TWI509058B - Liquid crystal compound, liquid crystal composition and liquid crystal display device - Google Patents

Liquid crystal compound, liquid crystal composition and liquid crystal display device Download PDF

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TWI509058B
TWI509058B TW103127952A TW103127952A TWI509058B TW I509058 B TWI509058 B TW I509058B TW 103127952 A TW103127952 A TW 103127952A TW 103127952 A TW103127952 A TW 103127952A TW I509058 B TWI509058 B TW I509058B
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liquid crystal
substituted
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crystal compound
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TW201604268A (en
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Ching Tien Lee
Hsin Cheng Liu
Chun Chih Wang
Tian-Meng Jiang
hui-qiang Tian
Li-Long Gao
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Daxin Materials Corp
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液晶化合物、液晶組合物以及液晶顯示元件Liquid crystal compound, liquid crystal composition, and liquid crystal display element

本發明是有關於一種液晶化合物,且特別是有關於一種具有高介電常數異向性及低轉動黏度的液晶化合物、含有該液晶化合物的液晶組合物以及液晶顯示元件。The present invention relates to a liquid crystal compound, and more particularly to a liquid crystal compound having high dielectric anisotropy and low rotational viscosity, a liquid crystal composition containing the liquid crystal compound, and a liquid crystal display element.

液晶顯示器具有重量輕、省電、無輻射與全彩顯示等優點,因此已成為最普遍的顯示器產品。近年來,隨著技術不斷提升,以及對高解析度、高反應速率與高畫質的要求,液晶顯示器已由扭轉向列(twisted nematic,TN)、超扭轉向列(super twisted nematic,STN)與雙穩態扭轉向列(bistable twisted nematic,BTN)等被動式驅動顯示方式,發展成具有薄膜電晶體(thin film transistor,TFT)的主動矩陣式液晶顯示器。隨著廣視角技術的需求,橫向電場(in-plane switching,IPS)、邊界電場切換(fringe field switching,FFS)、垂直配向(vertical alignment,VA)與聚合物穩定配向(polymer sustained alignment,PSA)等液晶顯示方式的開發與突破,對於未來面板的應用與發展是相當重要的。Liquid crystal displays have the advantages of light weight, power saving, no radiation and full color display, so they have become the most common display products. In recent years, with the continuous improvement of technology and the requirements for high resolution, high reaction rate and high image quality, liquid crystal displays have been twisted nematic (TN), super twisted nematic (STN). With the passive drive display mode such as bistable twisted nematic (BTN), it has developed into an active matrix liquid crystal display with a thin film transistor (TFT). With the demand of wide viewing angle technology, in-plane switching (IPS), fringe field switching (FFS), vertical alignment (VA) and polymer sustained alignment (PSA) The development and breakthrough of liquid crystal display methods are very important for the application and development of future panels.

對於液晶顯示器來說,目前需要的是具有高介電常數異向性(dielectric constant anisotropy,△ε)、低轉動黏度(rotational viscosity,γ1)、適當的折射率(birefringence)以及範圍廣的操作溫度的液晶介質。特別是,當液晶介質具有較高的介電常數異向性時,可以降低液晶顯示裝置的閾值電壓(threshold voltage,Vth);當液晶介質具有較低的轉動黏度時,可以加快應答(response)速度;當液晶介質具有較高的澄清點時,可擴大液晶介質的應用操作溫度範圍。For liquid crystal displays, what is needed is a dielectric constant anisotropy (Δε) and a low rotational viscosity (rotational). Viscosity, γ1), suitable refractive index, and a wide range of operating temperature liquid crystal media. In particular, when the liquid crystal medium has a high dielectric anisotropy, the threshold voltage (Vth) of the liquid crystal display device can be lowered; when the liquid crystal medium has a low rotational viscosity, the response can be accelerated. Speed; when the liquid crystal medium has a high clearing point, the application operating temperature range of the liquid crystal medium can be expanded.

