WO2013053193A1

WO2013053193A1 - Compound comprising 1,2-difluoroethylene and difluoromethylene ether structure, preparation and use thereof

Info

Publication number: WO2013053193A1
Application number: PCT/CN2012/001240
Authority: WO
Inventors: 刘琦; 吴凤; 谭玉东; ***; 李建森; 闵国庆; 胡全
Original assignee: 江苏和成显示科技股份有限公司
Priority date: 2011-10-14
Filing date: 2012-09-04
Publication date: 2013-04-18
Also published as: CN102336634A; CN102336634B

Abstract

The present invention relates to a compound of formula (I) and a preparation method thereof, wherein R represents an alkyl or alkenyl group of 1-15 carbon atoms, an alkoxyl or alkenyloxy group of 1-15 carbon atoms; ring A represents a trans-1,4-cyclohexylidene, trans-1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diylphenylene group or 1,4-phenylene unsubstituted or substituted by one or more fluorine atoms; Z represents a single bond, -CH₂CH₂-, -CH=CH->-C≡C-, -OCH₂-, -CH₂O-, -OCF₂-, -CF₂O-, -CF₂CF₂-, -CF=CF-, -OCO-, -COO-; L₁, L₂, L₃, L₄, L₅, L₆, L₇ and L₈ each independently represents a hydrogen atom or halogen atom; X represents -H, -CN, -F, -Cl, -OCF₃, -OCF₂H, -CF₃; and m represents the number 0 or 1. The present invention also relates to the use of the compound as a component of a liquid crystal medium, a liquid crystal, and an electro-optical display element comprising the liquid crystal medium.

Description

包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物及其制备和应用技术领域 Compound comprising 1,2-difluoroethylene and difluoromethylene ether structure, and preparation and application thereof

本发明涉及作为液晶介质的组分的化合物及其制备方法和应用，尤其是包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物及其制备方法和应用。背景技术 The present invention relates to a compound as a component of a liquid crystal medium, a process for the preparation thereof and an application thereof, particularly a compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether, and a process for the preparation thereof and use thereof. Background technique

液晶主要是用作显示器中的电介质，这是因为外加电压可以改变这类物质的光学性能。基于液晶的电光学器件是本领域技术人员公知的，其中可以包含各种效应。这类器件的实例是具有动态散射的液晶盒、 DAP (配向相变形）液晶盒、宾 /主型液晶盒、具有扭曲向列结构的 TN盒、 STN (超扭曲向列）液晶盒、 SBE (超双折射效应）液晶盒和 OMI (光膜干涉）液晶盒。最常见的显示器基于 Schadt-Helfrich效应并具有扭曲向列结构。此外，还存在用于平行于基板和液晶面的电场操作的液晶盒，例如 IPS (面内切换）液晶盒。特别的， TN、 STN和 IPS液晶盒，尤其是 TN和 IPS液晶盒是本发明的介质的目前具有商业意义的应用领域。液晶材料必须具有良好的化学和热稳定性以及良好的对电场和电磁辐射的稳定性。此外，液晶材料应该具有低粘度并在液晶盒内产生短寻址时间、低阈值电压和高对比度。它们还应该在普通操作温度下，即在高于和低于室温的可能的最宽范围内，具有适用于上述液晶盒的介晶相，例如向列型或胆型介晶相。由于液晶通常作为多种组分的混合物使用，重要的是这些组分容易彼此混容。其他性能，如果电阻率、介电各向异性和光学各向异性必须根据液晶盒类型和应用领域而满足各种要求。例如，具有扭曲向列结构的液晶盒的材料应该具有正介电各向异性和低电导率。使用在 MLC显示器、笔记本或者汽车仪表上的混合液晶，除了涉及对比度和响应时间有关的问题外，要想取得高的电阻率也出现了困难，随着电阻率的降低，显示器的对比度会变差，并可能产生余像消失的问题。液晶混合物的电阻率通常由于与显示器内表面的相互作用而随着显示器的使用年限降低，因此高的初始电阻率对于获得可接受的寿命非常重要。此外，重要的是，随着温度升高，并且在加热和 /或紫外线曝光后，电阻率出现最小可能的提高。现有技术的混合物的低温性能也不是特别好。需要即使在低温下也不出现结晶和 /或近晶相，且粘度的温度依赖性尽可能低。现有技术因此也不能完全满足要求。对于 TV和视频应用，需要具有短响应时间的显示器。特别的，如果使用具有低粘度值的液晶组合物，可以实现这种短响应时间。但是，稀释用添加剂通常降低了清亮点并由此降低混合液晶的工作范围。因此，仍然需要没有表现出这些缺点或仅在较低程度上表现出这些缺点的具有极高电阻率、同时具有大工作温度范围、短响应时间（即使在低温下）和低阈值电压的显示器。在 TN液晶盒中，需要促成液晶盒中的下列优点的介质： Liquid crystals are primarily used as dielectrics in displays because the applied voltage can alter the optical properties of such materials. Liquid crystal based electro-optical devices are well known to those skilled in the art and may include various effects. Examples of such devices are liquid crystal cells with dynamic scattering, DAP (alignment phase deformation) liquid crystal cells, guest/host type liquid crystal cells, TN boxes with twisted nematic structure, STN (Super Twisted Nematic) liquid crystal cells, SBE ( Super birefringence effect) Liquid crystal cell and OMI (light film interference) cell. The most common displays are based on the Schadt-Helfrich effect and have a twisted nematic structure. In addition, there are liquid crystal cells for electric field operation parallel to the substrate and the liquid crystal surface, such as an IPS (In-Plane Switching) liquid crystal cell. In particular, TN, STN and IPS liquid crystal cells, especially TN and IPS liquid crystal cells, are currently commercially useful applications for the media of the present invention. Liquid crystal materials must have good chemical and thermal stability as well as good stability to electric fields and electromagnetic radiation. In addition, the liquid crystal material should have a low viscosity and produce short address times, low threshold voltages, and high contrast in the liquid crystal cell. They should also have a mesogenic phase suitable for the above liquid crystal cell, such as a nematic or cholesteric mesophase, at ordinary operating temperatures, i.e., at the widest possible range above and below room temperature. Since liquid crystals are generally used as a mixture of a plurality of components, it is important that these components are easily mixed with each other. Other properties, if resistivity, dielectric anisotropy and optical anisotropy, must meet various requirements depending on the type of cell and the field of application. For example, a material having a liquid crystal cell having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity. Using mixed liquid crystals on MLC displays, notebooks, or car instruments, in addition to problems related to contrast and response time, it is difficult to achieve high resistivity. As the resistivity decreases, the contrast of the display will deteriorate. , and may cause problems with the disappearance of the afterimage. The resistivity of a liquid crystal mixture generally decreases with the age of the display due to interaction with the inner surface of the display, so a high initial resistivity is very important to achieve an acceptable lifetime. Furthermore, it is important that as the temperature increases, and after heating and/or UV exposure, there is a minimal possible increase in resistivity. The low temperature properties of the prior art mixtures are also not particularly good. It is required that crystals and/or smectic phases do not occur even at low temperatures, and the temperature dependence of viscosity is as low as possible. The prior art therefore does not fully satisfy the requirements. For TV and video applications, a display with a short response time is required. In particular, such a short response time can be achieved if a liquid crystal composition having a low viscosity value is used. However, the dilution additive generally reduces the clearing point and thereby reduces the operating range of the mixed liquid crystal. Therefore, there is still a need for a display having extremely high resistivity, a large operating temperature range, a short response time (even at low temperatures), and a low threshold voltage without exhibiting these disadvantages or exhibiting only these disadvantages to a lesser extent. In the TN liquid crystal cell, there is a need for a medium that contributes to the following advantages in the liquid crystal cell:

