−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
ｊ、ｋ、ｍ、ｎ、ｐおよびｑは独立して０または１であり、そしてこれらの合計は１、２、または３であり；
ｍが０であるとき、ｊおよびｋはどちらも０であり、式（１）におけるＲａは水素、アルコキシおよびアルコキシメチルのいずれでもなく、そして式（２）におけるＲａは１−アルケニルである。 The present invention includes the following items.
[1] Compound represented by formula (1) or formula (2):

Where Ra and Rb are independently hydrogen or alkyl having 1 to 20 carbons; in this alkyl, any —CH ₂ — is —O—, —S—, —CO— or —SiH ₂ —. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen may be replaced with a halogen;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl; in these rings, one or two non-adjacent —CH ₂ — is —O—, —S—, —CO - or -SiH 2 _- may be replaced by, and any hydrogen may be replaced by halogen;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, —COCH ₂ —, —CH _{2 SiH 2 -, - SiH 2 CH} 2 -, - (CH 2) 4 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
W represents — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Z ¹¹ , Z ¹² , Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —CH ₂ CO—, —COCH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O— , —O— (CH ₂ ) ₃ —, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
j, k, m, n, p and q are independently 0 or 1, and their sum is 1, 2 or 3;
When m is 0, j and k are both 0, Ra in formula (1) is not hydrogen, alkoxy or alkoxymethyl, and Ra in formula (2) is 1-alkenyl.

[2] The compound according to item [1], wherein the sum of j, k and m and the sum of n, p and q are independently 1 or 2.

ここに、ＲａおよびＲｂは独立して水素または炭素数１〜２０のアルキルであり；このアルキルにおいて、末端に位置しない任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−または−ＣＯ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；
Ａ^１、Ａ^１１、Ａ^１２、Ａ^２、Ａ^２１およびＡ^２２は、独立して１，４−シクロヘキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり；これらの環において、１つのまたは隣り合わない２つの−ＣＨ_２−は−Ｏ−、−Ｓ−、または−ＣＯ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられもよく；
Ｙは単結合、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−ＣＨ_２ＳｉＨ_２−、−ＳｉＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
Ｗは−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−ＣＨ_２ＳｉＨ_２−、−ＳｉＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３−Ｏ−、−Ｏ−（ＣＨ_２）_３−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
Ｚ^１１、Ｚ^１２、Ｚ^２、Ｚ^２１およびＺ^２２は、独立して単結合、−（ＣＨ_２）_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３−Ｏ−、−Ｏ−（ＣＨ_２）_３−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、または−ＯＣＦ_２（ＣＨ_２）_２−であり；
式（１−２）、式（１−５）および式（１−９）において、Ｒａは水素、アルコキシおよびアルコキシメチルのいずれでもなく；式（２−２）、式（２−５）および式（２−９）において、Ｒａは１−アルケニルである。 [3] The compound according to item [1], represented by any one of formulas (1-1) to (1-9) and formulas (2-1) to (2-9):

Here, Ra and Rb are independently hydrogen or alkyl having 1 to 20 carbons; in this alkyl, any —CH ₂ — that is not located at the terminal is —O—, —S—, or —CO—. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen may be replaced with a halogen;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3. , 4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl; in these rings, one or two non-adjacent —CH ₂ — is —O—, —S—, or -CO- may be replaced, and any hydrogen may be replaced by halogen;
Y is a single _{bond, - (CH 2) 2 -} , - CH = CH -, - CF = CF -, - CF 2 O -, - OCF 2 -, - CH 2 CO -, - COCH 2 -, - CH 2 _{SiH 2 -, - SiH 2 CH} 2 -, - (CH 2) 4 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
W represents — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Z ¹¹ , Z ¹² , Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —CH ₂ CO—, —COCH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O— , —O— (CH ₂ ) ₃ —, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
In Formula (1-2), Formula (1-5), and Formula (1-9), Ra is not hydrogen, alkoxy, or alkoxymethyl; Formula (2-2), Formula (2-5), and Formula In (2-9), Ra is 1-alkenyl.

[4] Ra and Rb are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxyalkyl having 2 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and alkenyl having 3 to 10 carbon atoms. Oxy, C1-C10 perfluoroalkyl, or C1-C10 perfluoroalkoxy;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 4,6-dioxane-2,5. -Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro 1,4-phenylene, 2,3-difluoro-1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl;
Z ¹¹ and Z ¹² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH _{2 ) 4 -, - CH = CH-} (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - in Yes;
Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — _{OCF 2 -, - CH = CH} -, - CF = CF -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH- ( CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( The compound according to item [3], which is CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —. .

[5] Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxyalkyl having 2 to 10 carbons or alkenyl having 2 to 10 carbons;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1 , 4-phenylene, or 2,3-difluoro-1,4-phenylene;
Z ¹¹ and Z ¹² are independently a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, —CH═CH _{- (CH 2) 2 -,} - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - and is;
Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH _{-, - (CH 2) 2} CF 2 O-, or -OCF _{2 (CH 2) 2} - and is;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( The compound according to item [3], which is CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —. .

[6] Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons;
^{A 1, A 11, A 12} , A 2, A 21 and ^{A 22} are, independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro, - 1,4-phenylene;
Z ¹¹ and Z ¹² are independently a single bond or —CH═CH—;
Z ² , Z ²¹ and Z ²² are each independently a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, or —OCF ₂ —;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( The compound according to item [3], which is CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —. .

[7] The compound according to any one of [3] to [6], wherein A ¹ or A ² is 1,4-cyclohexylene.

[8] The compound according to any one of [3] to [6], wherein A ¹ or A ² is 1,4-phenylene.

[9] In Formula (1-1) to Formula (1-9), Y or Z ² is a single bond, and in Formula (2-1) to Formula (2-9), Z ² is a single bond. [3] The compound according to any one of [6].

[10] A ¹ or A ² is 1,4-cyclohexylene, Y or Z ² in Formula (1-1) to Formula (1-9) is a single bond, and Formula (2-1) to The compound according to any one of [3] to [6], wherein Z ² is a single bond in formula (2-9).

[11] A ¹ or A ² is 1,4-phenylene, Y or Z ² is a single bond in Formula (1-1) to Formula (1-9), and Formula (2-1) to Formula (1-9) The compound according to any one of [3] to [6], wherein Z ² is a single bond in (2-9).

[12] In any one of formula (2-1), formula (2-3), formula (2-4), formula (2-6), formula (2-7), and formula (2-8) A compound according to any one of [3] to [6], wherein A ¹ is 1,4-cyclohexylene.

[13] is represented by formula (2-1); A ¹ is 1,4-cyclohexylene; and W is — (CH ₂ ) ₂ —, —CH ₂ O—, or —CF ₂ O—. The compound according to any one of [3] to [6].

[14] Formula (2-3); A ¹ and A ¹¹ are both 1,4-cyclohexylene; Z ¹¹ is a single bond; and W is — (CH ₂ ) ₂ —, — CH ₂ O-, or _-CF 2 is a O-, [3] ~ the compound according to any one of [6].

[15] Formula (2-6); A ¹ , A ¹¹ and A ¹² are all 1,4-cyclohexylene; Z ¹¹ and Z ¹² are both single bonds; and W is − _{(CH 2) 2 -, -} CH 2 O-, or _-CF 2 is a O-, [3] ~ the compound according to any one of [6].

[16] In any one of formula (1-2), formula (1-4), formula (1-5), formula (1-7), formula (1-8), and formula (1-9) And the compound according to any one of [3] to [6], wherein Z ² is —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, or —OCF ₂ —.

[17] represented by the formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A ^11. The compound according to item [3], wherein ¹¹ is both 1,4-cyclohexylene; and Y and Z ¹¹ are both single bonds.

[18] represented by formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A The compound according to item [3], wherein ¹¹ is 1,4-cyclohexylene; Y is —CH ₂ CH ₂ —; and Z ¹¹ is a single bond.

[19] Formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 The compound according to item [3], wherein A ¹¹ is 1,4-cyclohexylene; and Y and Z ¹¹ are both a single bond.

[20] represented by formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A ^11. The compound according to any one of [3] to [6], wherein ¹¹ is both 1,4-phenylene; and Y and Z ¹¹ are both single bonds.

[21] represented by formula (1-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-cyclohexylene; and the compound according to item [3], wherein Y is a single bond.

[22] represented by formula (1-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-cyclohexylene; and the compound according to item [3], wherein Y is —CH ₂ CH ₂ —.

[23] represented by formula (2-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-cyclohexylene; and the compound according to item [3], wherein W is — (CH ₂ ) ₂ —.

[24] represented by formula (2-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-cyclohexylene be cyclohexylene; and W is _-CH 2 O-, [3] the compound according to claim.

[25] represented by formula (2-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-phenylene; and W is — (CH ₂ ) ₂ —.

[26] represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A The compound according to the item [3], wherein ¹¹ is both 1,4-cyclohexylene; Z ¹¹ is a single bond; and W is — (CH ₂ ) ₂ —.

[27] represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A The compound according to item [3], wherein ¹¹ is both 1,4-cyclohexylene; Z ¹¹ is a single bond; and W is —CH ₂ O—.

[28] represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1 , 4-phenylene, and A ¹¹ is 1,4-cyclohexylene; Z ¹¹ is a single bond; and W is — (CH ₂ ) ₂ —.

[29] represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ , A ¹¹ There are both ^{1,4-phenylene; Z 11} represents a single bond; and W is - _{(CH 2) 2} - a, [3] the compound according to claim.

[30] represented by formula (2-6); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ , A ^In paragraph [3], ¹¹ and A ¹² are both 1,4-cyclohexylene; Z ¹¹ and Z ¹² are single bonds; and W is — (CH ₂ ) ₂ — or —CH ₂ O—. The described compound.

[31] represented by formula (1-2); Ra is alkyl having 1 to 10 carbons, and Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ² is 1 , 4-cyclohexylene; and the compound according to item [3], wherein Z ² is —OCH ₂ —.

[32] represented by formula (1-5); Ra is alkyl having 1 to 10 carbons, and Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ² and A The compound according to item [3], wherein ²¹ is both 1,4-cyclohexylene; Z ² is —OCH ₂ —, and Z ²¹ is a single bond.

[33] represented by formula (1-4); Ra and Rb are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ and A ² are both 1,4-phenylene And the compound according to item [3], wherein Y and Z ² are both a single bond.

[34] represented by formula (1-4); Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ is 1,4-cyclohexylene; The compound according to item [3], wherein A ² is 1,4-phenylene; and Y and Z ² are both a single bond.

[35] represented by formula (1-4); Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ is 1,4-phenylene, and The compound according to item [3], wherein A ² is 1,4-cyclohexylene; and Y and Z ² are both a single bond.

[36] A liquid crystal composition containing at least one of the compounds according to item [1] and may contain at least one optically active compound.

ここに、Ｒ^１は炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｘ^１はフッ素、塩素、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_２ＣＨＦ_２、または−ＯＣＦ_２ＣＨＦＣＦ_３であり；Ｂ^１およびＤは独立して１，４−シクロヘキシレン、１，４−フェニレン、１，３−ジオキサン−２，５−ジイルまたは少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；Ｅは１，４−シクロヘキシレン、１，４−フェニレン、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^４およびＺ^５は独立して−（ＣＨ_２)_２−、−（ＣＨ_２)_４−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−または単結合であり；そして、Ｌ^１およびＬ^２は独立して水素またはフッ素である。 [37] At least one compound according to item [1] and at least one compound selected from the group consisting of compounds represented by each of formula (3), formula (4) and formula (5): A liquid crystal composition that contains and may contain at least one optically active compound:

Here, R ¹ is alkyl having 1 to 10 carbons; in this alkyl, arbitrary —CH ₂ — may be replaced by —O—, and optional — (CH ₂ ) ₂ — represents —CH═ CH— may be replaced and any hydrogen may be replaced with fluorine; X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, -OCF ₂ CHF _2, or be a -OCF ₂ CHFCF _3; ^{B 1} and D is independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or at least 1 1,4-phenylene in which one hydrogen is replaced with fluorine; E is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced with fluorine It is Eniren; ^{Z 4} and ^{Z 5} are independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - COO -, - CF 2 O -, - OCF 2 -, - CH = CH- or A single bond; and L ¹ and L ² are independently hydrogen or fluorine.

ここに、Ｒ^２およびＲ^３は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｘ^２は−ＣＮまたは−Ｃ≡Ｃ−ＣＮであり；Ｇは１，４−シクロヘキシレン、１，４−フェニレン、１，３−ジオキサン−２，５−ジイルまたはピリミジン−２，５−ジイルであり；Ｊは１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２,５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^６は−（ＣＨ_２)_２−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または単結合であり；Ｌ^３、Ｌ^４およびＬ^５は独立して水素またはフッ素であり；そしてｂ、ｃおよびｄは独立して０または１である。 [38] At least one selected from the group consisting of at least one of the compounds described in item [1] and a compound represented by each of formula (6-1), formula (6-2) and formula (7) And a liquid crystal composition that may contain at least one optically active compound:

Wherein R ² and R ³ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— and any hydrogen may be replaced with fluorine; X ² is —CN or —C≡C—CN; G is 1,4-cyclohex Silene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; J is 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5 - diyl or at least one hydrogen is 1,4-phenylene which is replaced by fluorine,; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, - OCF 2 - or a single bond in ^{it; L} 3, L ⁴ you Fine and L ⁵ have independently hydrogen or fluorine; and b, c and d are independently 0 or 1.

ここに、Ｒ^４は炭素数１〜１０のアルキルであり、そしてＲ^５はフッ素または炭素数１〜１０のアルキルであり；これらのアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；ＭおよびＰ^１は独立して１，４−シクロヘキシレン、１，４−フェニレンまたはデカヒドロ−２，６−ナフチレンであり；Ｚ^７およびＺ^８は独立して−（ＣＨ_２)_２−、−ＣＯＯ−または単結合であり；Ｌ^６およびＬ^７は独立して水素またはフッ素であり；そして、Ｌ^６とＬ^７の少なくとも１つはフッ素である。 [39] Consists of at least one of the compounds described in item [1] and a compound represented by each of formula (8), formula (9), formula (10), formula (11), and formula (12). A liquid crystal composition comprising at least one compound selected from the group and optionally containing at least one optically active compound:

Where R ⁴ is alkyl having 1 to 10 carbons and R ⁵ is fluorine or alkyl having 1 to 10 carbons; in these alkyls, any —CH ₂ — is replaced by —O—. Any — (CH ₂ ) ₂ — may be replaced by —CH═CH— and any hydrogen may be replaced by fluorine; M and P ¹ are independently 1,4 - cyclohexylene, be 1,4-phenylene or decahydro-2,6-naphthylene; ^{Z 7} and ^{Z 8} are independently _{- (CH 2) 2 -,} - COO- or a single bond; ^{L 6} and L ⁷ is independently hydrogen or fluorine; and at least one of L ⁶ and L ⁷ is fluorine.

ここに、Ｒ^６およびＲ^７は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｑ、ＴおよびＵは独立して１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２、５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；そして、Ｚ^９およびＺ^１０は独立して−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−または単結合である。 [40] At least one compound according to item [1] and at least one compound selected from the group consisting of compounds represented by each of formula (13), formula (14) and formula (15): A liquid crystal composition that contains and may contain at least one optically active compound:

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.