本發明提供一種液晶化合物,將該液晶化合物應用於液晶組合物中,可使液晶組合物具有高介電常數異向性、低轉動黏度以及寬液晶相範圍,且採用該液晶組合物製作液晶顯示元件,可使液晶顯示元件具有更好顯示效能及品質。The present invention provides a liquid crystal compound which can be applied to a liquid crystal composition to provide a liquid crystal composition having a high dielectric anisotropy, a low rotational viscosity, and a wide liquid crystal phase range, and the liquid crystal composition is used to produce a liquid crystal display. The component can make the liquid crystal display element have better display performance and quality.

本發明的液晶化合物,由式1表示:式1,其中R1 為烷基或烯基,R1 中的一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代,其中當R1 中的一或多個-CH2 -未被-O-取代時,R1 的碳數為2至10,而當R1 中的一個或不相鄰的多個-CH2 -被-O-取代時,R1 的碳數仍為2至10;R2 為碳數為1至10的烷基;A1 、A2 、A3 及A4 獨立地為1,4-伸環己基或1,4-伸苯基,其中A1 到A4 上的一或多個氫原子可被鹵素取代;Z1 、Z2 及Z3 獨立地為單鍵、-C2 H4 -、-COO-、-OCO-、-CF2 O-、-OCF2 -、-C≡C-或-CH=CH-;以及 n、m獨立地為1或0。The liquid crystal compound of the present invention is represented by Formula 1: Formula 1, wherein R 1 is an alkyl group or an alkenyl group, one or more hydrogen atoms in R 1 may be substituted by a fluorine atom, and one or a plurality of adjacent -CH 2 - may be substituted by -O-, wherein R 1 in one or more -CH 2 - -O- unsubstituted substituent, the carbon number of R 1 is 2 to 10, and when R 1 in one or a plurality of non-adjacent -CH 2 - is - When O-substituted, R 1 has a carbon number of 2 to 10; R 2 is an alkyl group having 1 to 10 carbon atoms; and A 1 , A 2 , A 3 and A 4 are independently 1,4-cyclohexylene. Or 1,4-phenylene, wherein one or more hydrogen atoms on A 1 to A 4 may be substituted by halogen; Z 1 , Z 2 and Z 3 are independently a single bond, -C 2 H 4 -, - COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- or -CH=CH-; and n, m are independently 1 or 0.

本發明的液晶組合物包括如前所述的液晶化合物。The liquid crystal composition of the present invention comprises a liquid crystal compound as described above.

本發明的液晶顯示元件包括如前所述的液晶化合物。The liquid crystal display element of the present invention comprises a liquid crystal compound as described above.

基於上述,本發明提出一種液晶化合物以及包含此液晶化合物的液晶組合物和液晶顯示元件,其中液晶組合物具有高介電常數異向性、低轉動黏度、寬液晶相範圍、以及良好的耐酸性、耐熱性及耐UV性。Based on the above, the present invention provides a liquid crystal compound and a liquid crystal composition comprising the liquid crystal compound and a liquid crystal display element, wherein the liquid crystal composition has high dielectric anisotropy, low rotational viscosity, wide liquid crystal phase range, and good acid resistance Heat resistance and UV resistance.

為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施方式作詳細說明如下。The above described features and advantages of the present invention will be more apparent from the following description.

在本文中,由「一數值至另一數值」表示的範圍,是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此,記載了某一特定數值範圍,等同於揭露了該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍,如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。例如,記載「含量為10~80%」的範圍,就等同於揭露了「含量為20%~40%」的範圍,無論說明書中是否列舉其他數值。In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, a particular numerical range is recited and is equivalent to the disclosure of any numerical value in the range of the value and the numerical range defined by any value in the numerical range, as the The smaller value range is the same. For example, the description of the "content of 10 to 80%" is equivalent to the disclosure of the "content of 20% to 40%", regardless of whether other values are listed in the specification.