1、扩大的向列相范围（特别是低至低温） 1. Expanded nematic phase range (especially low to low temperature)

2、在极低温度下的可切换性 2, switchability at very low temperatures

3、提高的抗紫外线辐射性 3, improved UV radiation resistance

4、低阈值电压现有技术中得到的混合液晶不能在保持其他参数的同时实现这些优点。我们知道，响应时间（τ) 与旋转粘度（γ) 和盒厚（d) 有下列关系： τ^γ(1。为了满足短响应， d必须小。因为对于特定的显示模式， Δη·(1通常是固定的，因此，为实现液晶材料 Δη值约 0.2，单体的 Δη值必须大于 0.2，在满足工艺要求下， d越小越好，即光学各向异性（Δη) 要增大。为了得到显示模式所需的各种特性，液晶材料通常以各种液晶化合物的混合物形式使用，因此，需要液晶化合物具有良好的互溶性，特别是在低温下。但是随着 Δη的增大，其与其他液晶的相溶性变差，犹在低温下变的更甚。近年来，人们开始关注一些大光学各向异性（Δη)，大介电各向异性（Δε)，低旋转粘度（γ) 的液晶材料，也合成出一些出来，但是，其性能不太适应市场发展的需要，液晶材料的使用者仍然不太满意。在液晶化合物设计过程中，人们发现通过合理地引入二氟亚甲基醚连接基团，可以起到增宽向列相温度范围，增大介电各向异性值（Δε)，改善液晶化合物的溶解性能，降低旋转粘度（γ)，改善电压保持率（VHR)。如： CN101565624 A, 智索公司的中国专利 CN1158602A。通过合理地引入 1,2-二氟乙烯连接基团，增加分子的共轭程度，可以起到增宽向列相温度范围、增大光学各向异性值（Δη)、改善液晶化合物的溶解性能、降低旋转粘度（γ) 以及改善电压保持率 (VHR)的作用。如： EP1215270 A1 , CN101193999 A, C画 1302145 A, EP2116522 Al c 发明内容 4. Low Threshold Voltage The hybrid liquid crystal obtained in the prior art cannot achieve these advantages while maintaining other parameters. We know that the response time (τ) has the following relationship with the rotational viscosity (γ) and the box thickness (d): τ^γ(1. In order to satisfy the short response, d must be small. Because for a specific display mode, Δη·(1) Usually, it is fixed. Therefore, in order to achieve a liquid crystal material Δη value of about 0.2, the Δη value of the monomer must be greater than 0.2. Under the process requirements, d is preferably as small as possible, that is, the optical anisotropy (Δη) is increased. The various properties required for the display mode are obtained, and the liquid crystal material is usually used in the form of a mixture of various liquid crystal compounds, and therefore, it is required that the liquid crystal compound has good mutual solubility, particularly at a low temperature. However, as Δη increases, it The compatibility of other liquid crystals deteriorates, and it becomes even worse at low temperatures. In recent years, attention has been paid to some large optical anisotropies (Δη), large dielectric anisotropy (Δε), and low rotational viscosity (γ). Liquid crystal materials have also been synthesized, but their performance is not suitable for the needs of market development, and users of liquid crystal materials are still not satisfied. In the process, it was found that by reasonably introducing a difluoromethylene ether linking group, it is possible to broaden the nematic phase temperature range, increase the dielectric anisotropy value (Δε), improve the solubility of the liquid crystal compound, and reduce Rotational viscosity (γ), improved voltage retention (VHR). For example: CN101565624 A, Chinese patent CN1158602A of Zhisuo Company. By reasonably introducing 1,2-difluoroethylene linking group, increasing the degree of conjugate of the molecule, It functions to broaden the nematic phase temperature range, increase the optical anisotropy value (Δη), improve the solubility of the liquid crystal compound, lower the rotational viscosity (γ), and improve the voltage holding ratio (VHR). For example: EP1215270 A1, CN101193999 A, C drawing 1302145 A, EP 2116522 Al c SUMMARY OF THE INVENTION

本发明的目的是提供一种包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物，该化合物具有大的光学各向异性（Δη)，大的介电各向异性（Δε)，低的旋转粘度（γ) 以及宽的向列相温度范围。本发明的另一目的是提供一种包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物的制备方法。本发明的再一目的是提供一种包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物的液晶组合物。为解决上述问题，本发明提出如下技术方案：本发明的一个方面，提供一种包含 1，2-二氟乙烯和二氟亚甲基醚结构的化合物，所述化合物具有通（I) 所示的结构： SUMMARY OF THE INVENTION An object of the present invention is to provide a compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether, which has large optical anisotropy (Δη) and large dielectric anisotropy (Δε) , low rotational viscosity (γ) and a wide nematic phase temperature range. Another object of the present invention is to provide a compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether. Method. A further object of the present invention is to provide a liquid crystal composition comprising a compound of a structure of 1,2-difluoroethylene and difluoromethylene ether. In order to solve the above problems, the present invention proposes the following technical solution: In one aspect of the invention, there is provided a compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether, the compound having the formula (I) Structure:

其中： among them:

R代表 1-15个碳的垸基或烯基、 1-15个碳的垸氧基或烯氧基； R represents a fluorenyl or alkenyl group of 1 to 15 carbons, a decyloxy group or an alkenyloxy group of 1 to 15 carbons;