ここに、Ｒ^２およびＲ^３は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｘ^２は−ＣＮまたは−Ｃ≡Ｃ−ＣＮであり；Ｇは１，４−シクロヘキシレン、１，４−フェニレン、１，３−ジオキサン−２，５−ジイルまたはピリミジン−２，５−ジイルであり；Ｊは１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２,５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^６は−（ＣＨ_２)_２−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または単結合であり；Ｌ^３、Ｌ^４およびＬ^５は独立して水素またはフッ素であり；そしてｂ、ｃおよびｄは独立して０または１である。 [41] The item [37], further comprising at least one compound selected from the group consisting of compounds represented by formula (6-1), formula (6-2), and formula (7). Liquid crystal composition:

Wherein R ² and R ³ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— and any hydrogen may be replaced with fluorine; X ² is —CN or —C≡C—CN; G is 1,4-cyclohex Silene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; J is 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5 - diyl or at least one hydrogen is 1,4-phenylene which is replaced by fluorine,; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, - OCF 2 - or a single bond in ^{it; L} 3, L ⁴ you Fine and L ⁵ have independently hydrogen or fluorine; and b, c and d are independently 0 or 1.

ここに、Ｒ^６およびＲ^７は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｑ、ＴおよびＵは独立して１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２、５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；そして、Ｚ^９およびＺ^１０は独立して−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−または単結合である。 [42] The liquid crystal composition according to item [37], further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14) and formula (15). :

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with -CH = CH- and any hydrogen may be replaced with fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.

ここに、Ｒ^６およびＲ^７は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｑ、ＴおよびＵは独立して１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２、５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；そして、Ｚ^９およびＺ^１０は独立して−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−または単結合である。 [43] The liquid crystal composition according to item [38], further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14) and formula (15). :

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.

ここに、Ｒ^６およびＲ^７は独立して炭素数１〜１０のアルキルであり；このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２)_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｑ、ＴおよびＵは独立して１，４−シクロヘキシレン、１，４−フェニレン、ピリミジン−２、５−ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであり；そして、Ｚ^９およびＺ^１０は独立して−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−または単結合である。 [44] The liquid crystal composition according to item [39], further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14) and formula (15). :

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.

[45] Use of the liquid crystal composition according to any one of [36] to [44] for producing a liquid crystal display element.

[46] A liquid crystal display device comprising the liquid crystal composition according to any one of [36] to [44].

  The compound of the present invention has general physical properties necessary for liquid crystal compounds, stability to heat, light, etc., appropriate optical anisotropy, appropriate dielectric anisotropy, and excellent compatibility with other liquid crystal compounds. Have The liquid crystal composition of the present invention contains at least one of these compounds, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, and a low threshold voltage. Have. The liquid crystal display element of the present invention contains this composition and has a wide temperature range that can be used, a short response time, a large contrast ratio, and a low driving voltage.

式（１）および式（２）におけるＲａおよびＲｂは、独立して水素または炭素数１〜２０のアルキルである。このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−または−ＳｉＨ_２−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよい。ＲａまたはＲｂの例は、水素、アルキル、アルコキシ、アルコキシアルキル、アルコキシアルコキシ、アルキルチオ、アルキルチオアルコキシ、アシル、アシルアルキル、アシルオキシ、アシルオキシアルキル、アルコキシカルボニル、アルコキシカルボニルアルキル、アルケニル、アルケニルオキシ、アルケニルオキシアルキル、アルコキシアルケニル、アルキニル、アルキニルオキシ、シラアルキルおよびジシラアルキルである。少なくとも１つの水素がハロゲンで置き換えられたこれらの基も好ましい。好ましいハロゲンはフッ素および塩素である。さらに好ましいハロゲンはフッ素である。これらの基において分岐よりも直鎖の方が好ましい。ＲａおよびＲｂが分岐の基であっても光学活性であるときは好ましい。 The compound of the present invention is represented by either formula (1) or formula (2).

Ra and Rb in Formula (1) and Formula (2) are independently hydrogen or alkyl having 1 to 20 carbons. In this alkyl, any —CH ₂ — may be replaced by —O—, —S—, —CO— or —SiH ₂ —, and any — (CH ₂ ) ₂ — is —CH═CH—. Any hydrogen may be replaced with a halogen. Examples of Ra or Rb are hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, Alkoxyalkenyl, alkynyl, alkynyloxy, silaalkyl and disilaalkyl. Also preferred are those groups in which at least one hydrogen has been replaced by a halogen. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. In these groups, straight chain is preferable to branch. Even when Ra and Rb are branched groups, it is preferable when they are optically active.

  Preferred examples of Ra and Rb are alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxyalkyl having 2 to 10 carbons, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 10 carbons, These are perfluoroalkyl having 1 to 10 carbons and perfluoroalkoxy having 1 to 10 carbons. More preferred examples are alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxyalkyl having 2 to 10 carbons and alkenyl having 2 to 10 carbons. Further preferred Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and particularly preferred Rb is alkoxy having 1 to 10 carbons.

The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3 and _{-C 2 H 4 CH = CHC 2} H _{In an} alkenyl having a double bond at an odd position such as ₅ , a trans configuration is preferable. -CH ₂ CH ₌ CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as -CH 2 CH = _CHC 2 _{H 5} and _-CH 2 CH = _CHC 3 _{H 7} are preferred.

Specific examples of _{alkyl, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -C 6 H 13, -C 7 H 15 and -C ₈ H ₁₇ . Specific examples of the _{alkoxy, -OCH 3, -OC 2 H 5} , -OC 3 H 7, -OC 4 H 9, -OC 5 H 10, is -OC _{6 H 13} and _-OC 7 _{H 15.} Specific examples of alkoxyalkyl _{include, -CH 2 OCH 3, -CH 2} OC 2 H 5, -CH 2 OC 3 H 7, - (CH 2) 2 OCH 3, - (CH 2) 2 OC 2 H 5 _{, - (CH 2) 2 OC} 3 H 7, - (CH 2) 3 OCH 3, - (CH 2) 4 OCH 3 and _- a _(CH 2) 5 OCH _3.

Specific examples of alkenyl _{include, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH = CHC 2 H 5, -CH 2 CH = CHCH 3, - (CH 2) 2 _{CH = CH 2, -CH = CHC} 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 CH = CHCH 3 and _- a _{(CH 2) 3 CH = CH} 2. Specific examples of _alkenyloxy, -OCH _{2 CH} = CH _2, a -OCH 2 CH = CHCH ₃ and _{-OCH 2 CH = CHC 2 H 5} .

Specific examples of alkyl in which at least one hydrogen is replaced by _{halogen, - (CH 2) 2 F} , -CF 2 CH 2 F, -CF 2 CHF 2, -CH 2 CF 3, -CF 2 CF 3 _{, - (CH 2) 3 F} , - (CF 2) 2 CF 3, a -CF 2 CHFCF ₃ and -CHFCF ₂ CF _3. Specific examples of alkoxy in which at least one hydrogen is replaced by halogen include —O (CH ₂ ) ₂ F, —OCF ₂ CH ₂ F, —OCF ₂ CHF ₂ , —OCH ₂ CF ₃ , —OCF ₂ CF _{3, -O (CH 2) 3} F, -O (CF 2) 2 CF 3, a -OCF 2 CHFCF ₃ and -OCHFCF ₂ CF _3. Specific examples of alkenyl in which at least one hydrogen is replaced by _{halogen, -CH = CHF, -CH = CF} 2, -CF = CHF, -CH = CHCH 2 F, -CH = CHCF 3, and - ( CH ₂₎ a ₂ CH = CF _2.

Preferred specific examples of Ra or Rb _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -OCH 3, -OC 2 H 5, - _{OC 3 H 7, -OC 4 H} 9, -OC 5 H 10, -CH 2 OCH 3, - (CH 2) 2 OCH 3, - (CH 2) 3 OCH 3, -CH = CH 2, -CH = _{CHCH 3, -CH 2 CH = CH} 2, -CH = CHC 2 H 5, -CH 2 CH = CHCH 3, - (CH 2) 2 CH = CH 2, -CH = CHC 3 H 7, -CH 2 CH _{= CHC 2 H 5, - (} CH 2) 2 CH = CHCH 3, - (CH 2) 3 CH = CH 2, -OCH 2 CH = CH 2, -OCH 2 CH = CHCH 3, -OCH 2 CH = CHC _{2 H 5, -CF 2 CF 3} , -CF 2 CH _{2, -CF 2 CH 2 F,} - (CF 2) 2 CF 3, -CF 2 CHFCF 3, -CHFCF 2 CF 3, -OCF 2 CF 3, -OCF 2 CHF 2, -OCF 2 CH 2 F, - _{OCF 2 CF 2 CF 3, -OCF} 2 CHFCF 3, and a -OCHFCF ₂ CF _3.

More preferred specific examples of Ra or Rb _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -OCH 3, -OC 2 H 5, _{-OC 3 H 7, -OC 4 H} 9, -OC 5 H 10, -CH 2 OCH 3, -CH = CH 2, -CH = CHCH 3, -CH 2 CH = CH 2, -CH = CHC 2 H _{5, -CH 2 CH = CHCH 3} , - (CH 2) 2 CH = CH 2, -CH = CHC 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 CH = CHCH 3, and _{- (CH} 2) a 3 CH = CH _2.

Further preferred specific examples of Ra _{are, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -CH = CH 2, -CH = CHCH 3, _{- (CH 2) 2 CH =} CH 2, and _{- (CH} 2) a 2 CH = CHCH _3. More preferred specific examples of Rb are —OCH ₃ , —OC ₂ H ₅ , and —OC ₃ H ₇ .

A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² in formula (1) and formula (2) are each independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2 , 6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl. In these rings, one or two non-adjacent —CH ₂ — may be replaced with —O—, —S—, —CO— or —SiH ₂ —, and any hydrogen is replaced with a halogen. May be.

Examples of the cyclic group in which one or two non-adjacent —CH ₂ — are replaced by —O—, —S—, —CO— or —SiH ₂ — include the following formulas (16-1) to ( 16-30). Preferred examples among these are the formula (16-1), the formula (16-2), the formula (16-3), the formula (16-4), the formula (16-13), and the formula (16-21). is there.

  Examples of the cyclic group in which arbitrary hydrogen is replaced by halogen are cyclic groups represented by the following formulas (17-1) to (17-17). Preferred examples among these include formula (17-1), formula (17-2), formula (17-3), formula (17-5), formula (17-7), formula (17-8), Formula (17-10), Formula (17-14), Formula (17-16), and Formula (17-17).

Preferred examples of A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ or A ²² are 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 4,6-dioxane-2,5. -Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro 1,4-phenylene, 2,3-difluoro-1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl and naphthalene-2,6-diyl. More preferred examples are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene. It is. Further preferred examples are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1,4-phenylene. Particularly preferred examples of A ¹ or A ² are 1,4-cyclohexylene and 1,4-phenylene.

Y, W, Z ¹¹ , Z ¹² , Z ² , Z ²¹ and Z ²² in Formula (1) and Formula (2) are linking groups. Y is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH- , — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —. W represents — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —. Z ² , Z ¹¹ , Z ¹² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —. _{, -CF 2 O -, - OCF} 2 -, - CH = CH -, - CF = CF -, - CH 2 CO -, - COCH 2 -, - CH 2 SiH 2 -, - SiH 2 CH 2 -, - (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH— , — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —.

Preferred examples of Y include a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — _{CH = CH- (CH 2) -} , - (CH 2) -CH = CH -, - (CH 2) 2 CF 2 O- and -OCF _{2 (CH 2) 2} - it is. More preferred examples are a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, —CH═CH— (CH ₂ ) _{2. -, - (CH 2) 2} -CH = CH -, - (CH 2) 2 CF 2 O- and -OCF _{2 (CH 2) 2} - it is. Particularly preferred examples of Y are a single bond and — (CH ₂ ) ₂ —. Note that the configuration regarding the double bond of the bonding group such as —CH═CH—, —CH═CH— (CH ₂ ) ₂ —, and — (CH ₂ ) ₂ —CH═CH— is trans rather than cis. preferable.

Preferred examples of W are — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, — (CH _{2) 4 -, - (CH} 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - _{(CH 2)} 2 _CF 2 O- and -OCF _{2 (CH 2) 2} - it is. More preferred examples are — (CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₄ —, —CH. _{= CH- (CH 2) 2 -} , - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF 2 O- and -OCF _{2 (CH 2) 2} - it is. Particularly preferred examples of W are — (CH ₂ ) ₂ — and —CH ₂ O—. Note that the configuration regarding the double bond of the bonding group such as —CH═CH—, —CH═CH— (CH ₂ ) ₂ —, and — (CH ₂ ) ₂ —CH═CH— is trans rather than cis. preferable.

Preferred examples of Z ² , Z ¹¹ , Z ¹² , Z ²¹ or Z ²² are a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, _{-CH = CH- (CH 2) 2} -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF 2 O- and -OCF _{2 (CH 2) 2} - it is. More preferred examples are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) _2. CF ₂ O— and —OCF ₂ (CH ₂ ) ₂ —. And a particularly preferable example of Z ² , Z ¹¹ , Z ¹² , Z ²¹ or Z ²² is a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— and —OCF ₂ —. In addition, trans is preferable to cis in the configuration of a double bond of a bonding group such as —CH═CH—, —CH═CH— (CH ₂ ) ₂ —, and — (CH ₂ ) ₂ —CH═CH—. .

  In formula (1) and formula (2), j, k, m, n, p and q are independently 0 or 1, and the sum of these is 1, 2 or 3. That is, the compound (1) and the compound (2) are compounds having 2 to 4 rings. When m is 0, j and k are both 0, Ra in formula (1) is not hydrogen, alkoxy or alkoxymethyl, and Ra in formula (2) is 1-alkenyl. The sum of j, k and m is preferably 1 or 2, and the sum of n, p and q is also preferably 1 or 2.

As mentioned above, particularly preferred examples of A ¹ or A ² are 1,4-phenylene and 1,4-cyclohexylene. Thus, particularly preferred examples of formula (1) and formula (2) are: when A ¹ and A ² are both 1,4-phenylene, A ¹ is 1,4-phenylene and A ² is 1, When 4-cyclohexylene is used, A ¹ is 1,4-cyclohexylene, and A ² is 1,4-phenylene, and when both A ¹ and A ² are 1,4-cyclohexylene. It is.

As mentioned above, particularly preferred examples of Y are a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, and —CH═CH—. Particularly preferred examples of Z ² are a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— and —OCF ₂ —. That is, in Formula (1), at least one of Y and Z ² is a single bond, which is one preferred example of compound (1).

In Formula (1), when m is 0 and the sum of n, p and q is 1, 2 or 3, Z ² is —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or it is preferably - -OCF _2.

In formula (1), when m and k are 1 and j and n are 0, Ra is alkyl or alkenyl, Rb is alkoxy, and A ¹ and A ¹¹ are independently 1,4 - phenylene or 1,4-cyclohexylene, and is preferably Y, and ^{Z 11} are both single bonds.

In formula (1), when m is 1 and j, k, n, p and q are 0, Ra is alkyl or alkenyl, Rb is alkoxy, and A ¹ is 1,4-cyclohexyl. It is preferably silene and Y is a single bond or — (CH ₂ ) ₂ —. In this case, Y is - _{(CH 2) 2} - and further preferably from.

In formula (1), when m and k are 1 and j, n, p and q are 0, Ra is alkyl or alkenyl, Rb is alkoxy, and A ¹ and A ¹¹ are both 1 , 4-cyclohexylene, Y is — (CH ₂ ) ₂ —, and Z ¹¹ is preferably a single bond.

In Formula (1), when m is 0, n is 1, and p and q are both 0, Ra is alkyl, Rb is alkyl or alkenyl, and A ² is 1,4- Preferred is cyclohexylene and Z ² is —OCH ₂ —.

In the formula (1), when m and q are 0 and n and p are 1, Ra is alkyl, Rb is alkyl or alkenyl, and A ² and A ²¹ are both 1,4-cyclohexyl. Preferably, it is silene, Z ² is —OCH ₂ —, and Z ²¹ is a single bond.