在本文中,如果沒有特別指明某一基團是否經過取代,則該基團可表示經取代或未經取代的基團。例如,「烷基」可表示經取代或未經取代的烷基。Herein, if a group is not specifically indicated to be substituted, the group may represent a substituted or unsubstituted group. For example, "alkyl" can mean a substituted or unsubstituted alkyl group.

在本文中,有時以鍵線式(skeleton formula)表示化合物結構。這種表示法可以省略碳原子、氫原子以及碳氫鍵。當然,結構式中有明確繪出原子或原子基團的,則以繪示者為準。In this context, the structure of a compound is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the atom or atomic group is clearly drawn in the structural formula, the person who prescribes it shall prevail.

本發明的一實施方式提出一種液晶化合物,其具有高介電常數異向性、低轉動黏度、寬液晶相範圍以及良好的耐酸性、耐熱性及耐UV性。One embodiment of the present invention provides a liquid crystal compound having high dielectric anisotropy, low rotational viscosity, wide liquid crystal phase range, and good acid resistance, heat resistance, and UV resistance.

本實施方式的液晶化合物由以下式1表示:式1,其中R1 、R2 、A1 、A2 、A3 、A4 、Z1 、Z2 、Z3 、n和m的定義將於下文中進行詳細說明。The liquid crystal compound of the present embodiment is represented by the following formula 1: Formula 1, wherein the definitions of R 1 , R 2 , A 1 , A 2 , A 3 , A 4 , Z 1 , Z 2 , Z 3 , n and m will be described in detail below.

R1 為烷基或烯基,R1 中的一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代,其中當R1 中的一或多個-CH2 -未被-O-取代時,R1 的碳數為2至10,較佳的碳數為2至5,而當R1 中的一個或不相鄰的多個-CH2 -被-O-取代時,R1 的碳數仍為2至10,較佳的碳數為2至5。也就是說,在本實施方式中,R1 可以是未經取代的烷基或烯基、烷基或烯基中的一或多個氫原子被氟原子取代後的基團、烷基或烯基中的一個或不相鄰的多個-CH2 -被-O-取代後的基團,或烷基或烯基中的一或多個氫原子被氟原子取代且一個或不相鄰的多個-CH2 -被-O-取代後的基團,且無論R1 中的-CH2 -是否被-O-取代,R1 的碳數都是2至10,較佳的碳數是2至5。另外,前述烷基可以是直鏈或分支鏈的烷基,前述烯基可以是直鏈或分支鏈的烯基。R 1 is an alkyl or alkenyl group, one or more hydrogen atoms of R 1 may be substituted with a fluorine atom, or a plurality of non-adjacent -CH 2 - may be replaced by -O-, wherein R 1 is wherein when When one or more -CH 2 - is not substituted by -O-, R 1 has a carbon number of 2 to 10, preferably a carbon number of 2 to 5, and when one or none of R 1 is adjacent When -CH 2 - is substituted by -O-, R 1 has a carbon number of 2 to 10, and preferably has a carbon number of 2 to 5. That is, in the present embodiment, R 1 may be a group, an alkyl group or an alkene in which one or more hydrogen atoms in an unsubstituted alkyl or alkenyl group, an alkyl group or an alkenyl group are substituted by a fluorine atom. One or a plurality of non-adjacent groups of -CH 2 - are substituted by -O-, or one or more hydrogen atoms in the alkyl or alkenyl group are replaced by fluorine atoms and one or non-adjacent more -CH 2 - replaced by -O- the group, and whether in R 1 -CH 2 - substituted with -O- whether, R 1 is a carbon number of 2 to 10, carbon atoms is preferred 2 to 5. Further, the aforementioned alkyl group may be a linear or branched alkyl group, and the aforementioned alkenyl group may be a linear or branched alkenyl group.

在一實施方式中,R1 中的一或多個氫原子被氟原子取代。In one embodiment, one or more hydrogen atoms in R 1 are replaced by a fluorine atom.