环 A代表反式 1,4-亚环己基、反式 -1,3-二噁垸 -2,5-二基、吡啶 -2，5-二基、嘧啶 -2，5- 二基亚苯基或者被 1个或更多个氟原子取代或未取代的 1,4-亚苯基； Ring A represents trans 1,4-cyclohexylene, trans-1,3-dioxin-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diphenylene a 1,4-phenylene group substituted or unsubstituted with one or more fluorine atoms;

Z代表单键、 -CH₂CH₂-、 -CH=CH-、 -C≡C-、 -OCH₂-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF₂-、 -CF=CF -、 -OCO-、 -COO-; Z represents a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -OCH ₂ -, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF ₂ -, -CF=CF -, -OCO-, -COO-;

L₂、 L₃、 L₄、 L₅、 L₆、 L₇和 L₈各自独立地代表氢原子或卤素原子； L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and L ₈ each independently represent a hydrogen atom or a halogen atom;

X代表 -H、 -CN、 -F、 -Cl、 -OCF₃、 -OCF₂H 、 -CF₃; X represents -H, -CN, -F, -Cl, -OCF ₃ , -OCF ₂ H , -CF ₃ ;

m代表数字 0、 l o 在一些优选的实施方案中， R代表 1-7个碳的直链烷基或直链烯基、 1-7个碳的直链烷氧基或直链烯氧基。更优选的是， R为 -C₂H₅、 n-C₃H₇、 n-C₄H₉、 n-C₅H_u。在一些优选的实施方案中，环 A代表反式 1,4-亚环己基或者被 1个或更多个氟原子取代或未取代的 1，4-亚苯基。在一些优选的实施方案中， Z代表单键、 -CH₂CH₂-、 -OCH₂-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF₂-。在一些优选的实施方案中， In、 L₂、 L₃、 L₄、 L₅、 L₆、 L₇和 L₈各自独立地代表氢原子或氟原子。在一些优选的实施方案中， X优选 -H、 -F、 -OCF₃、 -OCF₂H 、 -CF₃，更优选的是 -F、在一些优选的实施方案中， m代表 0。 m represents the number 0, lo. In some preferred embodiments, R represents a linear alkyl or linear alkenyl group of 1 to 7 carbons, a linear alkoxy group of 1 to 7 carbons or a linear alkenyloxy group. More preferably, R is -C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , nC ₅ H _u . In some preferred embodiments, Ring A represents trans 1,4-cyclohexylene or 1,4-phenylene substituted or unsubstituted with one or more fluorine atoms. In some preferred embodiments, Z represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF ₂ -. In some preferred embodiments, In, L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and L ₈ each independently represent a hydrogen atom or a fluorine atom. In some preferred embodiments, X is preferably _{-H, -F, -OCF 3, -OCF} 2 H, -CF 3, and more preferably -F, In some preferred embodiments, m represents zero.

优选地，所述化合物选自由以下化合物组成的组-

；以及 Preferably, the compound is selected from the group consisting of -

; as well as

本发明的另一个方案提供一种制备上述化合物的方法，包括如下步骤： Another aspect of the present invention provides a method of preparing the above compound, comprising the steps of:

1 )在溶剂中，于低温下，即在 -50到 15°C的温度范围，将 1,1,1,2-四氟乙垸在 LDA作用下反应得到三氟乙烯锌试剂，再在催化剂的存在下经钯催化偶联，得到式 2 所示化合物式 2 1) reacting 1,1,1,2-tetrafluoroacetic acid under the action of LDA at a low temperature, that is, at a temperature ranging from -50 to 15 ° C to obtain a trifluoroethylene zinc reagent, and then in the catalyst Palladium-catalyzed coupling in the presence of a compound of formula 2

2 )在溶剂中，在 Aryl-MgX/LnCl₃作用下，由式 2所示化合物得到烯键具有顺反异构的化合物，再经转位反应得 3所示化合物式 32) In the solvent, under the action of Aryl-MgX/LnCl ₃ , the compound represented by the formula 2 is obtained to obtain a compound having a cis-trans isomerization, and then the transposition reaction is carried out to obtain a compound of the formula 3

3 ) 低温下，即在 -78到 -40Ό的温度范围，在异丙基溴化镁作用下，式 4所示化合物

3) Compounds of formula 4 under low temperature, ie in the temperature range of -78 to -40 Torr, under the action of isopropylmagnesium bromide

式 4 Equation 4

和硼酸三异丁酯反应生成式 5

Reacts with triisobutyl borate to form formula 5

式 5 . 再将所述式 5所示化合物和所述式 3所示化合物在催化剂的存在下经钯催化剂偶联反应得到通式（I) 所示化合物；所述步骤 1 )和步骤 3 )中的催化剂可以相同或不同，选自由四（三苯基膦）合钯（0)，二（三苯基膦）二氯化钯（II ), 醋酸钯（III) 和钯 /炭催化剂组成的组。在优选的实施方案中，步骤 2) 中使用的 LnCb选自由 LaCl₃， CeCl₃和 NdCl₃组成的组； LnCl₃的用量为 l-30mol%_; 并且，由式 2所示化合物得到烯键具有顺反异构的化合物的反应需在氮气氛下、 -30〜80Ό之间进行。在优选的实施方案中，当所述 LnCl₃为 LaCl₃时，还需要使用 LiCl，所述 LiCl的用量为 LaCl₃的 2倍。上述的通式（I)类化合物的一种制备方法，其合成路线用化学反应式表示如附图 1。上述反应式中的 R与上述通式（I) 中的 R取代基的范围一致，优选 -C₂H₅、 n-C₃H₇、 n-C₄H₉、 n-C₅H_u。环 A代表反式 1，4-亚环己基、反式 -1， 3-二噁垸 -2,5-二基、吡啶 -2，5-二基、嘧啶 -2,5-二基亚苯基或者被 1个或更多个氟原子取代或未取代的 1，4-亚苯基，优选被 1个或更多个氟原子取代或未取代的 1,4-亚苯基。 Z代表单键、 -CH₂CH₂-、-CH=CH-、- C≡C -、 -OCH₂-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF₂-、 -CF=CF -、 -OCO-、 -COO-;L卜 L₂ L₃、 L₄、 L₅、 L₆、 L₇和！^各自独立地代表氢原子或卤素原子； X代表 -H、 -CN、 -F、 -Cl、 -OCF₃、 -OCF₂H 、 -CF₃; m 代表数字 0、 1，优选 0。上述反应式所述的通式（I) 的化合物的制备方法的步骤用文字表述如下：示化合物