In formula (1), when m and n are 1 and j, k, p and q are all 0, Ra and Rb are independently alkyl or alkenyl, and A ¹ and A ² are both It is preferably 1,4-phenylene and both Y and Z ² are single bonds.

In Formula (1), when m and n are 1 and j, k, p and q are all 0, Ra and Rb are independently alkyl or alkenyl, and A ¹ is 1,4- Preferred is cyclohexylene, A ² is 1,4-phenylene, and both Y and Z ² are single bonds.

In formula (1), when m and n are 1 and j, k, p and q are 0, Ra and Rb are independently alkyl or alkenyl, and A ¹ is 1,4-phenylene. Preferably, A ² is 1,4-cyclohexylene and both Y and Z ² are single bonds.

In formula (2) and when m is 0, it is preferred that Z ² is a single bond.

In Formula (2), when m is 1 and the sum of n + p + q is 1 or 2, W is — (CH ₂ ) ₂ — or —CH ₂ O—, and Z ² is a single bond. It is preferable. More preferably, W is —CH ₂ O—.

In the formula (2), when m is 1, A ¹ is preferably 1,4-cyclohexylene.

In formula (2), when m is 1 and j, k, n, p and q are 0, Ra is alkyl or alkenyl, Rb is alkoxy, and A ¹ is 1,4-cyclohexyl. It is preferably silene and W is — (CH ₂ ) ₂ —.

In formula (2), when m and k are 1 and j, n, p and q are 0, A ¹ and A ¹¹ are both 1,4-cyclohexylene and W is — (CH _{2 2} ) and Z ¹¹ is preferably a single bond.

In the formula (2), when m, j and k are all 1 and n, p and q are 0, A ¹ , A ¹¹ and A ¹² are all 1,4-cyclohexylene, and Y Is — (CH ₂ ) ₂ —, and it is preferred that both Z ¹¹ and Z ¹² are single bonds.

In addition, compound (1) and compound (2) may contain more isotopes such as ² H (deuterium) and ¹³ C than the amount of natural abundance. At this time, there is no significant difference in the physical properties of the compounds.

Preferred examples of the formula (1) are the following formulas (1-1) to (1-9), and preferred examples of the formula (2) are the formulas (2-1) to (2-9).

これらの式中の記号は、式（１）および式（２）におけるそれぞれの記号と同じ意味を有し、それらの好ましい例も同じである。

The symbols in these formulas have the same meaning as the symbols in formula (1) and formula (2), and preferred examples thereof are also the same.

In Formula (1-1) to Formula (1-9), it is particularly preferable that at least one of Y and Z ² is a single bond. In Formula (2-1) to Formula (2-9), it is particularly preferable that Z ² is a single bond.

In Formula (1-1), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and A ¹ is 1,4-cyclohexylene. And Y is preferably a single bond or — (CH ₂ ) ₂ —.

In Formula (1-2), Ra is alkyl having 1 to 10 carbons, Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and A ² is 1,4-cyclohexylene. And Z ² is preferably —OCH ₂ —.

In Formula (1-2), Formula (1-4), Formula (1-5), Formula (1-7), Formula (1-8), and Formula (1-9), Z ² is —CH _{2 O -, - OCH 2 -,} - CF 2 O-, or -OCF ₂ - is preferably.

In Formula (1-3), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and both A ¹ and A ¹¹ are 1, 4 - cyclohexylene, and is preferably Y, and Z ¹¹ are both single bonds.

In Formula (1-3), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and both A ¹ and A ¹¹ are 1, 4 - cyclohexylene, Y is - _{(CH 2) 2} - and is, and is preferably ^{Z 11} is a single bond.

In Formula (1-3), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and A ¹ is 1,4-phenylene. A ¹¹ is preferably 1,4-cyclohexylene, and both Y and Z ¹¹ are preferably a single bond.

In Formula (1-3), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and both A ¹ and A ¹¹ are 1, 4 - phenylene, and is preferably Y, and Z ¹¹ are both single bonds.

In the formula (1-4), independently Ra and Rb are alkyl or alkenyl having 2 to 10 carbon atoms having 1 to 10 carbon atoms, ^{A 1} and ^{A 2} are both 1,4-phenylene, and Y And Z ² are preferably a single bond.

In Formula (1-4), Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, A ¹ is 1,4-cyclohexylene, A ² is 1, It is preferably 4-phenylene and both Y and Z ² are single bonds.

In Formula (1-4), Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, A ¹ is 1,4-phenylene, and A ² is 1,4. -Cyclohexylene, and both Y and Z ² are preferably a single bond.

In Formula (1-5), Ra is alkyl having 1 to 10 carbons, Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and A ² and A ²¹ are both 1, 4 - cyclohexylene, ^{Z 2} is -OCH ₂ - and is, and is preferably ^{Z 21} is a single bond.

In Formula (2-1), Formula (2-3), Formula (2-5), and Formula (2-5) to Formula (2-7), A ¹ is 1,4-cyclohexylene. preferable.

In Formula (2-1), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and W is — (CH ₂ ) ₂ — or -CH ₂ is O-, and it is preferred that ^{a 1} is 1,4-cyclohexylene.

In the formula (2-3), it is preferable that A ¹ and A ¹¹ are 1,4-cyclohexylene and Z ¹¹ is a single bond.

In Formula (2-3), Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, Rb is alkoxy having 1 to 10 carbons, and W is — (CH ₂ ) ₂ — or It is preferably —CH ₂ O—, A ¹ and A ¹¹ are both 1,4-cyclohexylene, and Z ¹¹ is a single bond.

In Formula (2-6), A ¹ , A ¹¹ and A ¹² are all 1,4-cyclohexylene, W is — (CH ₂ ) ₂ — or —CH ₂ O—, and Z ¹¹ and Z ¹² Are preferably single bonds.

Next, the liquid crystal composition of the present invention will be described.
The liquid crystal composition of the present invention is a composition containing at least one of the compound (1) and the compound (2) and may contain at least one optically active compound. The composition of the present invention can contain a liquid crystal compound other than the compound (1) and the compound (2). A preferred liquid crystal compound other than the compound (1) and the compound (2) is a compound selected from the group consisting of compounds represented by the following formulas (3) to (15).

In these formulas, R ¹ is alkyl having 1 to 10 carbons. In this alkyl, any non-terminally located —CH ₂ — may be replaced with —O—, optional — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any Hydrogen may be replaced by fluorine. X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ or —OCF ₂ CHFCF ₃ . B ¹ and D are independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine. is there. E is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine. Z ⁴ and Z ⁵ are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH— or a single bond. . L ¹ and L ² are independently hydrogen or fluorine.

In these formulas, R ² and R ³ are independently alkyl having 1 to 10 carbons. In this alkyl, any —CH ₂ — may be replaced with —O—, any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen is fluorine. It may be replaced. X ² is —CN or —C≡C—CN. G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl. J is 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine. Z ⁶ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond. L ³ , L ⁴ and L ⁵ are independently hydrogen or fluorine. B, c and d are each independently 0 or 1.

In these formulas, R ⁴ is alkyl having 1 to 10 carbons, and R ⁵ is fluorine or alkyl having 1 to 10 carbons. In these alkyls, any non-terminally located —CH ₂ — may be replaced with —O—, optional — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any The hydrogen of may be replaced by fluorine. M and P ¹ are independently 1,4-cyclohexylene, 1,4-phenylene or decahydro-2,6-naphthylene. Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, —COO— or a single bond. L ⁶ and L ⁷ are independently hydrogen or fluorine, and at least one of L ⁶ and L ⁷ is fluorine.

In these formulas, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons. In this alkyl, any non-terminally located —CH ₂ — may be replaced with —O—, optional — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any Hydrogen may be replaced by fluorine. Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine. Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.

  The first example of the liquid crystal composition in the present invention comprises at least one compound selected from the group consisting of the compound (1) and the compound (2), and the compound (3), the compound (4) and the compound (5). It is a composition containing at least one compound selected from the group, and may contain at least one optically active compound.

  The second example of the liquid crystal composition in the present invention is at least one compound selected from the group consisting of compound (1) and compound (2), compound (6-1), compound (6-2) and compound. It is a composition that contains at least one compound selected from the group consisting of (7) and may contain at least one optically active compound.

  A third example of the liquid crystal composition in the present invention is represented by at least one compound selected from the group consisting of the compound (1) and the compound (2), and each of the formulas (8) to (12). It is a composition containing at least one compound selected from the group consisting of compounds and may contain at least one optically active compound.

  A fourth example of the liquid crystal composition in the present invention includes at least one compound selected from the group consisting of the compound (1) and the compound (2), the compound (13), the compound (14), and the compound (15). It is a composition containing at least one compound selected from the group consisting of at least one optically active compound.

  The fifth example of the liquid crystal composition in the present invention is selected from the group consisting of the compound (6-1), the compound (6-2) and the compound (7) in addition to the combination of the compounds shown in the first example. A composition further comprising at least one compound. That is, at least one compound selected from the group consisting of compound (1) and compound (2), at least one compound selected from the group consisting of compound (3), compound (4) and compound (5), and The composition contains at least one compound selected from the group consisting of compound (6-1), compound (6-2) and compound (7), and may contain at least one optically active compound.

  The sixth example of the liquid crystal composition in the invention includes at least one selected from the group consisting of the compound (13), the compound (14) and the compound (15) in addition to the combination of the compounds shown in the first example. A composition further containing a compound. That is, at least one compound selected from the group consisting of compound (1) and compound (2), at least one compound selected from the group consisting of compound (3), compound (4) and compound (5), and The composition contains at least one compound selected from the group consisting of compound (13), compound (14) and compound (15), and may contain at least one optically active compound.

  The seventh example of the liquid crystal composition in the present invention includes at least one selected from the group consisting of the compound (13), the compound (14) and the compound (15) in addition to the combination of the compounds shown in the second example. A composition further comprising one compound. That is, at least one compound selected from the group consisting of compound (1) and compound (2), at least one selected from the group consisting of compound (6-1), compound (6-2) and compound (7) It is a composition containing at least one compound selected from the group consisting of one compound and compound (13), compound (14) and compound (15), and may contain at least one optically active compound.

In the formulas (3) to (15), the same symbols used in a plurality of formulas may have the same meaning or different meanings. Examples of when the same symbols have a different meaning, wherein R ¹ of formula (3) is alkyl, and is when R ¹ of formula (4) is alkenyl.

  Next, the compound of the present invention will be further described. The compounds of the present invention are 2-, 3- or 4-ring compounds having 2-difluoromethyl-3-fluoro-1,4-phenylene or 2-trifluoromethyl-3-fluoro-1,4-phenylene. . The compound of the present invention is extremely physically and chemically stable under the conditions under which the device is normally used, and has good compatibility with other liquid crystal compounds. The composition containing the compound of the present invention is stable under conditions in which the device is usually used. Even when the composition is stored at a low temperature, the compound does not precipitate as crystals (or a smectic phase). The compound of the present invention has general physical properties necessary for a liquid crystal material, appropriate optical anisotropy, and appropriate dielectric anisotropy.

  The physical properties such as optical anisotropy and dielectric anisotropy of the compound of the present invention can be arbitrarily adjusted by appropriately selecting the terminal group, ring and bonding group. The effects of the types of terminal groups, rings and linking groups on the physical properties of the compounds of the present invention will be described below.

  The compound of the present invention has negative dielectric anisotropy. If the substituent and the linking group are properly selected, the compound of the present invention exhibits a large negative dielectric anisotropy. A compound having a large negative dielectric anisotropy is a useful component for lowering the threshold voltage of a composition for IPS or VA.

  When Ra or Rb is a linear group, the temperature range of the liquid crystal phase is wide and the viscosity is small. When Ra or Rb is a branched chain group, the compatibility with other liquid crystal compounds is good. A compound in which Ra or Rb is an optically active group is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the device can be prevented. A compound in which Ra or Rb is not an optically active group is useful as a component of the composition. When Ra or Rb is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.

When at least two of A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are 1,4-cyclohexylene, the maximum temperature is high, the optical anisotropy is small, and the viscosity is small. When at least one ring is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is large. When at least two rings are 1,4-phenylene, the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the maximum temperature is high.

^Y, at least one single bond of ^{Z 11, Z 12, Z 2} , Z 21 and _{^{Z 22, - (CH 2)}} 2 -, - CF 2 O -, - OCF 2 -, - CH = CH- or -CF When = CF-, the viscosity is small. When this bonding group is a single bond, —OCF ₂ —, —CF ₂ O—, — (CH ₂ ) ₂ — or —CH═CH—, the viscosity is smaller. When this bonding group is —CH═CH—, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant) is large.

When W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or —CF═CF—, the viscosity is small. . When this bonding group is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —OCF ₂ —, —CF ₂ O— or —CH═CH—, the viscosity is smaller. When the bonding group is —CH═CH—, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant) is large. When this bonding group is —CH ₂ O—, the dielectric anisotropy is negative and larger.

A compound in which at least one of A ¹ and A ² is 1,4-phenylene which may be substituted with fluorine, and the bonding groups Z ¹ and Z ² directly connected to the ring are single bonds has an anisotropic dielectric constant It is negative and larger, and at the same time the optical anisotropy is large.

  Compounds (1-1) to (1-5) and compounds (2-1) to (2-5) which are bicyclic or tricyclic have a low viscosity. The compound (1-3) to compound (1-9) and the compound (1-3) to compound (1-9), which are tricyclic or tetracyclic, have a high maximum temperature. Thus, the compound which has the target physical property can be obtained by selecting suitably the kind of terminal group, a ring and a coupling group, and the number of rings. Therefore, the compounds of the present invention, in particular, the compound (1-1) to the compound (1-9) and the compound (2-1) to the compound (2-9) are components of a composition used for devices such as IPS and VA. Useful as.

In Compound (1-1), Compound (1-3), Compound (1-4), and Compound (1-6) to Compound (1-8), Z ¹ is — (CH ₂ ) ₂ — or —CH═ A compound that is CH- exhibits negatively large dielectric anisotropy, exhibits a particularly excellent balance of physical properties as a liquid crystal material, such as a wide temperature range of the liquid crystal phase and a low viscosity.

  The compounds of the present invention can be synthesized by appropriately combining techniques in organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting materials are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive・ It is described in the organic synthesis (Comprehensive Organic Synthesis, Pergamon Press), new experimental chemistry course (Maruzen).

With regard to an example of a method for generating a linking group, a scheme is first shown, and then the scheme is described in terms (I) to (XI). In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compound (1A) to Compound (1K) are converted into Compound (1), Compound (2), Compound (1-1) to Compound (1-9), or Compound (2-1) to Compound (2-9). Equivalent to.

(I) Formation of Single Bond A compound obtained by reacting arylboric acid (21) with compound (22) synthesized by a known method in the presence of a carbonate aqueous solution and a catalyst such as tetrakis (triphenylphosphine) palladium. Synthesize (1A). This compound (1A) is obtained by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.

(II) Formation of —COO— and —OCO— The compound (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (24). Compound having —COO— by dehydrating compound (24) and phenol (25) synthesized by a known method in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Synthesize (1B). A compound having —OCO— is also synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (26). Compound (26) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having —CF ₂ O— (M. Kuroboshi et al., Chem. Lett., 1992). , 827). Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST) (see WH Bunnelle et al., J. Org. Chem. 1990, 55, 768.). A compound having —OCF ₂ — is also synthesized by this method. These linking groups can also be generated by the method described in Peer. Kirsch et al., Anbew. Chem. Int. Ed. 2001, 40, 1480.