在一實施方式中,R1 中的一個或不相鄰的多個-CH2 -被-O-取代;例如,R1 可為烷氧基、烯氧基或醚基。In one embodiment, R 1 is one or more non-adjacent -CH 2 - replaced by -O-; e.g., R 1 may be an alkoxy group, an alkenyl group or an ether group.

在一實施方式中,R1 為烯基,其中,一或多個氫原子可被氟原子取代,且R1 中的一個或不相鄰的多個-CH2 -經-O-取代;亦即,R1 為同時含有-O-及雙鍵的基團。例如,R1 為-OCHCF2 、-OCF2 CHCF2 、-OCHCHCH3In one embodiment, R 1 is an alkenyl group, wherein one or more hydrogen atoms may be substituted by a fluorine atom, and one of R 1 or a plurality of non-adjacent-CH 2 - is substituted by -O-; That is, R 1 is a group containing both -O- and a double bond. For example, R 1 is -OCHCF 2 , -OCF 2 CHCF 2 , -OCHCHCH 3 .

在一實施方式中,R1 選自碳數為2至10的烷基、烷氧基、烯基、烯氧基或醚基,較佳是選自碳數為2至5的烷基、烷氧基、烯基、烯氧基或醚基,其中,R1 上的一或多個氫原子可被氟原子取代。In one embodiment, R 1 is selected from an alkyl, alkoxy, alkenyl, alkenyloxy or ether group having a carbon number of 2 to 10, preferably an alkyl group or an alkane having a carbon number of 2 to 5. An oxy, alkenyl, alkenyloxy or ether group in which one or more hydrogen atoms on R 1 may be substituted by a fluorine atom.

在一實施方式中,R1 為-OCHCF2 、-OCF2 CFCF2 或-OCH2 CF3In one embodiment, R 1 is -OCHCF 2 , -OCF 2 CFCF 2 or -OCH 2 CF 3 .

R2 為碳數為1至10的烷基。詳細而言,R2 為碳數為1至10的直鏈或分支鏈的烷基,例如:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、戊基、己基、庚基、辛基、壬基或癸基等。R 2 is an alkyl group having 1 to 10 carbon atoms. In detail, R 2 is a linear or branched alkyl group having a carbon number of 1 to 10, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl Base, pentyl, hexyl, heptyl, octyl, decyl or fluorenyl.

A1 、A2 、A3 及A4 獨立地為1,4-伸環己基或1,4-伸苯基,其中A1 到A4 上的一或多個氫原子可被鹵素取代。詳細而言,所述1,4-伸環己基及1,4-伸苯基上的一或多個氫原子可被氟原子、氯原子或溴原子取代。A 1 , A 2 , A 3 and A 4 are independently 1,4-cyclohexylene or 1,4-phenylene, wherein one or more hydrogen atoms on A 1 to A 4 may be substituted by halogen. In detail, one or more hydrogen atoms on the 1,4-cyclohexylene group and the 1,4-phenylene group may be substituted by a fluorine atom, a chlorine atom or a bromine atom.

在一實施方式中,A1 、A2 、A3 及A4 獨立地選自由所組成的族群。In one embodiment, A 1 , A 2 , A 3 and A 4 are independently selected from , and The group of people formed.

在一實施方式中,A1 、A2 、A3 及A4 獨立地選自由所組成的族群。In one embodiment, A 1 , A 2 , A 3 and A 4 are independently selected from and The group of people formed.

在一實施方式中,A1 、A2 、A3 及A4In one embodiment, A 1 , A 2 , A 3 and A 4 are .