Further, the compound represented by the formula 5 and the compound of the formula 3 are coupled by a palladium catalyst in the presence of a catalyst to obtain a compound of the formula (I); the step 1) and the step 3) The catalysts may be the same or different and are selected from the group consisting of tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, palladium(III) acetate and palladium/carbon catalyst. group. In a preferred embodiment, the LnCb used in step 2) is selected from the group consisting of LaCl ₃ , CeCl ₃ and NdCl ₃ The amount of LnCl ₃ used is from 1 to 30 mol% _; and, the reaction of obtaining a compound having a cis-trans isomerization from the compound of the formula 2 is carried out under a nitrogen atmosphere at -30 to 80 Torr. In a preferred embodiment, when the LnCl ₃ is LaCl ₃ , it is also required to use LiCl in an amount twice that of LaCl ₃ . A preparation method of the above compound of the formula (I), the synthesis route of which is represented by the chemical reaction formula as shown in Fig. 1. R in the above reaction formula corresponds to the range of the R substituent in the above formula (I), and is preferably -C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ or nC ₅ H _u . Ring A represents trans 1,4-cyclohexylene, trans-1, 3-dioxo-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diphenylene A 1,4-phenylene group which is substituted or unsubstituted with one or more fluorine atoms, preferably a 1,4-phenylene group which is substituted or unsubstituted with one or more fluorine atoms. Z represents a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C -, -OCH ₂ -, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF ₂ -, -CF=CF -, -OCO-, -COO-; L Bu L ₂ L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and ! ^ each independently represents a hydrogen atom or a halogen atom; X represents -H, -CN, -F, -Cl, -OCF ₃ , -OCF ₂ H , -CF ₃ ; m represents a number 0, 1, preferably 0. The procedure for the preparation of the compound of the formula (I) described in the above reaction formula is expressed by the following text:

以环境友好的 HFC-134a为原料，低温下在溶剂中，在 LDA作用下反应反应得到三氟乙烯锌试剂，再经钯催化偶联，得到式 2所示化合物；所述催化剂选自下述任意一种：四（三苯基膦）合钯（0)，二（三苯基膦）二氯化钯（II ), 醋酸钯（III)和钯 /炭催化剂; 优选四（三苯基膦）合钯（0)。合物

Taking the environmentally friendly HFC-134a as a raw material, reacting under low pressure in a solvent under the action of LDA to obtain a trifluoroethylene zinc reagent, and then palladium-catalyzed coupling to obtain a compound of the formula 2; the catalyst is selected from the following Any one: tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, palladium(III) acetate and palladium/carbon catalyst; preferably tetrakis(triphenylphosphine) ) Palladium (0). Compound

式 2所示化合物在溶剂中，在 Aryl-MgX/LnCl₃作用下，得到烯键具有顺反异构的化合物，再经转位反应得到式 3 所示化合物；其中式 3 的制备中使用的 LnCl₃优选 LaCl₃,CeCl₃,NdCl_{3 ;}其用量为 l-30mol%;如果使用 LaCl₃,还需要使用 LiCl,其用量为 LaCl₃ 的 2倍；反应温度为 -30〜80°C之间；反应需在氮气氛下进行。 The compound of the formula 2 is obtained by a reaction of Aryl-MgX/LnCl ₃ in a solvent to obtain a compound having an ocene bond having a cis-trans isomer, and then undergoing a transposition reaction to obtain a compound of the formula 3; wherein the compound of the formula 3 is used in the preparation of the formula 3 LnCl ₃ is preferably LaCl ₃ , CeCl ₃ , NdCl _{3 ;} the amount is _1-3 mol%; if LaCl ₃ is used, LiCl is also required, and the amount is 2 times of LaCl ₃ ; the reaction temperature is between -30 and 80 ° C The reaction needs to be carried out under a nitrogen atmosphere.

3 ) 制备通式（I) 所示化合物

3) Preparation of a compound of the formula (I)

式 4所示化合物，低温下，在异丙基溴化镁作用下，和硼酸三异丁酯反应生成式 5所示化合物;再和式 3 所示化合物经钯催化剂偶联反应得到目标产物；所述催化剂选自下述任意一种：四（三苯基膦）合钯（0)，二（三苯基膦）二氯化钯（11 )，醋酸钯（III) 和钯 /炭催化剂；优选四（三苯基膦）合钯（0)。本发明的再一个方案提供一种液晶组合物，包括一种或更多种上述化合物。包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物可以和其他液晶化合物混合组成液晶组合物。本发明的液晶组合物中，包含 1-35% (重量百分含量）的含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物，其余组分为现有技术公知的其他液晶化合物。上述的液晶组合物中，本发明的化合物的优选重量百分含量为 1-30%，最优选为 1-25%。上述的液晶组合物中所述的现有技术公知的液晶化合物，优选下列 A-E所示的化合物， The compound of the formula 4 is reacted with triisobutyl borate under low temperature, under the action of isopropylmagnesium bromide to form a compound of the formula 5; and the compound of the formula 3 is coupled with a palladium catalyst to obtain a target product; The catalyst is selected from any one of the following: tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium dichloride (11), palladium acetate (III) and palladium on carbon catalyst; Preference is given to tetrakis(triphenylphosphine)palladium(0). Still another aspect of the present invention provides a liquid crystal composition comprising one or more of the above compounds. The compound containing a structure of 1,2-difluoroethylene and difluoromethylene ether can be mixed with other liquid crystal compounds to constitute a liquid crystal composition. The liquid crystal composition of the present invention comprises 1-35% by weight of a compound having a structure of 1,2-difluoroethylene and difluoromethylene ether, and the remaining components are other liquid crystals known in the prior art. Compound. In the above liquid crystal composition, the compound of the present invention preferably has a weight percentage of from 1 to 30%, most preferably from 1 to 25%. The liquid crystal compound known in the prior art described in the above liquid crystal composition is preferably a compound represented by the following A-E.