(IV) Formation of — (CH ₂ ) ₂ CF ₂ O— and —OCF ₂ (CH ₂ ) ₂ — Synthesis by the method disclosed in US Pat. No. 4,834,905 and US Pat. Compound (1D) is synthesized according to the method of Item (III) using propionate derivative (27). A compound having —OCF ₂ — (CH ₂ ) ₂ — is also synthesized by this method.

(V) Formation of —CH═CH— The compound (23) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain the aldehyde (29). A phosphoryl ylide generated by treating a phosphonium salt (30) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (29) to synthesize a compound (1E). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(VI) Formation of — (CH ₂ ) ₂ —CH═CH— and —CH═CH— (CH ₂ ) ₂ — Using the phosphonium salt (31) instead of the phosphonium salt (30), Compound (1F) is synthesized according to the method. Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary. A compound having —CH═CH— (CH ₂ ) ₂ — is also synthesized by this method.

Formation of (VII)-(CH ₂ ) ₂ — Compound (1G) is synthesized by hydrogenating compound (1E) in the presence of a catalyst such as palladium / carbon.

(VIII) Formation of — (CH ₂ ) ₄ — Compound (1F) Compound (1H) is synthesized by catalytic hydrogenation in the presence of a catalyst such as palladium carbon.

(IX) Formation of —CF═CF— The compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (32). Compound (22) is treated with n-butyllithium and then reacted with compound (32) to synthesize compound (1I).

(IX) Formation of —CH ₂ O— or —OCH ₂ — The compound (29) is reduced with a reducing agent such as sodium borohydride to obtain the compound (33). This is halogenated with hydrobromic acid or the like to obtain compound (34). Compound (1J) is synthesized by reacting compound (34) with compound (25) in the presence of potassium carbonate or the like.

Formation of (X) — (CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — Compound (1K) was synthesized according to the method of Item (IX) using Compound (37) instead of Compound (34). To do.

これらの式における記号は式（１）における記号と同じ意味を有する。このことは以下に示されるスキームにおいても同様である。 Next, an example of a method for synthesizing a compound in which X is difluoromethyl in formula (1) is shown in the following scheme.

The symbols in these formulas have the same meaning as the symbols in formula (1). The same applies to the scheme shown below.

  For example, the compound (39) is synthesized by the method disclosed in JP-A-58-126823, JP-A-58-121225, JP-A-59-016840, or JP-A-59-042329. The 3-fluorobenzene derivative (38) is synthesized by reacting sec-butyllithium and then dimethylformamide or formylpiperidine. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Compound (1) is synthesized by reacting compound (39) with a fluorinating agent such as DAST. This reaction is carried out in a solvent such as a halogenated hydrocarbon such as dichloromethane at a temperature between −100 ° C. and the boiling point of the solvent.

これらの式において、Ｒは炭素数１〜１９のアルキルである。 Next, an example of a synthesis method for the compound (45) in which n, p and q are all 0 and Rb is alkoxy will be shown.

In these formulas, R is alkyl having 1 to 19 carbons.

  Compound (41) is synthesized by sequentially reacting compound (40) with sodium hydride and chloromethyl methyl ether (MOMCl). These reactions are preferably carried out in a solvent such as tetrahydrofuran at a temperature between −20 ° C. and the boiling point of the solvent. Compound (42) is synthesized by reacting compound (41) with sec-butyllithium and then dimethylformamide or formylpiperidine. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Compound (43) is synthesized by reacting compound (42) with a fluorinating agent such as DAST. This reaction is carried out in a solvent such as a halogenated hydrocarbon such as dichloromethane at a temperature between −100 ° C. and the boiling point of the solvent. Compound (44) is synthesized by deprotection of compound (43). This reaction is carried out by reacting dilute hydrochloric acid such as 2M hydrochloric acid in an alcohol such as ethanol at a temperature between room temperature and the boiling point of the solvent. Compound (45) is synthesized by an etherification reaction of compound (44). This reaction is carried out by reacting compound (44) with an alkyl halide such as alkyl iodide at a temperature between room temperature and the boiling point of the solvent in the presence of a base such as sodium carbonate in a solvent such as dimethylformamide.

Next, the sum of n, p and q is 1 or more, and Z ² is —OCO—, —OCF ₂ —, —OCF ₂ (CH ₂ ) ₂ —, —OCH ₂ —, or —O (CH ₂ ). An example of the synthesis method regarding the compound (46) to the compound (50) which is _3- is shown.

  The compounds (46) to (50) are respectively synthesized by using the compound (44) in place of the alcohol (phenol) intermediate in the above-described method for producing a linking group.

Y, Z ¹¹ , Z ¹² , Z ² , Z ²¹ or Z ²² is a single bond, and the directly connected ring A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ or A ²² is 1,4-phenylene. Compounds (60) and (63) can be synthesized by the following method in addition to the above synthesis method.

The compound (52) is synthesized by lithiation of the compound (51) with n-butyllithium, followed by reaction with a borate ester such as trimethyl borate and further hydrolysis with hydrochloric acid, sulfuric acid or the like. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Compound (53) is synthesized by reacting and oxidizing compound (52) with a peroxide such as hydrogen peroxide or peracetic acid. These reactions are preferably carried out in an ether hydrocarbon such as diethyl ether or tetrahydrofuran, or a carboxylic acid such as formic acid or acetic acid, at a temperature between −20 ° C. and the boiling point of the solvent. Compound (57) was synthesized by applying the same reaction procedure using Compound (53) instead of Compound (40) in the reaction route for synthesizing Compound (44) from Compound (40) described above. To do. Compound (58) is synthesized by reacting compound (57) with trifluoromethanesulfonic anhydride ((Tf) ₂ O) in the presence of a base such as pyridine or triethylamine. These reactions are preferably performed in a solvent such as a halogenated hydrocarbon such as dichloromethane at a temperature between −20 ° C. and room temperature. Compound (60) is synthesized by reacting compound (58) with boric acid compound (59). These reactions are preferably carried out at room temperature using a metal catalyst in the presence of a base such as potassium phosphate or potassium carbonate in a solvent such as an aromatic hydrocarbon such as toluene or an ether hydrocarbon such as dioxane or ethylene glycol dimethyl ether. To a boiling point of the solvent. Tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, palladium carbon, etc. are used as the metal catalyst.

  Compound (63) uses Compound (44) and Compound (62) instead of Compound (57) and Compound (59) in the reaction route for synthesizing Compound (60) from Compound (57) described above, Synthesize by applying the same reaction procedure.

Next, an example of a method for synthesizing a compound in which X is trifluoromethyl in formula (2) is shown in the following scheme.

  For example, the compound (64) is synthesized by the method disclosed in JP-A-58-126823, JP-A-58-121225, JP-A-59-016840, or JP-A-59-042329. The 3-fluorobenzene derivative (38) is reacted with sec-butyllithium and then with iodine. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Compound (1) was prepared according to the method of Qing-Yun Chen et al. Described in J. Chem. Soc., Chem. Commun., 1989, 705, and methyl fluorosulfonyldifluoroacetate in the presence of cuprous iodide. It is synthesized by reacting. This reaction is carried out in an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide at a temperature between 60 ° C. and the boiling point of the solvent.

Compound (69) wherein n, p and q are 0 in formula (2), Rb is alkoxy, W is —CH═CH— and compound (70) wherein W is — (CH ₂ ) ₂ — An example of the synthesis method is shown in the following scheme. The compound (69) and the compound (70) correspond to the formula (2-1), the formula (2-3), and the formula (2-6).

これらの式におけるＲは炭素数１〜１９のアルキルである。

R in these formulas is alkyl having 1 to 19 carbon atoms.

  For example, compound (66) is synthesized by reacting compound (65) described in Synlett 1999, No. 4, 389-396 with sec-butyllithium and then N-formylpiperidine. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Compound (68) is synthesized by allowing Grignard reagent (67) to act on compound (66) and then dehydrating the resulting alcohol in the presence of an acid catalyst such as p-toluenesulfonic acid. Further, the compound (69) is synthesized by acting a THF solution of cesium fluoride or tetrabutylammonium fluoride in N, N-dimethylformamide on (68). Compound (70) can be synthesized by adding hydrogen to compound (69) in the presence of a catalyst such as Pd / C.

In the formula (2), an example of a synthesis method of the compound (76) in which n, p, and q are 0, Rb is alkoxy, and W is —CH ₂ O— is shown in the following scheme. Compound (76) corresponds to formula (2-1), formula (2-3) and formula (2-6).

これらの式におけるＲは炭素数１〜１９のアルキルである。

R in these formulas is alkyl having 1 to 19 carbon atoms.

  For example, compound (71) can be synthesized according to Synlett 1999, No. It is synthesized by reacting compound (65) described in 4,389-396 with sec-butyllithium and then bromine. These reactions are preferably carried out in a solvent such as diethyl ether or an ether hydrocarbon such as tetrahydrofuran at a temperature between −100 ° C. and room temperature. Further, the compound (72) is synthesized by acting a compound (71) on a THF solution of cesium fluoride or tetrabutylammonium fluoride in N, N-dimethylformamide. Compound (73) is synthesized by reacting compound (72) with n-butyllithium and then a borate ester such as dimethylborate. Compound (74) is synthesized by allowing hydrogen peroxide to act on compound (73). Compound (76) can be synthesized by reacting compound (74) with a halide such as compound (75) under basic conditions.

Next, in the formula (2), n, p and q are 0, Rb is alkoxy, W is —COO—, —CF ₂ O—, — (CH ₂ ) ₂ CF ₂ O— or — (CH ₂ ) An example of the synthesis method regarding the compounds (77) to (80), which is ₃ O—, is shown. Compound (77) to compound (80) correspond to formula (2-1), formula (2-3), and formula (2-6).

これらの式におけるＲは炭素数１〜１９のアルキルである。

R in these formulas is alkyl having 1 to 19 carbon atoms.

  Compounds (77) to (80) are respectively synthesized by using compound (74) in place of the alcohol (phenol) intermediate in the above-described method for producing a linking group.

  Next, the composition of the present invention will be described in more detail. The components of this composition are compound (1) and compound (2), preferably a plurality of compounds selected from compound (1-1) to compound (1-9) and compound (2-1) to compound (2-9) Only the compound may be sufficient. A preferred composition contains at least one compound selected from compound (1-1) to compound (1-9) and compound (2-1) to compound (2-9) in a proportion of 1 to 99%. This composition also contains a component selected from the group consisting of compound (3) to compound (15). When preparing the composition, components are selected in consideration of the magnitude of the dielectric anisotropy of compound (1) and compound (2).

  A preferred composition containing a compound selected from the compound (1) and the compound (2) having a negative dielectric anisotropy and a medium value is as follows. This preferred composition contains at least one compound selected from the group consisting of compound (3), compound (4) and compound (5). Another preferred composition contains at least one compound selected from the group consisting of compound (6-1), compound (6-2) and compound (7). Another preferred composition contains at least two compounds selected from each of these two groups. These compositions are the compounds (13), (14) and (15) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from the group consisting of. These compositions may further contain at least one compound selected from the group consisting of compounds (8) to (12) for the purpose of further adjusting the physical properties. These compositions may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  Another preferred composition contains at least one compound selected from the group consisting of compound (13), compound (14) and compound (15). This composition may further contain at least one compound selected from the group consisting of compounds (8) to (12) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystalline compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  A preferred composition containing a compound selected from the compound (1) and the compound (2) exhibiting a large negative negative dielectric anisotropy is as follows. A preferred composition contains at least one compound selected from the group consisting of compound (8) to compound (13). This composition may further contain at least one compound selected from the group consisting of compound (13), compound (14) and compound (15). This composition may further contain at least one compound selected from the group consisting of compounds (3) to (7) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to VA devices and the like.

  Another preferred composition contains at least one compound selected from the group consisting of compound (13), compound (14) and compound (15). This composition may further contain at least one compound selected from the group consisting of compound (8) to compound (12). This composition may further contain at least one compound selected from the group consisting of compound (3) to compound (7). This composition may further contain compounds such as other liquid crystal compounds and additives.

  A preferred composition containing a compound selected from compound (1) and compound (2) having a negative dielectric anisotropy and a small numerical value is as follows. A preferred composition contains at least one compound selected from the group consisting of compound (3), compound (4) and compound (5). Another preferred composition contains at least one compound selected from the group consisting of compound (6-1), compound (6-2) and compound (7). Another preferred composition contains at least two compounds selected from each of the two such groups. These compositions are the compounds (13), (14) and (15) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from the group consisting of. This composition may further contain at least one compound selected from the group consisting of compounds (8) to (12) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystalline compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  Another preferred composition contains at least one compound selected from the group consisting of compound (8) to compound (12). This composition may further contain at least one compound selected from the group consisting of compound (13), compound (14) and compound (15). This composition may further contain at least one compound selected from the group consisting of compounds (3) to (7) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to VA devices and the like.

  Since the compound (3), the compound (4) and the compound (5) have a positive and large dielectric anisotropy, they are mainly used for a composition for an AM-TN device. In this composition, the amount of these compounds is 1-99%. A preferred amount is 10-97%. A more preferred amount is 40 to 95%. When compound (13), compound (14) or compound (15) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  Since the compound (6-1), the compound (6-2), and the compound (7) have a large dielectric anisotropy and are very large, they are mainly used in compositions for STN devices. In this composition, the amount of these compounds is 1-99%. A preferred amount is 10-97%. A more preferred amount is 40 to 95%. When compound (13), compound (14) or compound (15) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  Since the compound (8) to the compound (12) have a negative dielectric anisotropy, they are mainly used for a composition for a VA device. The preferred amount of these compounds is 80% or less. A more preferred amount is 40 to 80%. When compound (13), compound (14) or compound (15) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  The dielectric anisotropy of the compound (13), the compound (14) and the compound (15) is small. Compound (13) is mainly used for the purpose of adjusting viscosity or optical anisotropy. The compounds (14) and (15) are used for the purpose of increasing the maximum temperature to widen the temperature range of the liquid crystal phase or adjusting the optical anisotropy. Increasing the amount of compound (13), compound (14) and compound (15) increases the threshold voltage of the composition and decreases the viscosity. Accordingly, a large amount may be used as long as the threshold voltage requirement of the composition is satisfied.

  Preferred examples of compound (3) to compound (15) include compound (3-1) to compound (3-9), compound (4-1) to compound (4-97), and compound (5-1) to compound. (5-33), Compound (6-1) to Compound (6-56), Compound (7-1) to Compound (7-3), Compound (8-1) to Compound (8-4), Compound ( 9-1) to Compound (9-6), Compound (10-1) to Compound (10-4), Compound (11-1), Compound (12-1), Compound (13-1) to Compound (13) -14), compound (14-1) to compound (14-31), and compound (15-1) to compound (15-6). The symbols in these compounds have the same meaning as the respective symbols in compound (3) to compound (15).

  The composition of the present invention is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating. Appropriate additives may be added to the composition to adjust the physical properties of the composition. Such additives are well known to those skilled in the art. A composition for a GH device may be prepared by adding a dichroic dye which is a compound such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. On the other hand, a chiral dopant is added for the purpose of inducing a helical structure of the liquid crystal to give a necessary twist angle. Examples of the chiral dopant are the following optically active compounds (Op-1) to (Op-13).

  When adding a chiral dopant to the composition to adjust the twist pitch, the preferred pitch for TN devices and TN-TFT devices is in the range of 40-200 μm; the preferred pitch for STN devices is in the range of 6-20 μm. Yes: The preferred pitch for BTN devices is in the range of 1.5-4 μm: A relatively large amount of chiral dopant is added to the composition for PC devices. For the purpose of adjusting the temperature dependence of the pitch, at least two chiral dopants may be added.