Z1 、Z2 及Z3 獨立地為單鍵、-C2 H4 -、-COO-、-OCO-、-CF2 O-、-OCF2 -、-C≡C-或-CH=CH-。在一實施方式中,Z1 、Z2 及Z3 獨立地選自由單鍵及-CF2 O-所組成的族群。Z 1 , Z 2 and Z 3 are independently a single bond, -C 2 H 4 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- or -CH=CH -. In one embodiment, Z 1 , Z 2 and Z 3 are independently selected from the group consisting of a single bond and -CF 2 O-.

n、m獨立地為1或0。也就是說,式1表示的液晶化合物具有三至五個環結構。在一實施方式中,n和m皆為0;亦即, 式1表示的液晶化合物具有三個環結構,且其中的結構與R2 直接相接。n, m are independently 1 or 0. That is, the liquid crystal compound represented by Formula 1 has a structure of three to five rings. In one embodiment, n and m are both 0; that is, the liquid crystal compound represented by Formula 1 has three ring structures, and wherein The structure is directly connected to R 2 .

另外,在一實施方式中,式1表示的液晶化合物選自由以下式1-a至式1-d表示的化合物所組成的族群:式1-a,式1-b,式1-c,以及式1-d, 其中式1-a至式1-d中的R1 及R2 的定義已於上文中說明。Further, in one embodiment, the liquid crystal compound represented by Formula 1 is selected from the group consisting of compounds represented by the following Formula 1-a to Formula 1-d: Equation 1-a, Equation 1-b, Equation 1-c, and Formula 1-d, wherein the definitions of R 1 and R 2 in the formula 1-a to the formula 1-d have been explained above.

在一實施方式中,式1表示的液晶化合物例如選自由以下液晶化合物1-a-1~1-a-3、1-b-1~1-b-3、1-c-1及1-d-1所組成的族群:1-a-1,1-a-2,1-a-3,1-b-1,1-b-2,1-b-3,1-c-1,以及1-d-1。In one embodiment, the liquid crystal compound represented by Formula 1 is selected, for example, from the following liquid crystal compounds 1-a-1 to 1-a-3, 1-b-1 to 1-b-3, 1-c-1, and 1- The group consisting of d-1: 1-a-1, 1-a-2, 1-a-3, 1-b-1, 1-b-2, 1-b-3, 1-c-1, and 1-d-1.

由於式1表示的液晶化合物的骨架中具有結構 且R1 的碳數是2至10,因此具有高介電常數異向性、低轉動黏度以及寬液晶向列相範圍。另外,透過調整不同的連接基團或取代基(例如氟原子),可使得式1表示的液晶化合物進一步達到降低轉動黏度同時保持耐酸性、耐熱性及耐UV性的目的。Since the liquid crystal compound represented by Formula 1 has a skeleton The structure and R 1 have a carbon number of 2 to 10, and thus have a high dielectric anisotropy, a low rotational viscosity, and a wide liquid crystal nematic phase range. Further, by adjusting different linking groups or substituents (for example, fluorine atoms), the liquid crystal compound represented by Formula 1 can further achieve the purpose of lowering the rotational viscosity while maintaining acid resistance, heat resistance, and UV resistance.

本發明的另一實施方式提出一種液晶組合物,該液晶組合物除了包括式1表示的液晶化合物外,更包括選自由式2所表示之化合物中的至少一者:式2,其中R3 為碳數為1至10的烷基或碳數為2至10的烯基,且在前述烷基或烯基中,一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代;R4 為鹵素、碳數為1至10的烷基或碳數為2至10的烯基,且於前述烷基或烯基中,一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代;A5 、A6 及A7 獨立地為1,4-伸環己基或1,4-伸苯基,其中A5 到A7 上的一或多個氫原子可被鹵素取代;Z4 及Z5 獨立地為單鍵、-C2 H4 -、-COO-、-OCO-、-CF2 O-、-OCF2 -、-C≡C-或-CH=CH-;以及o為1或0。Another embodiment of the present invention provides a liquid crystal composition comprising, in addition to the liquid crystal compound represented by Formula 1, at least one selected from the group consisting of compounds represented by Formula 2: Formula 2 wherein R 3 is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the aforementioned alkyl or alkenyl group, one or more hydrogen atoms may be substituted by a fluorine atom, one Or a plurality of non-adjacent -CH 2 - may be substituted by -O-; R 4 is a halogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and the aforementioned alkyl group or alkene In the group, one or more hydrogen atoms may be substituted by a fluorine atom, and one or a plurality of adjacent -CH 2 - may be substituted by -O-; A 5 , A 6 and A 7 are independently 1,4-stretched Cyclohexyl or 1,4-phenylene, wherein one or more hydrogen atoms on A 5 to A 7 may be substituted by halogen; Z 4 and Z 5 are independently a single bond, -C 2 H 4 -, -COO -, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- or -CH=CH-; and o is 1 or 0.