本发明的又一个方面提供一种包括所述液晶组合物作为构成要素的液晶元件。本发明提供的通式（I) 所示的液晶化合物与现有技术其他液晶化合物相比，具有很大的光学各向异性（Δη)，较大的介电各向异性（Δε)，低的旋转粘度（γ) 以及较宽的向列相温度范围，在低温下具有良好的混溶性，它们的化学性质均是稳定的；通式（I) 制备过程中原料易得，而且选用的是环境友好的 HFC-134a, 合成路线简单易行，对反应设备要求不很高，适合规模化工业生产，利于作为显示用液晶材料使用，可用于改善液晶组合物的响应时间（即降低旋转粘度）；提升对光、热的抗破坏能力；降低驱动电压，减少能耗；扩大工作温度范围。经过多次试验优选，本发明最终确定的几种含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物的性能更加稳定，质量更加可靠。附图说明

Still another aspect of the invention provides a liquid crystal element including the liquid crystal composition as a constituent element. The liquid crystal compound represented by the general formula (I) provided by the present invention has a large optical anisotropy (Δη) and a large dielectric anisotropy (Δε), which is low compared with other liquid crystal compounds of the prior art. Rotational viscosity (γ) and wide nematic phase temperature range, good miscibility at low temperature, their chemical properties are stable; general formula (I) raw materials are readily available during preparation, and the environment is selected Friendly HFC-134a, the synthesis route is simple and easy, the reaction equipment is not very demanding, suitable for large-scale industrial production, and is used as a liquid crystal material for display, which can be used to improve the response time of the liquid crystal composition (ie, reduce the rotational viscosity); Improve the resistance to light and heat; reduce the driving voltage, reduce energy consumption; expand the operating temperature range. After a plurality of tests, the compounds of the structure comprising 1,2-difluoroethylene and difluoromethylene ether finally determined by the present invention are more stable and more reliable in quality. DRAWINGS

图 1是通式（I) 类化合物的合成路线。 Figure 1 is a synthetic route of a compound of the general formula (I).

图 2是化合物 1-2-1的质谱图。具体实施方式 Figure 2 is a mass spectrum of the compound 1-2-1. detailed description

以下将结合具体实施方案来说明本发明。需要说明的是，下面的实施例为本发明的优化组合，仅用来说明本发明，而不用来限制本发明。在不偏离本发明主旨或范围的情况下，可进行本发明构思内的其他组合和各种改良。在以下实施例中所采用的各成分，除另有说明外，均为市售产品或者由本申请的发明人按照公知的方法（参见 CN101143808 A, CN1869792 A.CN1253530 C，CN 101193999 A) 进行合成。这些合成技术是常规的，所得到各液晶化合物经测试符合电子类化合物标准。除下文中另有说明，液晶组合物的制备是按照本领域的常规方法进行的，如采取加热、超声波、悬浮等方式按照规定比例混合制得。实施例 1 上述的一种包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物的一种制备方法，其合成路线 1中表示。按照上述的合成路线制备的化合物 1-2-1的具体工艺步骤如下： The invention will now be described in connection with specific embodiments. It is to be understood that the following examples are illustrative of the invention and are not intended to limit the invention. Other combinations and various modifications within the inventive concept can be made without departing from the spirit or scope of the invention. The components used in the following examples are all commercially available or otherwise synthesized by the inventors of the present application in accordance with a known method (see CN101143808 A, CN1869792 A.CN1253530 C, CN 101193999 A). These synthetic techniques are conventional, and each of the obtained liquid crystal compounds has been tested to meet the standards of electronic compounds. Unless otherwise stated hereinafter, the preparation of the liquid crystal composition is carried out according to a conventional method in the art, such as heating, ultrasonication, suspension, etc., in a predetermined ratio. Embodiment 1 A method for producing a compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether, which is represented in Synthesis Scheme 1. The specific process steps of the compound 1-2-1 prepared according to the above synthetic route are as follows:

1 ) 对溴苯三氟乙烯的合成 1) Synthesis of p-bromobenzene trifluoroethylene

a. 250ml单口瓶中加入 57.7 ml二异丙胺， 180 mlTHF,氮气保护，乙醇浴降温至 -20Ό , 控温 0至 -20°C滴加 160 ml n-BuLi,滴毕，在 0至 -20°C搅拌 1小时，制得 1 mol/L LDA0.4mol 待用。 a. Add 57.7 ml of diisopropylamine, 180 ml of THF to a 250 ml single-mouth bottle, protect with nitrogen, and cool to -20 Torr in an ethanol bath. 160 ml of n-BuLi was added dropwise at a temperature of 0 to -20 ° C, and the mixture was stirred at 0 to -20 ° C for 1 hour to obtain 1 mol/L LDA 0.4 mol for use.

b. 1000ml三口瓶中加入 27.2g无水氯化锌， 100 ml THF, 氮气保护，乙醇浴降温至 -5(TC，通入 20.4g CF₃CH₂F，控温 -40至 -50Ό针管通入液面下缓慢注入上述 0.4 mol LDA, 加完后搅拌 2小时，制得三氟乙烯锌试剂待用。 b. Add 2.02g anhydrous zinc chloride, 100ml THF, nitrogen protection to the 1000ml three-neck bottle, cool down to -5 (TC, pass 20.4g CF ₃ CH ₂ F, temperature control -40 to -50Ό needle pass The above 0.4 mol LDA was slowly injected under the liquid surface, and after stirring, the mixture was stirred for 2 hours to prepare a trifluoroethylene zinc reagent for use.

c. 上述锌试剂中加入 28.3g对溴碘苯， Llg 4，3-钯，氮气保护，室温 20〜30°C反应过夜。加入 200ml水淬灭反应，稀盐酸调节 PH到 6左右，加入 200ml乙酸乙脂分液，水层用乙酸乙脂萃取两次，合并有机层，水洗两次，饱和食盐水洗一次，无水硫酸纳干燥，浓缩溶剂，石油醚过柱脱色，浓缩溶剂，得 18g透明液体，即为对溴苯三氟乙烯。收率 76%。 c. The above zinc reagent was added with 28.3 g of p-bromoiodobenzene, Llg 4,3-palladium, nitrogen gas, and reacted at room temperature at 20 to 30 ° C overnight. Add 200 ml of water to quench the reaction, adjust the pH to about 6 with dilute hydrochloric acid, add 200 ml of ethyl acetate to separate the liquid, extract the aqueous layer twice with ethyl acetate, combine the organic layers, wash twice with water, wash once with saturated brine, anhydrous sodium sulfate. Dry, concentrate the solvent, decolorize the petroleum ether through the column, and concentrate the solvent to obtain 18 g of a transparent liquid, which is p-bromobenzenetrifluoroethylene. Yield 76%.