  The composition of the present invention can be used for devices such as PC, TN, STN, BTN, ECB, OCB, IPS, and VA. These elements may be driven by PM or AM. NCAP (nematic curvilinear aligned phase) elements produced by microencapsulating this composition, and PD (polymer dispersed) elements in which a three-dimensional network polymer is formed in the composition, for example, PN (polymer network) elements Can also be used.

  Next, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples. No. Compound numbers such as 1 correspond to those of the compounds shown in the table in Example 10. The obtained compound is identified by a nuclear magnetic resonance analysis spectrum, a mass spectrum or the like. In a nuclear magnetic resonance analysis spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. The amount (percentage) of the compound is% by weight based on the total weight of the composition. The physical property values are measured according to the method described in Standard of Electronic Industries Association of Japan, EIAJ ED-2521A, or a modified method thereof.

  The ratio (percentage) of the component or the liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound. The composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component. However, it is not easy to accurately calculate the ratio of components by gas chromatographic analysis of the composition. This is because the correction coefficient depends on the type of liquid crystal compound. Fortunately, the correction factor is approximately 1. Furthermore, the influence of the 1% by weight difference in the component compounds on the properties of the composition is small. Therefore, in the present invention, the area ratio of the component peak in the gas chromatograph can be regarded as the weight percent of the component compound. In other words, the result of gas chromatographic analysis (peak area ratio) can be considered to be equivalent to the weight percent of the liquid crystal compound without correction.

  In the measurement of characteristic values, there are three methods: when a single compound is used as it is as a sample, when a compound is mixed with mother liquid crystals and used as a sample, and when a composition is used as a sample as it is. When the compound is mixed with the mother liquid crystal, the following method is taken. Samples were prepared by mixing 15 wt% compound and 85 wt% mother liquid crystals. The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15. When the smectic phase (or crystal) precipitates at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed.

  Among the values obtained by measurement, the values obtained using the compound alone as a sample and the values obtained using the composition as a sample are described as experimental data. Values obtained by mixing a compound with mother liquid crystals and used as a sample may be described as experimental data as they are, or may be described as values obtained by extrapolation.

  When a compound is mixed with mother liquid crystals and used as a sample, there are a plurality of mother liquid crystals. An example of the mother liquid crystal is mother liquid crystal A. The composition of the mother liquid crystal A is as follows.

Mother liquid crystal A:

[Transition temperature of liquid crystal phase (℃)]
Measurement was performed by one of the following methods.
1) A sample was placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which the sample changed phase was measured.
2) Using a scanning calorimeter DSC-7 system manufactured by PerkinElmer, the measurement was performed at a rate of 3 ° C / min.

[Identification of liquid crystal phase and notation of phase sequence]
The crystal was represented as C. If a crystal is distinguished into two crystals, it is denoted as C ₁ or C _2, respectively. The smectic phase was represented as S. The liquid (isotropic) was expressed as Iso. The nematic phase was represented as N. In the smectic phase, when a smectic B phase, a smectic C phase or a smectic A phase can be distinguished, they are represented as S _B , S _C or S _A , respectively. As a notation of transition temperature, “C 92.9 N 196.9 Iso” means that the transition temperature (CN) from the crystal to the nematic phase is 92.9 ° C., and the transition temperature from the nematic phase to the liquid (NI). Is 196.9 ° C. The same applies to other notations.

[Maximum temperature of nematic phase (NI; ° C)]
A sample is placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature is measured when a part of the sample changes from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

[Minimum temperature of a nematic phase _{(T C;} ℃)]
A sample having a nematic phase is stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase is observed. For example, remains of the sample -20 ° C. in a nematic phase, when the change in the -30 ° C. crystals (or a smectic phase), is described as <-20 ° C. The _{T C.} The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

[Compatibility of compounds]
A mother liquid crystal having a nematic phase is prepared by mixing several compounds having a similar structure. A composition in which the compound to be measured and this mother liquid crystal are mixed is obtained. An example of the mixing ratio is 15% compound and 85% mother liquid crystal. This composition is stored at a low temperature such as −20 ° C. and −30 ° C. for 30 days. It is observed whether a part of this composition has changed to a crystal (or smectic phase). Change the mixing ratio and storage temperature as necessary. From the measurement results, conditions for precipitating crystals (or smectic phases) and conditions for precipitating crystals (or smectic phases) are determined. These conditions are a measure of compatibility.

[Viscosity (η; measured at 20 ° C .; mPa · s)]
An E-type viscometer is used for measuring the viscosity.

[Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.)]
The measurement was performed with an Abbe refractometer using light having a wavelength of 589 nm and a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index n‖ was measured when the polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the equation: Δn = n∥−n⊥.

[Dielectric anisotropy (Δε; measured at 25 ° C.)]
1) Sample with positive dielectric anisotropy: A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

2) Sample with negative dielectric anisotropy: A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

[Threshold voltage (Vth; measured at 25 ° C .; V)]
(1) Composition having positive dielectric anisotropy Normally white mode (normally white mode) in which the distance (gap) between two glass substrates is (0.5 / Δn) μm and the twist angle is 80 degrees. A sample is put in a liquid crystal display element in white mode. Δn is a value of optical anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz is applied to this element. The voltage of the rectangular wave is increased, and the value of the voltage when the transmittance of light passing through the element reaches 90% is measured.
(2) Composition having a negative dielectric anisotropy In a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 μm and processed into homeotropic alignment Put the sample. A rectangular wave having a frequency of 32 Hz is applied to this element. The voltage of the rectangular wave is increased, and the value of the voltage when the transmittance of light passing through the element becomes 10% is measured.

[Proton Nuclear Magnetic Resonance Analysis ( ¹ H-NMR)]
For the measurement, DRX-500 (manufactured by Bruker Biospin Co., Ltd.) was used. A solution in which a deuterated sample such as CDCl ₃ was dissolved in a solvent was measured using a nuclear magnetic resonance apparatus at room temperature. Tetramethylsilane (TMS) was used as the reference material having zero value of δ value.

[Gas chromatogram (GC) analysis]
For the measurement, a GC-14B gas chromatograph manufactured by Shimadzu Corporation was used. The carrier gas is helium (2 ml / min). The sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by weight), and 1 μl thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used. The area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. The weight percentage of the component compounds is not completely the same as the area ratio of each peak. However, in the present invention, when these capillary columns are used, the weight percentage of the component compounds may be regarded as the same as the area ratio of each peak. This is because there is no significant difference in the correction coefficients of the component compounds.

Synthesis of 4- (4-propylcyclohexyl) cyclohexyl-2-fluoro-3-difluoromethyl-ethoxybenzene (Compound No. 1-3-1)

The THF solution of 2-fluoro-4-ethoxybromobenzene is dripped at 40-60 degreeC to the shaved magnesium dried at the 1st process. To this solution, a THF solution of 4- (propylcyclohexyl) cyclohexanone is added dropwise at 40-60 ° C., and the mixture is further stirred for 2 hours. The reaction mixture is poured into saturated aqueous ammonium chloride and extracted with toluene. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting crude 1-hydroxy-4- (4-propylcyclohexyl) cyclohexyl-2-fluoroethoxybenzene is used in the second step without purification.

Second Step The crude 1-hydroxy-4- (4-propylcyclohexyl) cyclohexyl-2-fluoroethoxybenzene obtained in the first step is dissolved in toluene. Add p-toluenesulfonic acid monohydrate and heat to reflux for 2 hours while dehydrating using a Dean-Stark apparatus. The reaction mixture is poured into saturated aqueous sodium hydrogen carbonate and extracted with toluene. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography to obtain 4- (4-propylcyclohexyl) cyclohexenyl-2-fluoroethoxybenzene.

Third Step 4- (4-Propylcyclohexyl) cyclohexenyl-2-fluoroethoxybenzene obtained in the second step is dissolved in a toluene-solmix mixed solvent. Raney nickel catalyst is added to this solution under a nitrogen atmosphere, and a hydrogenation reaction is performed at room temperature and pressure for 2 days. After the reaction is complete, the catalyst is removed by filtration. The filtrate is concentrated under reduced pressure, and the residue is purified by silica gel column chromatography to obtain 4- (4-propylcyclohexyl) cyclohexyl-2-fluoroethoxybenzene. This is further purified by repeated recrystallization to obtain pure 4- (4-propylcyclohexyl) cyclohexyl-2-fluoroethoxybenzene.

Fourth Step 4- (4-Propylcyclohexyl) cyclohexyl-2-fluoroethoxybenzene obtained in the third step is dissolved in terahydrofuran and cooled to −70 ° C. under an acetone-dry ice refrigerant in a nitrogen atmosphere. To this solution, sec-butyllithium (cyclohexane, n-hexane solution) is added dropwise under a nitrogen atmosphere, and the mixture is stirred at −65 ° C. or lower for 2 hours. Subsequently, dimethylformamide is dripped at -65 degreeC, and is stirred for 2 hours after dripping. The reaction mixture is poured into saturated aqueous ammonium chloride and extracted with hexane. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give 4- (4-propylcyclohexyl) cyclohexyl-2- Fluoro-3-formylethoxybenzene is obtained.

Fifth Step 4- (4-Propylcyclohexyl) cyclohexyl-2-fluoro-3-formylethoxybenzene obtained in the fourth step was dissolved in dichloromethane and cooled to 0 ° C. in a nitrogen atmosphere, followed by diethylaminosulfur trifluoride (DAST). ) And further stirred at room temperature for 20 hours. The solution is poured into aqueous sodium bicarbonate and extracted with heptane. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give 4- (4-propylcyclohexyl) cyclohexyl-2- Fluoro-3-difluoromethyl-ethoxybenzene is obtained. This is further purified by repeated recrystallization to give pure 4- (4-propylcyclohexyl) cyclohexyl-2-fluoro-3-difluoromethyl-ethoxybenzene.

Synthesis of 4- (4-propylcyclohexyl) phenyl-2-fluoro-3-difluoromethyl-ethoxybenzene (Compound No. 1-3-5)

First Step 100 ml of a THF solution of 22.8 g (104 mmol) of 3-fluoro-4-ethoxybromobenzene was added dropwise at 40 to 60 ° C. with stirring to 3.03 g (124.8 mmol) of dried shaved magnesium. It heated and refluxed for 1 hour after dripping. This solution was cooled to −70 ° C. with a refrigerant, and a THF solution (THF 70 ml) of trimethyl borate 16 ml (135.2 mmol) was added dropwise with stirring. After stirring at −70 ° C. for 3 hours and further stirring at room temperature for 20 hours, the reaction solution was cooled to 5 ° C. and 50 ml of 6M hydrochloric acid was added. After separating the organic layer, the aqueous layer was extracted with 100 ml of ethyl acetate. The organic layer was mixed, washed with water and saturated brine successively, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and crude 3 22.3 g of fluoro-4-ethoxyphenylboronic acid was obtained. The obtained boric acid derivative was used in the second step without purification.

Second Step 22.3 g of the crude 3-fluoro-4-ethoxyphenylboronic acid obtained in the first step was dissolved in 200 ml of tetrahydrofuran, and 23.6 g of 30% hydrogen peroxide solution was maintained at around 35 ° C. in a warm bath ( 208 mmol) was added. After the addition, the reaction solution was stirred at room temperature for 24 hours, and then the reaction solution was poured into 300 ml of water, then sodium bisulfite was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was extracted with 300 ml of ethyl acetate, and the extracted layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as an eluent to obtain 17.6 g (113 mmol) of 3-fluoro-4-ethoxyphenol.

Third Step Under a nitrogen atmosphere, 17.1 g (109 mmol) of 3-fluoro-4-ethoxyphenol obtained in the second step was added to a suspension of 5.2 g (130.8 mmol) of sodium hydride in THF (170 ml). The solution was dropped between 10 ° C. and stirred at the same temperature for 30 minutes. Next, a solution of 9.9 ml (130.8 mmol) of chloromethyl methyl ether in THF (10 ml) was added dropwise at 5 to 10 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water and extracted with 300 ml of heptane. The extract layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as an eluent to obtain 16.5 g of 3-fluoro-4-ethoxyphenyl = methoxymethyl ether.

Fourth Step 16 g (79.9 mmol) of 3-fluoro-4-ethoxyphenyl = methoxymethyl ether obtained in the third step was dissolved in 160 ml of terahydrofuran and dissolved in an acetone-dry ice refrigerant to -70 ° C. under a nitrogen atmosphere. Cooled down. To this solution, 89 ml (87.9 mmol) of sec-butyllithium (0.99 M, cyclohexane, n-hexane solution) was added dropwise under a nitrogen atmosphere, and the mixture was stirred at −70 ° C. for 1 hour. Next, 6.8 ml (87.9 mmol) of dimethylformamide was added dropwise at −70 ° C., and the mixture was stirred at the same temperature for 2 hours after the addition. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with 300 ml of hexane. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as an eluent. The product was purified to obtain 16.5 g of 2-formyl-3-fluoro-4-ethoxyphenyl = methoxymethyl ether.

Fifth Step 8 g (35 mmol) of 2-formyl-3-fluoro-4-ethoxyphenyl = methoxymethyl ether obtained in the fourth step was dissolved in 80 ml of dichloromethane, cooled to 0 ° C. in a nitrogen atmosphere, and then diethylaminosulfur trifluoride. (DAST) 9.5 ml (71.8 mmol) was added, and the mixture was further stirred at room temperature for 20 hours. This solution was poured into an aqueous sodium hydrogen carbonate solution and extracted with 200 ml of heptane. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as a developing solvent. Get. This was further purified by repeated crystallization to obtain 7.6 g of 2-difluoromethyl-3-fluoro-4-ethoxyphenyl = methoxymethyl ether.

Sixth Step 7.5 g (30 mmol) of 2-difluoromethyl-3-fluoro-4-ethoxyphenyl = methoxymethyl ether obtained in the fifth step was dissolved in 30 ml of ethanol and stirred at room temperature with 30 ml (60 mmol) of 2M hydrochloric acid. Was added and heated to reflux for 2 hours after the addition. The reaction mixture was poured into water and extracted with 150 ml of ethyl acetate, and the organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as an eluent to obtain 6.0 g of 2-difluoromethyl-3-fluoro-4-ethoxyphenol.

Seventh step 2.5 g (12 mmol) of 2-difluoromethyl-3-fluoro-4-ethoxyphenol obtained in the sixth step and 2 ml of pyridine were dissolved in 50 ml of dichloromethane, and trifluoromethanesulfonic anhydride was added at a nitrogen atmosphere of 5 to 10 ° C. 2.6 ml (15.6 mmol) was added and stirred at the same temperature for 1.5 hours. The reaction mixture was poured into an aqueous sodium hydrogen carbonate solution and extracted with 100 ml of dichloromethane. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude triflate derivative. The crude triflate derivative (5.5 g) obtained was 3.2 g (13.2 mmol) 4- (propylcyclohexyl) phenylboric acid, 1.6 g (13.2 mmol) potassium bromide, 5.1 g (24 mmol) potassium phosphate. Then, 50 ml of dioxane and 0.4 g (0.3 mmol) of tetrakistriphenylphosphine palladium as a coupling catalyst were mixed and heated to reflux for 5 hours. The reaction mixture was poured into water and extracted with 100 ml of toluene, and then the organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / heptane as an eluent, and further purified by repeating recrystallization from a mixed solvent of heptane / ethanol to obtain pure 4- (4-propylcyclohexyl). ) Phenyl-2-fluoro-3-difluoromethyl-ethoxybenzene was obtained. The melting point of this compound was 82.2 ° C.