在本實施方式中,以液晶組合物的總重計,式1表示的液晶化合物的含量為2wt%至50wt%,較佳為2.5wt%至25wt%,而式2表示的化合物的含量為1wt%至99wt%,較佳為50wt%至91wt%。In the present embodiment, the content of the liquid crystal compound represented by Formula 1 is 2 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, based on the total weight of the liquid crystal composition, and the content of the compound represented by Formula 2 is 1 wt. % to 99% by weight, preferably 50% by weight to 91% by weight.

在一實施方式中,式2表示的化合物包括以下液晶化合 物2-a~2-c:2-a;2-b;2-c。In one embodiment, the compound represented by Formula 2 includes the following liquid crystal compounds 2-a to 2-c: 2-a; 2-b; 2-c.

由於本實施方式的液晶組合物含有前述由式1表示的液晶化合物,因此具有高介電常數異向性、低轉動黏度、寬液晶相範圍、以及良好的耐酸性、耐熱性及耐UV性。Since the liquid crystal composition of the present embodiment contains the liquid crystal compound represented by Formula 1, it has high dielectric anisotropy, low rotational viscosity, wide liquid crystal phase range, and good acid resistance, heat resistance, and UV resistance.

本發明的又一實施方式提出一種液晶顯示元件,該液晶顯示元件的特徵在於,包括任一種前述實施方式中的液晶組合物。當然,該液晶顯示元件也可以具有其他已知的液晶顯示元件的構件,例如基板、偏光片、彩色濾光片或配向膜等等。除了內含的液晶組合物以外,此液晶顯示元件的製造方法和構成元件可以從習知技術中任意選擇,因此不在此贅述。Still another embodiment of the present invention provides a liquid crystal display element characterized by comprising the liquid crystal composition of any of the foregoing embodiments. Of course, the liquid crystal display element may also have other known members of the liquid crystal display element, such as a substrate, a polarizer, a color filter or an alignment film, and the like. The manufacturing method and constituent elements of the liquid crystal display element can be arbitrarily selected from the prior art except for the liquid crystal composition contained therein, and thus will not be described herein.

由於本實施方式的液晶顯示元件採用了含有前述由式1表示的液晶化合物的液晶組合物,因此不但具有閾值電壓低以及應答速度快的優點,還適於在較寬的溫度範圍下使用且具良好的顯示品質。Since the liquid crystal display element of the present embodiment employs the liquid crystal composition containing the liquid crystal compound represented by Formula 1 described above, it has advantages of low threshold voltage and fast response speed, and is also suitable for use over a wide temperature range. Good display quality.

〔實驗〕〔experiment〕

下文將參照實施例,更具體地描述本發明。雖然描述了以下實驗,但是在不逾越本發明範疇的情況下,可適當地改變所 用材料、其量及比率、處理細節以及處理流程等等。因此,不應根據下文所述的實驗對本發明作出限制性地解釋。The invention will be described more specifically hereinafter with reference to the embodiments. Although the following experiments are described, the contents can be appropriately changed without exceeding the scope of the present invention. Use materials, their quantities and ratios, processing details, and process flow. Therefore, the invention should not be construed restrictively on the basis of the experiments described below.

由於以下實施例和比較例使用多種液晶化合物,為求表示的簡潔,下文將以代號的組合來表示不同的液晶化合物,其中以O代表氧原子,以及每一代號分別表示的結構單元整理於表一。Since the following examples and comparative examples use a plurality of liquid crystal compounds, for the sake of simplicity of the description, different liquid crystal compounds will be denoted by a combination of code numbers, wherein O represents an oxygen atom, and each structural unit represented by each code is arranged in a table. One.