2) E-1-溴 -4- ( 1,2-二氟 -2- (4-丙基苯基) 乙烯基）苯的合成 2) Synthesis of E-1-bromo-4-(1,2-difluoro-2-(4-propylphenyl)vinyl)benzene

d. 500ml三口瓶中加入 5.4g镁， 2粒碘， 20ml THF，交换氮气保护，缓慢滴加用 80 ml THF稀释的 37.3g 4-丙基溴苯溶液，反应引发，继续缓慢滴加剩下的溶液，滴毕，保持弱回流反应 2小时，制得 4-丙基苯基溴化镁试剂备用。 d. Add 5.4g magnesium, 2 iodine, 20ml THF to 500ml three-necked flask, exchange nitrogen protection, slowly add 37.3g 4-propylbromobenzene solution diluted with 80ml THF, the reaction is triggered, continue to slowly add the remaining The solution was diluted and kept under a weak reflux for 2 hours to prepare a 4-propylphenylmagnesium bromide reagent.

e. 500ml三口瓶中加入无水氯化镧 2.3g，无水氯化锂 2.1g， 20ml THF, 交换氮气保护，保持 -10至 1(TC缓慢滴加上述 4-丙基苯基溴化镁试剂，滴毕，继续控温反应半小时，备用。 e. Add 500g of anhydrous cesium chloride to the 500ml three-necked bottle, 2.1g of anhydrous lithium chloride, 20ml of THF, exchange nitrogen protection, keep -10 to 1 (TC slowly add the above 4-propyl phenyl magnesium bromide Reagent, drop, continue to control the temperature for half an hour, spare.

f. 500ml三口瓶中加入 37g对溴苯三氟乙烯， 50ml THF, 控温 -10°C至 0'C，氮气保护下，缓慢滴入上述溶液，滴完后反应 1小时， TLC检测反应终点，加入 50ml水淬灭反应， HC1调节 PH到 6左右，乙酸乙脂萃取，水洗，饱和 NaHC0₃洗涤，饱和 NaCl洗涤，无水硫酸钠干燥，旋干溶剂，用石油醚作流动相过硅胶柱，乙醇重结晶，得 13.7g白色固体，即为所需中间体，收率 26%。 f. Add 500g p-bromobenzene trifluoroethylene, 50ml THF to a 500ml three-necked flask, control temperature -10 ° C to 0 ° C, slowly dip into the above solution under nitrogen protection, react 1 hour after the completion of the TLC, test the end of the reaction Add 50ml water to quench the reaction, adjust the pH to about 6 by HC1, extract with ethyl acetate, wash with water, wash with saturated NaHC0 _3, wash with saturated NaCl, dry with anhydrous sodium sulfate, spin dry solvent, use petroleum ether as mobile phase through silica gel column. The ethanol was recrystallized to obtain 13.7 g of a white solid, which was the desired intermediate, yield 26%.

3 ) 4- (二氟（3，4，5-三氟苯氧基）甲基) -3,5-二氟苯硼酸的合成 3) Synthesis of 4-(difluoro(3,4,5-trifluorophenoxy)methyl)-3,5-difluorobenzeneboronic acid

g. 1000ml三口瓶中加入 38.9g4- (二氟（3,4,5-三氟苯氧基）甲基) -3,5-二氟溴苯， 200ml THF, 控温 -20°C〜3(TC，氮气保护下，缓慢滴入 lmol/L异丙基溴化镁溶液 150 ml，滴完后继续搅拌反应 2小时，将此反应液控温在 -20°C〜10°C，氮气保护下，缓慢滴入用 200 ml 干燥 THF稀释的 34.5g硼酸三异丁酯溶液中，滴完，搅拌反应 1小时， TLC检测反应终点，加入 200ml冰水淬灭反应， HC1调节 PH到 6左右，乙酸乙脂萃取，水洗，饱和 NaHC0₃ 洗涤，饱和 NaCl洗涤，无水硫酸钠干燥，旋干溶剂，用石油醚打浆，过滤得 26g类白色固体，即为所需硼酸中间体，收率 73%。 g. Add 38.9g of 4-(difluoro(3,4,5-trifluorophenoxy)methyl)-3,5-difluorobromobenzene, 200ml THF to 1000ml three-necked flask, temperature control -20 °C~3 (TC, under nitrogen protection, slowly drip 150ml of lmol/L isopropylmagnesium bromide solution, continue stirring for 2 hours after the completion of the dropwise addition, and control the temperature of the reaction solution at -20 °C~10 °C, nitrogen protection Next, slowly drip into 34.5 g of triisobutyl borate solution diluted with 200 ml of dry THF. After the dropwise addition, the reaction was stirred for 1 hour, and the reaction end point was detected by TLC. The reaction was quenched by adding 200 ml of ice water, and the pH of HC1 was adjusted to about 6, Ethyl acetate extraction, washing with water, washing with saturated NaHC0 _3, washing with saturated NaCI, drying over anhydrous sodium sulfate, drying over anhydrous sodium sulfate, solvent solvent, pulsing with petroleum ether, and filtering to obtain 26 g of white solid as the desired boronic acid intermediate, yield 73% .

4) 化合物 1-2-1的合成 4) Synthesis of compound 1-2-1

h. 500ml茄形瓶中加入 13.7g E-l-溴 -4- ( 1,2-二氟 -2- (4-丙基苯基）乙烯基）苯， 17.3g 4- (二氟（3,4,5-三氟苯氧基）甲基) -3,5-二氟苯硼酸， 40ml lmol/L碳酸钠溶液， 200ml乙二醇二甲醚， l.lg 4，3-钯，氮气保护，升温到 8CTC回流反应 6小时。 TLC检测反应终点，加入 200ml乙酸乙脂和 50ml水分液，水层用乙酸乙脂萃取两次，合并有机层，水洗两次，饱和食盐水洗一次，无水硫酸纳干燥，浓缩溶剂，柱层析后得 16g白色固体，即为化合物 1-2-1，收率 69.6%。 MS (m/z): 566(m+), 419, 390, 209, 195， 185。化合物 1-2-1的液晶性能： h. Add 500 g of eggplant-shaped flask to 13.7 g of El-bromo-4-(1,2-difluoro-2-(4-propylphenyl)vinyl)benzene, 17.3 g of 4-(difluoro(3,4) ,5-trifluorophenoxy)methyl)-3,5-difluorobenzeneboronic acid, 40 ml of 1 mol/L sodium carbonate solution, 200 ml of ethylene glycol dimethyl ether, l.lg 4,3-palladium, nitrogen protection, The temperature was raised to 8 CTC reflux for 6 hours. TLC was used to detect the end point of the reaction. Add 200 ml of ethyl acetate and 50 ml of water. The aqueous layer was extracted twice with ethyl acetate. The organic layer was combined, washed twice with water, once with saturated brine, dried over anhydrous sodium sulfate, concentrated solvent, column chromatography This gave 16 g of a white solid, which was compound 1-2-1, yield 69.6%. MS (m/z): 566 (m+), 419, 390, 209, 195, 185. Liquid crystal properties of compound 1-2-1:

Δη: 0.32 Δε: 26.2 CP Δη: 0.32 Δε: 26.2 CP

化合物 1-2-1的质谱图见附图 2。上述反应式中的 R与上述通式（I) 中的 R取代基的范围一致，优选 -C₂H₅、 n-C₃H₇、 n-C₄¾、 n-C₅H 环 A代表反式 1,4-亚环己基、反式 -1， 3-二噁垸 -2,5-二基、吡啶 -2,5-二基、嘧啶 -2,5-二基亚苯基或者被 1个或更多个氟原子取代或未取代的 1，4-亚苯基，优选被 1个或更多个氟原子取代或未取代的 1,4-亚苯基。 Z代表单键、 -CH₂CH₂-、-CH=CH-、- C≡C -、 -OCH₂-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF₂-、 -CF=CF -、 -OCO-、 -COO-;L^ L₂、 L₃、 L₄、 L₅、 L₆、 L₇和 L₈各自独立地代表氢原子或卤素原子； X代表 -H、 -CN、 -F、 -Cl、 -OCF₃、 -OCF₂H 、 -CF₃; m代表数字 0、 1，优选 0。采用这些取代基组成不同的包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物的性质与实施例中的物质接近，合成路线与实施例中相同，只是选用不同原料。下:

The mass spectrum of compound 1-2-1 is shown in Figure 2. R in the above reaction formula is identical to the range of the R substituent in the above formula (I), and preferably -C ₂ H ₅ , nC ₃ H ₇ , nC _{4 3⁄4} , nC ₅ H ring A represents trans 1,4- Cyclohexylene, trans-1,3-dioxin-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diphenylene or one or more The fluorine atom-substituted or unsubstituted 1,4-phenylene group is preferably a 1,4-phenylene group which is substituted or unsubstituted with one or more fluorine atoms. Z represents a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C -, -OCH ₂ -, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF ₂ -, -CF=CF -, -OCO-, -COO-; L^ L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and L ₈ each independently represent a hydrogen atom or a halogen atom; Representative -H, -CN, -F, -Cl, -OCF 3, -OCF 2 H, -CF 3; m represents a number 0, 1, 0 is preferable. The nature of the compounds comprising the 1,2-difluoroethylene and difluoromethylene ether structures using these substituents is similar to that of the examples, and the synthesis route is the same as in the examples, except that different materials are selected. under:

Δη: 0.32 Δε: 26.2 CP: 228.8°C Δη: 0.32 Δε: 26.2 CP: 228.8 °C

以下实施例中各测试项目的简写代号分别表示为-

The abbreviated codes of the test items in the following embodiments are respectively expressed as -

TN I fC) 清亮点（向列-各向同性相转变温度） γΐ 旋转粘度（mpa*s， 25 ) TN I fC) Clearing point (nematic-isotropic phase transition temperature) γΐ Rotational viscosity (mpa*s, 25 )

Δη 光学各向异性（589nm， 20 °C ) Δη optical anisotropy (589nm, 20 °C)

Δε 介电各向异性（ΙΚΗζ, 25 °C ) Δε dielectric anisotropy (ΙΚΗζ, 25 °C)

其中，流动粘度 γΐ使用 TOY06254进行测试；折射率各向异性使用阿贝折光仪在钠光灯（589nm) 光源下、 20°C测试得；介电测试盒为 TN90型，盒厚 7μιη。表 1. 对照例液晶组合物的成分及重量配比 Among them, the flow viscosity γΐ was tested using TOY06254; the refractive index anisotropy was measured using an Abbe refractometer in sodium The light (589nm) light source was tested at 20 °C; the dielectric test box was TN90 type, and the box thickness was 7μιη. Table 1. Composition and weight ratio of the comparative liquid crystal composition

实施例 2 Example 2

表 2所列的各化合物及重量份数配制成本发明的液晶组合物，其填充于液晶显示器两基板之间进行性能测试，测试数据也列于表 2。表 2. 实施例 2的组分及重量份数 Each of the compounds and parts by weight listed in Table 2 were formulated into a liquid crystal composition of the present invention, which was filled between two substrates of a liquid crystal display for performance test, and the test data is also shown in Table 2. Table 2. Components and parts by weight of Example 2

从对照例和实施例 2可以显著的得出以下结论： From the comparative example and the example 2, the following conclusions can be remarkably obtained:

使用了本发明的通式 I所包含的化合物，实施例 2的折射率与对照例相比有了明显的提升，可以用到更薄的 cell中，从而得到更短的响应时间； By using the compound of the formula I of the present invention, the refractive index of the embodiment 2 is remarkably improved as compared with the comparative example, and it can be used in a thinner cell, thereby obtaining a shorter response time;

使用了本发明的通式 I所包含的化合物，实施例 2的旋转粘度与对照例相比有了一定程度的下降，从而得到更短的响应时间； Using the compound of the formula I of the present invention, the rotational viscosity of Example 2 was somewhat lowered as compared with the comparative example, thereby obtaining a shorter response time;

使用了本发明的通式 I所包含的化合物，实施例 2的清亮点与对照例相比有了明显的提升，从而得到更宽的上限工作温度范围； Using the compound of the formula I of the present invention, the clearing point of Example 2 was significantly improved as compared with the comparative example, thereby obtaining a wider upper working temperature range;

使用了本发明的通式 I所包含的化合物，实施例 2的介电各向异性与对照例相比有了明显的增大，从而得到更低的驱动电压，降低能耗。 Using the compound of the formula I of the present invention, the dielectric anisotropy of Example 2 was significantly increased as compared with the comparative example, thereby obtaining a lower driving voltage and lowering the energy consumption.