Synthesis of 4- (4-propylcyclohexyl) methyl = 2-fluoro-3-difluoromethyl-4-methylphenyl ether (Compound No. 1-2-8)

First Step Under a nitrogen atmosphere, 2-fluoro-4-methylphenol is added dropwise to a THF suspension of sodium hydride at around 5 ° C. and stirred at the same temperature for 30 minutes. Next, a THF solution of chloromethyl methyl ether is added dropwise at around 5 ° C., and the mixture is stirred at room temperature for 2 hours after the addition. The reaction mixture is poured into ice water and extracted with heptane. The extract layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting concentrated residue is purified by silica gel column chromatography to obtain 2-fluoro-4-methylphenyl = methoxymethyl ether.

Second Step 2-Fluoro-4-methylphenyl = methoxymethyl ether obtained in the first step is dissolved in terahydrofuran and cooled to −70 ° C. in an acetone-dry ice refrigerant under a nitrogen atmosphere. To this solution, sec-butyllithium is added dropwise under a nitrogen atmosphere, and the solution is stirred at -70 ° C for 1 hour. Subsequently, dimethylformamide is dripped at -70 degreeC, and is stirred at the same temperature for 2 hours after dripping. The reaction mixture is poured into saturated aqueous ammonium chloride and extracted with hexane. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue is purified by silica gel column chromatography to obtain 2-fluoro-3-formyl-4-methylphenyl = methoxymethyl ether.

Third Step 2-Fluoro-3-formyl-4-methylphenyl = methoxymethyl ether obtained in the second step is dissolved in dichloromethane and cooled to 0 ° C. in a nitrogen atmosphere, and then diethylaminosulfur trifluoride (DAST) is added. The mixture is further stirred at room temperature for 20 hours. The solution is poured into an aqueous sodium bicarbonate solution and extracted with heptane. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography to obtain 2-fluoro-3-difluoromethyl-4-methylphenyl = methoxymethyl ether.

Fourth Step 2-Fluoro-3-difluoromethyl-4-methylphenyl methoxymethyl ether obtained in the third step is dissolved in ethanol, 2M hydrochloric acid is added with stirring at room temperature, and the mixture is heated to reflux for 2 hours after the addition. . The reaction mixture is poured into water and extracted with ethyl acetate. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography to obtain 2-fluoro-3-difluoromethyl-4-methylphenol.

Step 5 2-Fluoro-3-difluoromethyl-4-methylphenol obtained in Step 4 is mixed in DMF with 4-propylcyclohexyliodomethane and potassium carbonate in a nitrogen atmosphere and stirred with heating at 100 ° C. for 8 hours. . The reaction mixture is poured into water and extracted with toluene. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography, and further purified by repeating recrystallization to obtain pure 4- (4-propylcyclohexyl) methyl = 2-fluoro-3-difluoromethyl-4-methylphenyl ether. .

Synthesis of 4-pentyl-2′-difluoromethyl-3′-fluoro-4 ″ -ethylterphenyl (Compound No. 1-4-6)

First Step 4-Ethylphenylboric acid is mixed with 3-fluoro-4-iodoanisole, potassium carbonate and tetrakistriphenylphosphine palladium as a coupling catalyst in a toluene / ethanol mixed solvent and heated to reflux for 8 hours. The reaction mixture is poured into water and extracted with 100 ml of toluene, and the organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography, and further purified by repeating recrystallization to obtain pure 3-fluoro-4- (4-ethylphenyl) anisole.

Second Step 3-Fluoro-4- (4-ethylphenyl) anisole obtained in the first step is dissolved in dichloromethane, cooled to −60 ° C. under a refrigerant, and boron tribromide is added dropwise. After dropping, the mixture is stirred for 2 hours at the same temperature, and further stirred at room temperature for 8 hours. The reaction mixture is poured into water, and the dichloromethane layer is separated. The dichloromethane layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography to obtain 3-fluoro-4- (4-ethylphenyl) phenol.

Third Step Under a nitrogen atmosphere, 3-fluoro-4- (4-ethylphenyl) phenol obtained in the second step is added dropwise to a THF suspension of sodium hydride at around 5 ° C. and stirred at the same temperature for 30 minutes. . Next, a THF solution of chloromethyl methyl ether is added dropwise at around 5 ° C., and the mixture is stirred at room temperature for 2 hours after the addition. The reaction mixture is poured into ice water and extracted with heptane. The extract layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting concentrated residue is purified by silica gel column chromatography to obtain 3-fluoro-4- (4-ethylphenyl) phenyl = methoxymethyl ether.

Fourth Step 3-Fluoro-4- (4-ethylphenyl) phenyl methoxymethyl ether obtained in the third step is dissolved in terahydrofuran and cooled to −70 ° C. under an acetone-dry ice refrigerant in a nitrogen atmosphere. . To this solution, sec-butyllithium is added dropwise under a nitrogen atmosphere, and the solution is stirred at -70 ° C for 1 hour. Subsequently, dimethylformamide is dripped at -70 degreeC, and is stirred at the same temperature for 2 hours after dripping. The reaction mixture is poured into saturated aqueous ammonium chloride and extracted with hexane. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue is purified by silica gel column chromatography to obtain 2-formyl-3-fluoro-4- (4-ethylphenyl) phenyl = methoxymethyl ether.

Fifth Step 2-Formyl-3-fluoro-4- (4-ethylphenyl) phenyl = methoxymethyl ether obtained in the fourth step was dissolved in dichloromethane and cooled to 0 ° C. in a nitrogen atmosphere, and then diethylaminosulfur trifluoride. (DAST) is added and further stirred at room temperature for 20 hours. The solution is poured into an aqueous sodium bicarbonate solution and extracted with heptane. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography to obtain 2-difluoromethyl-3-fluoro-4- (4-ethylphenyl) phenyl = methoxymethyl ether.

Step 6 2-Difluoromethyl-3-fluoro-4- (4-ethylphenyl) phenyl methoxymethyl ether obtained in Step 5 was dissolved in ethanol, and 2M hydrochloric acid was added with stirring at room temperature. Heat to reflux for 2 hours. The reaction mixture is poured into water and extracted with ethyl acetate. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography to obtain 2-difluoromethyl-3-fluoro-4- (4-ethylphenyl) phenol.

Seventh Step 2-Difluoromethyl-3-fluoro-4- (4-ethylphenyl) phenol and pyridine obtained in the sixth step are dissolved in dichloromethane, and trifluoromethanesulfonic anhydride is added in the vicinity of 5 ° C. under a nitrogen atmosphere. Stir at the same temperature for 2 hours. The reaction mixture is poured into an aqueous sodium hydrogen carbonate solution and extracted with dichloromethane. The organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude triflate derivative. The resulting crude triflate derivative is mixed with 4-pentylphenylboric acid, potassium bromide, and potassium phosphate in dioxane, tetrakistriphenylphosphine palladium is added as a coupling catalyst, and the mixture is heated to reflux for 8 hours. The reaction mixture is poured into water and extracted with toluene, and the organic layer is washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography, and further purified by repeated recrystallization to obtain pure 4-pentyl-2′-difluoromethyl-3′-fluoro-4 ″ -ethylterphenyl.

Synthesis of β- (4- (4-propylcyclohexyl) cyclohexyl) -2-difluoromethyl-3-fluoro-4-ethoxystyrene (Compound No. 1-3-15)

First Step 30 ml of a THF solution of 15.0 g (68.5 mmol) of 3-fluoro-4-ethoxybromobenzene was added dropwise at 40 to 60 ° C. with stirring to 1.8 g (75.4 mmol) of dried shaved magnesium. did. Next, 100 ml of a THF solution of 22.3 g (89.1 mmol) of (4- (4-propylcyclohexyl) cyclohexyl) acetaldehyde was added dropwise to this solution and stirred for 2 hours. The reaction mixture was poured into 100 ml of saturated aqueous ammonium chloride and extracted with 200 ml of toluene. The organic layer was washed successively with 100 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and crude 1-hydroxy-1- (3-fluoro-4-ethoxyphenyl) -2- 25.9 g of (4- (4-propylcyclohexyl) cyclohexyl) ethane was obtained.

Second Step 25.9 g of crude 1-hydroxy-1- (3-fluoro-4-ethoxyphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethane obtained in the first step was dissolved in toluene. did. 0.8 g (4 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux for 2 hours while dehydrating using a Dean-Stark apparatus. The reaction mixture was poured into 200 ml of saturated sodium bicarbonate water and extracted with 200 ml of toluene. The organic layer was washed successively with 200 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane / toluene = 8/2) and recrystallized from heptane to obtain β- (4- (4-propylcyclohexyl) cyclohexyl) -3-fluoro-4- 13.2 g of ethoxystyrene was obtained.

Third Step β- (4- (4-Propylcyclohexyl) cyclohexyl) -3-fluoro-4-ethoxystyrene 13.2 g (35.4 mmol) obtained in the second step was dissolved in 150 ml of THF and acetone was added in a nitrogen atmosphere. -Cooled to -70 ° C under dry ice refrigerant. To this solution, 46 ml (46 mmol) of sec-butyllithium (cyclohexane, 1M n-hexane solution) was added dropwise under a nitrogen atmosphere, and the mixture was stirred at −65 ° C. or lower for 2 hours. Next, 7.8 g (106.2 mmol) of dimethylformamide was added dropwise at −65 ° C., followed by further stirring for 2 hours. The reaction mixture was poured into 200 ml of saturated aqueous ammonium chloride and extracted with 200 ml of heptane. The organic layer was washed successively with 300 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: heptane / toluene = 7/3). Β- (4- (4-propylcyclohexyl) cyclohexyl) -2-formyl-3-fluoro-4-ethoxystyrene was obtained.

Step 4 β- (4- (4-propylcyclohexyl) cyclohexyl) -2-formyl-3-fluoro-4-ethoxystyrene 5.5 g (13.7 mmol) obtained in Step 3 was dissolved in 100 ml of dichloromethane. After cooling to 0 ° C. under a nitrogen atmosphere, 6.6 g (41.1 mmol) of diethylaminosulfur trifluoride (DAST) was added, and the mixture was further stirred at room temperature for 20 hours. This solution was poured into 300 ml of saturated aqueous sodium hydrogen carbonate solution and extracted with 200 ml of heptane. The organic layer was washed successively with 300 ml of water and 200 ml of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane / toluene = 9/1) and recrystallized twice from a mixed solvent of heptane / ethanol to obtain pure β- (4- (4-propylcyclohexyl). 2.1 g of cyclohexyl) -2-difluoromethyl-3-fluoro-4-ethoxystyrene was obtained. This compound exhibits a liquid crystal phase, and its transition point is as follows.
C 69.0 N 168.7 Iso
¹ H-NMR (CDCl ₃ ): δ (ppm); 7.23 (d, 1H), 7.02 (t, 1H), 6.97 (t, 1H), 6.71 (d, 1H), 6.00 (dd, 1H), 4.10 (q, 2H), 2.09-2.04 (m, 1H), 1.86-1.70 (m, 8H), 1.44 (t, 3H), 1.34-1.27 (m, 2H), 1.17-0.94 (m, 11H), 0.87 (t, 3H), 0.89-0.81 (m, 2H) .

実施例５で得られるβ−（４−（４−プロピルシクロヘキシル）シクロヘキシル）−２−ジフルオロメチル−３−フルオロ−４−エトキシスチレン１．６ｇをトルエン−ソルミックス混合溶媒２５ｍＬに溶解した。この溶液に窒素雰囲気下にてパラジウム炭素触媒を加え、常温常圧にて２日間水素添加反応を行った。反応終了後、触媒を濾過により除去した。濾液を減圧下に濃縮し、残さを（溶離液：ヘプタン／トルエン＝９／１）にて精製し、１−（２−ジフルオロメチル−３−フルオロ−４−エトキシフェニル）−２−（４−（４−プロピルシクロヘキシル）シクロヘキシル）エタンを得る。このものをさらにヘプタン／エタノール混合溶媒から２回再結晶し、純粋な１−（２−ジフルオロメチル−３−フルオロ−４−エトキシフェニル）−２−（４−（４−プロピルシクロヘキシル）シクロヘキシル）エタンを得た。この化合物は液晶相を示し、その転移点は以下の通りであった。
Ｃ ７６．６ （ＳｍＡ ４９．１） Ｎ １２０．４ Ｉｓｏ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：δ（ｐｐｍ）；７．０２（ｔ，１Ｈ）、７．００（ｄ，１Ｈ）、６．９６（ｔ，１Ｈ）、４．１１（ｑ，２Ｈ）、１．８６−１．７１（ｍ，８Ｈ）、１．４６（ｔ，３Ｈ）、１．３７−１．１５（ｍ，６Ｈ）、１．０４−０．９３（ｍ，８Ｈ）、０．９０（ｔ，３Ｈ）、０．９１−０．８３（ｍ，２Ｈ）． Synthesis of 1- (2-difluoromethyl-3-fluoro-4-ethoxyphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethane (Compound No. 1-3-13)

1.6 g of β- (4- (4-propylcyclohexyl) cyclohexyl) -2-difluoromethyl-3-fluoro-4-ethoxystyrene obtained in Example 5 was dissolved in 25 mL of a toluene-solmix mixed solvent. A palladium carbon catalyst was added to this solution in a nitrogen atmosphere, and a hydrogenation reaction was performed at room temperature and normal pressure for 2 days. After completion of the reaction, the catalyst was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was purified with (eluent: heptane / toluene = 9/1) to give 1- (2-difluoromethyl-3-fluoro-4-ethoxyphenyl) -2- (4- (4-Propylcyclohexyl) cyclohexyl) ethane is obtained. This was further recrystallized twice from a heptane / ethanol mixed solvent to obtain pure 1- (2-difluoromethyl-3-fluoro-4-ethoxyphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethane. Got. This compound showed a liquid crystal phase, and its transition point was as follows.
C 76.6 (SmA 49.1) N 120.4 Iso
¹ H NMR (CDCl ₃ ): δ (ppm); 7.02 (t, 1H), 7.00 (d, 1H), 6.96 (t, 1H), 4.11 (q, 2H), 1 .86-1.71 (m, 8H), 1.46 (t, 3H), 1.37-1.15 (m, 6H), 1.04-0.93 (m, 8H), 0.90 (T, 3H), 0.91-0.83 (m, 2H).

Synthesis of β- (4- (4-propylcyclohexyl) cyclohexyl) -2-trifluoromethyl-3-fluoro-4-ethoxystyrene (Compound No. 2-3-3-3)

First Step 10.0 g (35.7 mmol) of 2-fluoro-2-trifluoromethyl-6-trimethylsilylethoxybenzene in which 42.4 mL of sec-butyllithium (1.0 mol / L) was dissolved in 60 mL of THF under a nitrogen atmosphere. The solution was added dropwise at −78 ° C. and stirred at the same temperature for 2 hours. Next, 22 ml of a THF solution of 10.7 g (42.8 mmol) of (4- (4-propylcyclohexyl) cyclohexyl) acetaldehyde was added dropwise to this solution and stirred at the same temperature for 1 hour, then warmed to room temperature and stirred overnight. . The reaction mixture was poured into 100 ml of saturated aqueous ammonium chloride and extracted with 200 ml of toluene. The organic layer was washed successively with 100 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and crude 1-hydroxy-1- (2-trifluoromethyl-3-fluoro-4- 20.7 g of ethoxy-5-trimethylsilylphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethane was obtained.

Second Step Crude 1-hydroxy-1- (2-trifluoromethyl-3-fluoro-4-ethoxy-5-trimethylsilylphenyl) -2- (4- (4-propylcyclohexyl) obtained in the first step (Cyclohexyl) ethane (20.7 g) was dissolved in toluene. 0.68 g (3.57 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated to reflux for 2 hours while dehydrating using a Dean-Stark apparatus. The reaction mixture was poured into 200 ml of saturated sodium bicarbonate water and extracted with 200 ml of toluene. The organic layer was washed successively with 200 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and crude β- (4- (4-propylcyclohexyl) cyclohexyl) -2-trifluoromethyl. 16.03 g of -3-fluoro-4-ethoxy-5-trimethylsilylstyrene was obtained.

Step 3 Crude β- (4- (4-propylcyclohexyl) cyclohexyl) -2-trifluoromethyl-3-fluoro-4-ethoxy-5-trimethylsilylstyrene (16.03 g) was dissolved in THF (35 mL), and tetrabutyl was added thereto. 23.4 mL of ammonium fluoride / THF solution (1 mol / L) was added dropwise and stirred for 2 hours. The reaction solution was poured into 100 mL of water and extracted with 200 mL of toluene. The organic layer was washed with 100 mL of saturated brine and dried over anhydrous magnesium sulfate. The residue was purified by silica gel column chromatography (eluent: heptane / toluene = 8/2), recrystallized twice from a heptane / ethanol mixed solvent, and β- (4- (4-propylcyclohexyl) cyclohexyl)- 7.89 g of 2-trifluoromethyl-3-fluoro-4-ethoxystyrene was obtained. This compound showed a liquid crystal phase, and its transition point was as follows.
C 83.0 N 149.3 Iso
¹ H-NMR (CDCl ₃ ): δ (ppm); 7.17 (d, 1H), 7.01 (t, 1H), 6.59 (d, 1H), 5.91 (dd, 1H), 4.09 (q, 2H), 2.07-2.01 (m, 1H), 1.85-1.70 (m, 8H), 1.44 (t, 3H), 1.34-1. 27 (m, 2H), 1.15-0.93 (m, 11H), 0.87 (t, 3H), 0.89-0.81 (m, 2H).

実施例７で得られたβ−（４−（４−プロピルシクロヘキシル）シクロヘキシル）−２−トリフルオロメチル−３−フルオロ−４−エトキシスチレン７．８９ｇをトルエン−ソルミックス混合溶媒２００ｍＬに溶解した。この溶液に窒素雰囲気下にてパラジウム炭素触媒を加え、常温常圧にて２日間水素添加反応を行った。反応終了後、触媒を濾過により除去した。濾液を減圧下に濃縮し、残さをシリカゲルカラムクロマトグラフィー（溶離液：ヘプタン：トルエン＝４：１）にて精製し、１−（２−トリフルオロメチル−３−フルオロ−４−エトキシフェニル）−２−（４−（４−プロピルシクロヘキシル）シクロヘキシル）エタンを得る。このものをさらにヘプタン／エタノール混合溶媒から２回再結晶し、純粋な１−（２−トリフルオロメチル−３−フルオロ−４−エトキシフェニル）−２−（４−（４−プロピルシクロヘキシル）シクロヘキシル）エタン５．３５ｇを得た。この化合物は液晶相を示し、その転移点は以下の通りであった。
Ｃ ６８．０ （ＳｍＡ ４４．９） Ｎ １１２．８ Ｉｓｏ
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ（ｐｐｍ）；７．０１（ｔ，１Ｈ）、６．９２（ｄ，１Ｈ）、４．０８（ｑ，２Ｈ）、２．６９（ｍ，２Ｈ）、１．８１−１．６８（ｍ，８Ｈ）、１．４３（ｔ，３Ｈ）、１．４５−１．３９（ｍ，２Ｈ）、１．３３−１．１２（ｍ，６Ｈ）、１．００−０．９２（ｍ，８Ｈ）、０．８７（ｔ，３Ｈ）、０．９０−０．８０（ｍ，２Ｈ）． Synthesis of 1- (2-trifluoromethyl-3-fluoro-4-ethoxyphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethane (Compound No. 2-3-12)

Β- (4- (4-Propylcyclohexyl) cyclohexyl) -2-trifluoromethyl-3-fluoro-4-ethoxystyrene (7.89 g) obtained in Example 7 was dissolved in 200 mL of a toluene-solmix mixed solvent. A palladium carbon catalyst was added to this solution in a nitrogen atmosphere, and a hydrogenation reaction was performed at room temperature and normal pressure for 2 days. After completion of the reaction, the catalyst was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: heptane: toluene = 4: 1) to give 1- (2-trifluoromethyl-3-fluoro-4-ethoxyphenyl)- 2- (4- (4-Propylcyclohexyl) cyclohexyl) ethane is obtained. This was further recrystallized twice from a heptane / ethanol mixed solvent to obtain pure 1- (2-trifluoromethyl-3-fluoro-4-ethoxyphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl). 5.35 g of ethane was obtained. This compound showed a liquid crystal phase, and its transition point was as follows.
C 68.0 (SmA 44.9) N 112.8 Iso
¹ H-NMR (CDCl ₃ ): δ (ppm); 7.01 (t, 1H), 6.92 (d, 1H), 4.08 (q, 2H), 2.69 (m, 2H), 1.81-1.68 (m, 8H), 1.43 (t, 3H), 1.45-1.39 (m, 2H), 1.33-1.12 (m, 6H), 00-0.92 (m, 8H), 0.87 (t, 3H), 0.90-0.80 (m, 2H).

Synthesis of 4- (4- (4-propylcyclohexyl) cyclohexyl) methoxy-3-trifluoromethyl-2-fluoroethoxybenzene (Compound No. 2-3-13)

First Step Under a nitrogen atmosphere, 25.7 g (71.4 mmol) of 2-fluoro-2-trifluoromethyl-6-trimethylsilylethoxybenzene dissolved in 60 mL of THF is 85.7 mL of sec-butyllithium (1.0 mol / L). Was added dropwise at −78 ° C. and stirred at the same temperature for 2 hours. Next, 13.7 g (85.7 mmol) of bromine was added dropwise to this solution, and the mixture was stirred at the same temperature for 1 hour, then warmed to room temperature and stirred overnight. The reaction mixture was poured into 100 ml of water and extracted with 200 ml of toluene. The organic layer was washed successively with 100 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and crude 2-trifluoromethyl-3-fluoro-4-ethoxy-5-trimethylsilylbromobenzene. Of 27.8 g.

Second Step 27.8 g of crude 2-trifluoromethyl-3-fluoro-4-ethoxy-5-trimethylsilylbromobenzene obtained in the first step was dissolved in 100 mL of THF. Thereto, 100 mL of tetrabutylammonium fluoride THF solution (1.0 mol / L) was added dropwise and stirred overnight. The reaction mixture was poured into 200 ml of water and extracted with 200 ml of toluene. The organic layer was washed successively with 200 ml of water and 100 ml of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane) to obtain 15.0 g of 2-trifluoromethyl-3-fluoro-4-ethoxybromobenzene.

Third Step 15.0 g 13.2 g (52.2 mmol) of (2-trifluoromethyl-3-fluoro-4-ethoxybromobenzene) obtained in the second step was dissolved in 50 ml of THF, and acetone-dry ice refrigerant in a nitrogen atmosphere. The solution was then cooled to −70 ° C. Under a nitrogen atmosphere, 40 ml (62.6 mmol) of n-butyllithium (1.56 mol / L n-hexane solution) was added dropwise to the solution, and after addition, at −65 ° C. Then, 13.0 g (125.2 mmol) of trimethyl borate dissolved in 30 mL of THF was added dropwise at −65 ° C. After the addition, the mixture was further stirred for 1 hour, then warmed to room temperature and stirred overnight. The mixture was poured into 200 ml of 3N hydrochloric acid and extracted with 200 ml of ethyl acetate, and the organic layer was washed successively with 300 ml of water and 100 ml of saturated brine, After drying with anhydrous magnesium sulfate, and concentrated under reduced pressure, the 2-trifluoromethyl-3-fluoro-4-ethoxyphenyl borate crude yield 13.8 g.

Fourth Step To 13.8 g (52.2 mmol) of crude 2-trifluoromethyl-3-fluoro-4-ethoxyphenylboric acid obtained in the third step dissolved in 100 ml of THF, 30% aqueous hydrogen peroxide 16 .2 g (104.4 mmol) was added dropwise and the mixture was further stirred at room temperature for 2 hours. This solution was poured into 300 ml of a saturated aqueous sodium hydrogen sulfite solution and extracted with 200 ml of ethyl acetate. The organic layer was washed successively with 300 mL of saturated aqueous sodium hydrogensulfite solution, 300 mL of water and 200 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by distillation and further recrystallized twice from a heptane / ethanol mixed solvent to obtain 5.67 g of pure 2-trifluoromethyl-3-fluoro-4-ethoxyphenol.

Fifth Step 3.0 g (13.4 mmol) of 2-trifluoromethyl-3-fluoro-4-ethoxyphenol obtained in the fourth step was dissolved in 70 mL of N, N-dimethylformamide, and 4- (4 -Propylcyclohexyl) cyclohexylbromomethane 4.44 g (14.7 mmol), potassium carbonate 2.03 g (14.7 mmol), and tetrabutylammonium bromide 0.22 g (0.67 mmol) were added, and the mixture was heated to reflux for 3 hours. After cooling to room temperature, the solution was poured into 300 ml of water and extracted with 200 ml of toluene. The organic layer was washed successively with 300 ml of water and 200 ml of saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane: toluene = 7: 1) and recrystallized twice from a heptane / ethanol mixed solvent to obtain pure 4- (4- (4- Propylcyclohexyl) cyclohexyl) methoxy-3-trifluoromethyl-2-fluoroethoxybenzene (Compound No. 2-3-13) (3.01 g) was obtained. This compound exhibited a liquid crystal phase.
¹ H-NMR (CDCl ₃ ): δ (ppm); 6.69 (d, 1H), 6.59 (t, 1H), 4.12 (q, 2H), 3.73 (d, 2H), 1.97-1.91 (m, 2H), 1.80-1.70 (m, 7H), 1.37 (t, 3H), 1.34-1.27 (m, 2H), 1. 15-0.94 (m, 11H), 0.87 (t, 3H), 0.89-0.81 (m, 2H).

  By applying the above synthesis method and Examples 1 to 9, the following compound No. 1-1-1. Synthesize 2-9-9.

母液晶Ａの物性は次のとおりであった。上限温度（ＮＩ）＝７４．０℃；粘度（η_２０）＝１８．９ｍＰａ・ｓ；光学異方性（Δｎ）＝０．０８７；誘電率異方性（Δε）＝−１．３。 The following five compounds were mixed to prepare a composition having a nematic phase (base liquid crystal A). (Mother liquid crystal A)

The physical properties of the mother liquid crystal A were as follows. Maximum temperature (NI) = 74.0 ° C .; viscosity (η ₂₀ ) = 18.9 mPa · s; optical anisotropy (Δn) = 0.087; dielectric anisotropy (Δε) = − 1.3.

It consists of 85% of the mother liquid crystal A and 15% of 4- (4-propylcyclohexyl) phenyl-2-fluoro-3-difluoromethyl-ethoxybenzene (compound No. 1-3-5) obtained in Example 2. Composition B was prepared. The physical properties of composition B are as follows.
Optical anisotropy (Δn) = 0.096; dielectric anisotropy (Δε) = − 2.4.
Compound No. By adding 1-3-5, it was found that the dielectric anisotropy becomes negatively large and has a low driving voltage when a liquid crystal display device is formed.

85% of the mother liquid crystal A and 4- (4-propylcyclohexyl) cyclohexyl) ethyl) -2-fluoro-3-trifluoromethyl-ethoxybenzene (Compound No. 2-3-12) obtained in Example 8 A composition B consisting of 15% was prepared. The physical properties of composition B were as follows.
Optical anisotropy (Δn) = 0.086; dielectric anisotropy (Δε) = − 2.21.
Compound No. It has been found that by adding 2-3-12, the dielectric anisotropy becomes negatively large, and the liquid crystal display element has a low driving voltage.

[Comparative Example 1]
A composition comprising 85% of composition A described in Example 10 and 15% of 4- (4-propylcyclohexyl) phenyl-2-fluoro-3-difluoromethyl-ethoxybenzene described in WO2000 / 03963. D was prepared. The physical properties of Composition D were as follows.
Optical anisotropy (Δn) = 0.096; dielectric anisotropy (Δε) = − 2.1.

  Representative compositions of the present invention are summarized in Use Examples 1-7. First, compounds that are components of the composition and their amounts (% by weight) are shown, and then physical properties of the composition are shown. The compounds were indicated by the symbols of the left terminal group, linking group, ring structure, and right terminal group according to the conventions in Table 1. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is trans. If there is no end group symbol, it means that the end group is hydrogen.

[Usage example 1]
3-HBB (2CF2H, 3F) -O2 (1-3-5) 6%
2-BB (2CF2H, 3F) H-3 (1-4-5) 3%
2-BB (2CF2H, 3F) B-3 (1-4-6) 6%

1V2-BEB (F, F) -C 6%
3-HB-C 9%
2-BTB-1 10%
5-HH-VFF 24%
3-HHB-1 4%
VFF-HHB-1 8%
VFF2-HHB-1 11%
3-H2BTB-2 5%
3-H2BTB-3 4%
3-H2BTB-4 4%
NI = 76.5 ° C .; Δn = 0.136; η (20 ° C.) = 25.0 mPa · s; Δε = 4.8.

[Usage example 2]
3-HBB (2CF2H, 3F) -O2 (1-3-5) 10%
2-BB (2CF2H, 3F) H-3 (1-4-5) 5%

3-HH-4 8%
3-HHB-1 6%
3-HHB (F, F) -F 10%
3-H2HB (F, F) -F 9%
3-HBB (F, F) -F 10%
3-BB (F, F) XB (F, F) -F 25%
1O1-HBBH-5 7%
2-HHBB (F, F) -F 3%
3-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 4%
NI = 83.0 ° C .; Δn = 0.115; η (20 ° C.) = 36.9 mPa · s; Δε = 8.2.

[Usage example 3]
3-HHVB (2CF2H, 3F) -O2 (1-3-15) 7%
3-HHVB (2CF3,3F) -O2 (2-3-3) 6%
1-B (2CF2H, 3F) O1H-3 (1-2-8) 5%

3-HH-4 5%
3-HH-5 5%
3-HH-O1 3%
3-HH-O3 3%
3-HB-O1 5%
3-HB-O2 5%
3-HB (2F, 3F) -O2 10%
5-HB (2F, 3F) -O2 10%
3-HHEH-3 2%
3-HHEH-5 2%
4-HHEH-3 2%
2-HHB (2F, 3F) -1 4%
3-HHB (2F, 3F) -2 4%
3-HHB (2F, 3F) -O2 12%
5-HHB (2F, 3F) -O2 10%

[Usage example 4]
3-HVB (2CF2H, 3F) -O2 (1-1-13) 5%
3-HVB (2CF3,3F) -O2 (2-1-2) 5%
3-HHB (2CF2H, 3F) -O2 (1-3-1) 5%

3-HH-4 5%
3-HH-5 5%
3-HH-O1 6%
3-HH-O3 6%
3-HB-O1 5%
3-HB-O2 5%
3-HB (2F, 3F) -O2 10%
3-HHEH-3 5%
3-HHEH-5 5%
4-HHEH-3 5%
2-HHB (2F, 3F) -1 4%
3-HHB (2F, 3F) -O2 12%
5-HHB (2F, 3F) -O2 12%

[Usage example 5]
1V-HB (2CF2H, 3F) -O2 (1-1-4) 10%
3-HHVB (2CF2H, 3F) -O2 (1-3-15) 5%

3-HH-4 5%
3-HH-5 5%
3-HH-O1 4%
3-HH-O3 4%
3-HB-O1 4%
3-HB-O2 3%
3-HB (2F, 3F) -O2 10%
5-HB (2F, 3F) -O2 5%
3-HHEH-3 5%
3-HHEH-5 5%
4-HHEH-3 5%
2-HHB (2F, 3F) -1 4%
3-HHB (2F, 3F) -2 4%
3-HHB (2F, 3F) -O2 12%
5-HHB (2F, 3F) -O2 10%

[Usage Example 6]
3-HVB (2CF2H, 3F) -O2 (1-1-13) 7%
2-BB (2CF2H, 3F) H-3 (1-4-5) 5%

3-HH-4 5%
3-HH-5 5%
3-HH-O1 6%
3-HH-O3 6%
3-HB-O1 5%
3-HB-O2 5%
3-HB (2F, 3F) -O2 10%
5-HB (2F, 3F) -O2 10%
3-HHEH-3 4%
3-HHEH-5 3%
2-HHB (2F, 3F) -1 4%
3-HHB (2F, 3F) -2 4%
3-HHB (2F, 3F) -O2 12%
5-HHB (2F, 3F) -O2 9%

[Usage example 7]
3-HBB (2CF2H, 3F) -O2 (1-3-5) 10%
2-BB (2CF2H, 3F) H-3 (1-4-5) 5%

3-HH-4 5%
3-HH-5 5%
3-HH-O1 3%
3-HH-O3 3%
3-HB-O1 4%
3-HB-O2 4%
3-HB (2F, 3F) -O2 10%
5-HB (2F, 3F) -O2 10%
3-HHEH-3 5%
3-HHEH-5 5%
4-HHEH-3 5%
2-HHB (2F, 3F) -1 4%
3-HHB (2F, 3F) -2 4%
3-HHB (2F, 3F) -O2 10%
5-HHB (2F, 3F) -O2 8%
NI = 77.8 ° C .; Δn = 0.083; η (20 ° C.) = 39.1 mPa · s; Δε = −3.7.
When 0.25 part of (Op-5) was added to 100 parts of the above composition, the pitch was 58.5 μm.