Claims

1. 一种包含 1,2-二氟乙烯和二氟亚甲基醚结构的化合物，所述化合物具有通式（I) 所示的结构- A compound comprising a structure of 1,2-difluoroethylene and difluoromethylene ether, the compound having a structure represented by the formula (I) -

其中： among them:

R代表 1-15个碳的烷基或烯基、 1-15个碳的垸氧基或烯氧基； R represents an alkyl or alkenyl group of 1 to 15 carbons, a decyloxy group or an alkenyloxy group of 1 to 15 carbons;

环 A代表反式 1,4-亚环己基、反式 -1,3-二噁垸 -2,5-二基、吡啶 -2,5-二基、嘧啶 -2,5- 二基亚苯基或者被 1个或更多个氟原子取代或未取代的 1，4-亚苯基； Ring A represents trans 1,4-cyclohexylene, trans-1,3-dioxin-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diphenylene a 1,4-phenylene group substituted or unsubstituted with one or more fluorine atoms;

Z代表单键、 -CH₂CH₂-、 -CH=CH-、- C≡C -、 -OC¾-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF₂-、 -CF=CF -、 -OCO-、 -COO-, Z represents a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C -, -OC3⁄4-, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF ₂ -, -CF=CF -, -OCO-, -COO-,

L,、 L₂、 L₃、 L₄、 L₅、 L₆、 L₇和 1^₈各自独立地代表氢原子或卤素原子； L, L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and 1 ₈ each independently represent a hydrogen atom or a halogen atom;

X代表 -H、 -CN、 -F、 -Cl、 -OCF₃、 -OCF₂H、 -CF₃; X represents -H, -CN, -F, -Cl, -OCF ₃ , -OCF ₂ H, -CF ₃ ;

m代表数字 0、 1。 m stands for the number 0, 1.

2. 根据权利要求 1所述的化合物，其中 R代表 1-7个碳的直链垸基或直链烯基、 1-7 个碳的直链垸氧基或直链烯氧基。 The compound according to claim 1, wherein R represents a linear fluorenyl group or a linear alkenyl group of 1 to 7 carbons, a linear decyloxy group of 1 to 7 carbons or a linear alkenyloxy group.

3. 根据权利要求 1所述的化合物，其中环 A代表反式 1,4-亚环己基或者被 1个或更多个氟原子取代或未取代的 1，4-亚苯基。 The compound according to claim 1, wherein the ring A represents a trans 1,4-cyclohexylene group or a 1,4-phenylene group substituted or unsubstituted with one or more fluorine atoms.

4. 根据权利要求 1所述的化合物，其中 Z代表单键、 -CH₂CH₂-、 -OCH₂-、 -CH₂0-、 -OCF₂-、 -CF₂0-、 -CF₂CF 4. The compound according to claim 1, wherein Z represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ 0-, -OCF ₂ -, -CF ₂ 0-, -CF ₂ CF

5. 根据权利要求 1所述的化合物，其中 L卜 L₂、 L₃、 L₄、 L₅、 L₆、 L₇和 L₈各自独立地代表氢原子或氟原子。 The compound according to claim 1, wherein L b L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and L ₈ each independently represent a hydrogen atom or a fluorine atom.

6. 根据权利要求 1所述的化合物，其中 X代表 -F、 -OCF₃。 6. A compound according to claim 1, wherein X represents -F, -OCF _3.

7. 根据权利要求 1所述的化合物，其中 m代表 0。 7. The compound of claim 1 wherein m represents zero.

8. 根据权利要求 1所述的化合物，所述化合物选自由以下化合物组成的组:

81 8. The compound of claim 1 selected from the group consisting of:

81

9. 根据权利要求 1〜8中任何一项所述的化合物的制备方法，包括如下步骤- 1 ) 在溶剂中，于低温下，将 1，1,1，2-四氟乙烷在 LDA作用下反应得到三氟乙烯锌试剂，再在催化剂的存在下经钯催化偶联，得到式 2 所示化合物式 2The method for producing a compound according to any one of claims 1 to 8, which comprises the following steps - 1) in the solvent, at a low temperature, the action of 1,1,1,2-tetrafluoroethane in LDA The reaction is carried out to obtain a trifluoroethylene zinc reagent, and then palladium-catalyzed coupling in the presence of a catalyst to obtain a compound of the formula 2

2)在溶剂中，在 Aryl-MgX/LnCl₃作用下，由式 2所示化合物得到烯键具有顺反异构的化合物，再经转位反应得到式 3所示化合物式 32) In the solvent, under the action of Aryl-MgX/LnCl ₃ , a compound having the olefinic bond having a cis-trans isomer is obtained from the compound of the formula 2, and then a transposition reaction is carried out to obtain a compound of the formula 3 represented by the formula 3

3 ) 低温下，在异丙基溴用下，式 4所示化合物

3) Compounds of formula 4 under low temperature and isopropyl bromide

式 4 Equation 4

和硼酸三异丁酯反应生成式

Reaction with triisobutyl borate

式 5 再将所述式 5所示化合物和所述式 3所示化合物在催化剂的存在下经钯催化剂偶联反应得到通式（I) 所示化合物； Further, the compound of the formula 5 and the compound of the formula 3 are further subjected to a palladium catalyst coupling reaction in the presence of a catalyst to obtain a compound of the formula (I);

所述步骤 1 )和步骤 3 )中的催化剂可以相同或不同，选自由四（三苯基膦）合钯（0)，二（三苯基膦）二氯化钯（11 )，醋酸钯（III) 和钯 /炭催化剂组成的组。 The catalysts in the step 1) and the step 3) may be the same or different and are selected from the group consisting of tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium dichloride (11), palladium acetate ( III) and a group consisting of palladium/carbon catalysts.

10. 根据权利要求 9所述的化合物的制备方法，其中步骤 2) 中使用的 LnCl₃选自由 LaCl₃, CeCl₃和 NdCl₃组成的组； LnCl₃的用量为 l-30mol%; 并且，由式 2所示化合物得到烯键具有顺反异构的化合物的反应需在氮气氛下、 -30〜80°C之间进行。 The method for producing a compound according to claim 9, wherein the LnCl ₃ used in the step 2) is selected from the group consisting of LaCl ₃ , CeCl ₃ and NdCl ₃ ; the amount of LnCl ₃ is from 1 to 30 mol%; The reaction of the compound of the formula 2 to give a compound having an olefinic bond having a cis-trans isomerization is carried out under a nitrogen atmosphere at a temperature of from -30 to 80 °C.

11. 根据权利要求 10所述的化合物的制备方法，其中当所述 LnCl₃为 LaCl₃时，还需要使用 LiCl, 所述 LiCl的用量为 LaCl₃的 2倍。 The method for producing a compound according to claim 10, wherein when the LnCl ₃ is LaCl ₃ , it is further required to use LiCl, and the amount of the LiCl is twice that of LaCl ₃ .

12. 一种液晶组合物，包括一种或更多种如权利要求 1〜8中的任一项所述的化合物 _t A liquid crystal composition comprising one or more compounds _t according to any one of claims _{1 to}

13. 一种以权利要求 12所述的液晶组合物为构成要素的液晶元件。 A liquid crystal element comprising the liquid crystal composition according to claim 12 as a constituent element.