According to the present invention, it exhibits negative dielectric anisotropy, general physical properties necessary for liquid crystal compounds, stability to heat, light, etc., appropriate optical anisotropy, appropriate dielectric anisotropy, other Provided is a liquid crystal compound having an excellent balance of physical properties such as having excellent compatibility with a liquid crystal compound. A liquid crystal composition containing at least one of the liquid crystal compounds has an appropriate nematic phase, a small viscosity, an appropriate optical anisotropy, and a low threshold voltage. By incorporating this composition, a liquid crystal display device having a wide usable temperature range, a short response time, a large contrast ratio, a low driving voltage, and the like can be produced.

Claims (46)

Compound represented by formula (1) or formula (2):

Where Ra and Rb are independently hydrogen or alkyl having 1 to 20 carbons; in this alkyl, any —CH ₂ — is —O—, —S—, —CO— or —SiH ₂ —. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen may be replaced with a halogen;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl; in these rings, one or two non-adjacent —CH ₂ — is —O—, —S—, —CO - or -SiH 2 _- may be replaced by, and any hydrogen may be replaced by halogen;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, —COCH ₂ —, —CH _{2 SiH 2 -, - SiH 2 CH} 2 -, - (CH 2) 4 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
W represents — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Z ¹¹ , Z ¹² , Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —CH ₂ CO—, —COCH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O— , —O— (CH ₂ ) ₃ —, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
j, k, m, n, p and q are independently 0 or 1, and their sum is 1, 2 or 3;
When m is 0, j and k are both 0, Ra in formula (1) is not hydrogen, alkoxy or alkoxymethyl, and Ra in formula (2) is 1-alkenyl.   2. The compound of claim 1, wherein the sum of j, k and m and the sum of n, p and q are independently 1 or 2. The compound according to claim 1, which is represented by any one of formula (1-1) to formula (1-9) and formula (2-1) to formula (2-9):

Here, Ra and Rb are independently hydrogen or alkyl having 1 to 20 carbons; in this alkyl, any —CH ₂ — that is not located at the terminal is —O—, —S—, or —CO—. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen may be replaced with a halogen;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3. , 4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl; in these rings, one or two non-adjacent —CH ₂ — is —O—, —S—, or -CO- may be replaced, and any hydrogen may be replaced by halogen;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, —COCH ₂ —, —CH _{2 SiH 2 -, - SiH 2 CH} 2 -, - (CH 2) 4 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
W represents — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CO—, _{-COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Z ¹¹ , Z ¹² , Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, — CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —CH ₂ CO—, —COCH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ —O— , —O— (CH ₂ ) ₃ —, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
In Formula (1-2), Formula (1-5), and Formula (1-9), Ra is not hydrogen, alkoxy, or alkoxymethyl; Formula (2-2), Formula (2-5), and Formula In (2-9), Ra is 1-alkenyl. Ra and Rb are independently alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxyalkyl having 2 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkenyloxy having 3 to 10 carbon atoms, carbon A perfluoroalkyl having 1 to 10 carbon atoms or a perfluoroalkoxy having 1 to 10 carbon atoms;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 4,6-dioxane-2,5. -Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro 1,4-phenylene, 2,3-difluoro-1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl;
Z ¹¹ and Z ¹² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ −, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ — Yes;
Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — _{OCF 2 -, - CH = CH} -, - CF = CF -, - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH- ( CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, — (CH ₂ ) ₂ CF ₂ O—, or —OCF ₂ (CH ₂ ) ₂ —;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( _{CH 2) 3 -O -, -} O- (CH 2) 3 -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - a compound according to claim 3. Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxyalkyl having 2 to 10 carbons or alkenyl having 2 to 10 carbons;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1 , 4-phenylene, or 2,3-difluoro-1,4-phenylene;
Z ¹¹ and Z ¹² are independently a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, —CH═CH _{- (CH 2) 2 -,} - (CH 2) 2 -CH = CH -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - and is;
Z ² , Z ²¹ and Z ²² are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH _{-, - (CH 2) 2} CF 2 O-, or -OCF _{2 (CH 2) 2} - and is;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( _{CH 2) 3 -O -, -} O- (CH 2) 3 -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - a compound according to claim 3. Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons;
A ¹ , A ¹¹ , A ¹² , A ² , A ²¹ and A ²² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro- 1,4-phenylene;
Z ¹¹ and Z ¹² are independently a single bond or —CH═CH—;
Z ² , Z ²¹ and Z ²² are each independently a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, or —OCF ₂ —;
Y is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ , — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ CF ₂ O—, or — OCF ₂ (CH ₂ ) ₂ —;
W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( _{CH 2) 3 -O -, -} O- (CH 2) 3 -, - (CH 2) 2 CF 2 O-, or -OCF _{2 (CH 2) 2} - a compound according to claim 3. The compound according to any one of claims 3 to 6, wherein A ¹ or A ² is 1,4-cyclohexylene. The compound according to any one of claims 3 to 6, wherein A ¹ or A ² is 1,4-phenylene. 4. In formula (1-1) to formula (1-9), Y or Z ² is a single bond, and in formula (2-1) to formula (2-9), Z ² is a single bond. The compound of any one of -6. A ¹ or A ² is 1,4-cyclohexylene, Y or Z ² in formula (1-1) to formula (1-9) is a single bond, and formula (2-1) to formula (2) in -9) ^{Z 2} is a single bond, compounds according to any one of claims 3-6. A ¹ or A ² is 1,4-phenylene, Y or Z ² is a single bond in formula (1-1) to formula (1-9), and formula (2-1) to formula (2- 9) is Z ² is a single bond in the compound according to any one of claims 3-6. Represented by any one of formula (2-1), formula (2-3), formula (2-4), formula (2-6), formula (2-7) and formula (2-8); And the compound of any one of Claims 3-6 whose A1 is ¹ , 4- cyclohexylene. A ¹ is 1,4-cyclohexylene; and W is — (CH ₂ ) ₂ —, —CH ₂ O—, or —CF ₂ O—, which is represented by formula (2-1); Item 7. The compound according to any one of Items 3 to 6. A ¹ and A ¹¹ are both 1,4-cyclohexylene; Z ¹¹ is a single bond; and W is — (CH ₂ ) ₂ —, —CH ₂ O -, or _-CF 2 is O-, a compound according to any one of claims 3-6. A ¹ , A ¹¹ and A ¹² are all 1,4-cyclohexylene; Z ¹¹ and Z ¹² are both single bonds; and W is — (CH _{2 ) 2 -, - CH 2 O-} , or _-CF 2 is O-, a compound according to any one of claims 3-6. Represented by any one of formula (1-2), formula (1-4), formula (1-5), formula (1-7), formula (1-8) and formula (1-9); Then, ^{Z 2} is _{-CH 2 O -, - OCH 2} -, - CF 2 O-, or -OCF ₂ - the compound according to any one of claims 3-6. Represented by formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; and A ¹ and A ¹¹ are both 1,4-be cyclohexylene; and Y and ^{Z 11} are both single bonds, a compound according to claim 3. Represented by formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; and A ¹ and A ¹¹ are both 1,4-be cyclohexylene; Y is _-CH 2 CH ₂ - and is; and ^{Z 11} is a single bond, a compound according to claim 3. Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- There ^{phenylene; a 11} is located at the 1,4-cyclohexylene; and Y and ^{Z 11} are both single bonds, a compound according to claim 3. Represented by formula (1-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; and A ¹ and A ¹¹ are both it is a 1,4-phenylene; and Y and ^{Z 11} are both single bonds, a compound according to any one of claims 3-6. Represented by formula (1-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- 4. A compound according to claim 3 which is cyclohexylene; and Y is a single bond. Represented by formula (1-1); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- it is a cyclohexylene; and Y is _-CH 2 CH ₂ - a compound according to claim 3. Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- it is a cyclohexylene; and W is - _{(CH 2) 2} - a compound according to claim 3. Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- it is a cyclohexylene; and W is _-CH 2 O-, a compound according to claim 3. Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- There phenylene; and W is - _{(CH 2) 2} - a compound according to claim 3. Represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A ¹¹ are both 1,4 There ^{cyclohexylene; Z 11} represents a single bond; and W is - _{(CH 2) 2} - a compound according to claim 3. Represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A ¹¹ are both be a ^{1,4-cyclohexylene; Z 11} is a single bond; and W is _-CH 2 O-, a compound according to claim 3. Represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ is 1,4- phenylene, and be ^{a 11} is ^{1,4-cyclohexylene; Z 11} represents a single bond; and W is - _{(CH 2) 2} - a compound according to claim 3. Represented by formula (2-3); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ and A ¹¹ are both be a ^{1,4-phenylene; Z 11} represents a single bond; and W is - _{(CH 2) 2} - a compound according to claim 3. Represented by formula (2-6); Ra is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and Rb is alkoxy having 1 to 10 carbons; A ¹ , A ¹¹ and A ¹² are both located in the ^{1,4-cyclohexylene; Z 11} and ^{Z 12} represents a single bond; and W is - _{(CH 2) 2} - or _-CH 2 O-, a compound according to claim 3. Ra is alkyl having 1 to 10 carbons and Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ² is 1,4- it is a cyclohexylene; and ^{Z 2} is -OCH ₂ - the compound of claim 3. Represented by formula (1-5); Ra is alkyl having 1 to 10 carbons, and Rb is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ² and A ²¹ are both 1,4-be cyclohexylene; ^{Z 2} is -OCH ₂ - a, and ^{Z 21} is a single bond, a compound according to claim 3. Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ and A ² are both 1,4-phenylene; Then, Y and Z ² are both single bonds, a compound according to claim 3. Ra and Rb are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ is 1,4-cyclohexylene and A ² There be 1,4-phenylene; and, Y and Z ² are both single bonds, a compound according to claim 3. Ra and Rb are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons; A ¹ is 1,4-phenylene, and A ² is represented by formula (1-4) it is a 1,4-cyclohexylene; and, Y and Z ² are both single bonds, a compound according to claim 3.   A liquid crystal composition containing at least one of the compounds according to claim 1 and optionally containing at least one optically active compound. At least one compound according to claim 1 and at least one compound selected from the group consisting of compounds represented by each of formula (3), formula (4) and formula (5), Liquid crystal composition that may contain one optically active compound:

Here, R ¹ is alkyl having 1 to 10 carbons; in this alkyl, arbitrary —CH ₂ — may be replaced by —O—, and optional — (CH ₂ ) ₂ — represents —CH═ CH— may be replaced and any hydrogen may be replaced with fluorine; X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, -OCF ₂ CHF _2, or be a -OCF ₂ CHFCF _3; ^{B 1} and D is independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or at least 1 1,4-phenylene in which one hydrogen is replaced with fluorine; E is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced with fluorine It is Eniren; ^{Z 4} and ^{Z 5} are independently _{- (CH 2) 2 -,} - (CH 2) 4 -, - COO -, - CF 2 O -, - OCF 2 -, - CH = CH- or A single bond; and L ¹ and L ² are independently hydrogen or fluorine. At least one of the compounds according to claim 1 and at least one compound selected from the group consisting of compounds represented by each of formula (6-1), formula (6-2) and formula (7): A liquid crystal composition that contains and may contain at least one optically active compound:

Wherein R ² and R ³ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— and any hydrogen may be replaced with fluorine; X ² is —CN or —C≡C—CN; G is 1,4-cyclohex Silene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; J is 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5 - diyl or at least one hydrogen is 1,4-phenylene which is replaced by fluorine,; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, - OCF 2 - or a single bond in ^{it; L} 3, L ⁴ you Fine and L ⁵ have independently hydrogen or fluorine; and b, c and d are independently 0 or 1. A compound selected from the group consisting of at least one of the compounds according to claim 1 and a compound represented by each of formula (8), formula (9), formula (10), formula (11), and formula (12). And a liquid crystal composition that may contain at least one optically active compound:

Where R ⁴ is alkyl having 1 to 10 carbons and R ⁵ is fluorine or alkyl having 1 to 10 carbons; in these alkyls, any —CH ₂ — is replaced by —O—. Any — (CH ₂ ) ₂ — may be replaced by —CH═CH— and any hydrogen may be replaced by fluorine; M and P ¹ are independently 1,4 - cyclohexylene, be 1,4-phenylene or decahydro-2,6-naphthylene; ^{Z 7} and ^{Z 8} are independently _{- (CH 2) 2 -,} - COO- or a single bond; ^{L 6} and L ⁷ is independently hydrogen or fluorine; and at least one of L ⁶ and L ⁷ is fluorine. At least one compound according to claim 1 and at least one compound selected from the group consisting of compounds represented by each of formula (13), formula (14) and formula (15), and at least Liquid crystal composition that may contain one optically active compound:

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond. The liquid crystal composition according to claim 37, further comprising at least one compound selected from the group consisting of compounds represented by formula (6-1), formula (6-2), and formula (7). :

Wherein R ² and R ³ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— and any hydrogen may be replaced with fluorine; X ² is —CN or —C≡C—CN; G is 1,4-cyclohex Silene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; J is 1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5 - diyl or at least one hydrogen is 1,4-phenylene which is replaced by fluorine,; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, - OCF 2 - or a single bond in ^{it; L} 3, L ⁴ you Fine and L ⁵ have independently hydrogen or fluorine; and b, c and d are independently 0 or 1. The liquid crystal composition according to claim 37, further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14), and formula (15):

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond. The liquid crystal composition according to claim 38, further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14), and formula (15):

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond. 40. The liquid crystal composition according to claim 39, further comprising at least one compound selected from the group consisting of compounds represented by formula (13), formula (14) and formula (15):

Wherein R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons; in this alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced by -CH = CH- and any hydrogen may be replaced by fluorine; Q, T and U are independently 1,4-cyclohexylene, 1,4-phenylene, Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; and Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — ( CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O— or a single bond.   45. Use of the liquid crystal composition according to any one of claims 36 to 44 for producing a liquid crystal display element. The liquid crystal display element containing the liquid-crystal composition of any one of Claims 36-44.