〈液晶化合物的合成方法〉<Synthesis method of liquid crystal compound> 合成例1Synthesis Example 1

製備液晶化合物1-a-1(2toPU-O1CF3)的合成方法如下所示。A method for synthesizing the liquid crystal compound 1-a-1 (2toPU-O1CF3) is shown below.

化合物a1的合成:Synthesis of compound a1:

於500ml乾燥潔淨的三口瓶中加入100g的1,1,1-三羥甲基丙烷、132g的碳酸二乙酯(diethyl carbonate,DEC)、0.25g的氫氧化鉀以及10ml的乙醇。接著,攪拌前述混合物,並加熱迴流2小時。之後,於150℃下常壓蒸除溶劑後,將溫度降至120℃。最後進行減壓蒸餾,以得到呈無色透明液體的化合物a1(產率:64.7%)。100 g of 1,1,1-trimethylolpropane, 132 g of diethyl carbonate (DEC), 0.25 g of potassium hydroxide and 10 ml of ethanol were placed in a 500 ml dry clean three-necked flask. Next, the mixture was stirred and heated to reflux for 2 hours. Thereafter, after evaporating the solvent under normal pressure at 150 ° C, the temperature was lowered to 120 ° C. Finally, distillation under reduced pressure was carried out to obtain Compound a1 (yield: 64.7%) as a colorless transparent liquid.

化合物a2的合成:Synthesis of compound a2:

於2L潔淨的三口瓶中加入82g的化合物a1、111g吡啶以及400ml二氯甲烷。接著,在氮氣保護下攪拌前述混合物,並降溫至0℃~5℃。控溫在0℃~5℃下,滴加由163g的4-溴苯甲醯氯以及200ml的二氯甲烷組成的溶液。滴加完畢後,自然升溫並攪拌過夜。之後,向三口瓶中加入500ml的水,攪拌5min後進行分液得水相及有機相。接著,用100ml的二氯甲烷提取水相 兩次,以及用100ml的氯化鈉水溶液洗滌合併後的有機相兩次至pH值接近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,將濾液進行矽膠管柱層析(沖提液為石油醚:乙酸乙酯=9:1)收集層析液並濃縮後使用1倍量的乙醇進行再結晶,並將其放入冰箱冷凍8小時以上後取出以進行抽氣過濾。最後,使用少量凍乙醇淋洗以得到呈白色固體的化合物a2(實際產量:145g,產率:68.7%,純度(以氣相層析儀GC進行量測):98.109%,熔點(mp):50.63℃~52.56℃)。To a 2 L clean three-necked flask was added 82 g of compound a1, 111 g of pyridine and 400 ml of dichloromethane. Next, the mixture was stirred under a nitrogen atmosphere and cooled to 0 ° C to 5 ° C. The temperature control was carried out at 0 ° C to 5 ° C, and a solution consisting of 163 g of 4-bromobenzamide chloride and 200 ml of dichloromethane was added dropwise. After the addition was completed, the temperature was naturally raised and stirred overnight. Thereafter, 500 ml of water was added to the three-necked flask, and after stirring for 5 minutes, liquid separation and organic phase were carried out. Next, extract the aqueous phase with 100 ml of dichloromethane. The combined organic phases were washed twice with 100 ml of an aqueous solution of sodium chloride twice until the pH was near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was subjected to gel column chromatography (the extract was petroleum ether: ethyl acetate = 9:1). The chromatographic solution was collected, concentrated, and recrystallized using 1 time of ethanol, and placed in a refrigerator. After 8 hours or more, it was taken out for suction filtration. Finally, a small amount of frozen ethanol was used to rinse to give Compound a2 as a white solid (actual yield: 145 g, yield: 68.7%, purity (measured by gas chromatograph GC): 98.109%, melting point (mp): 50.63 ° C ~ 52.56 ° C).

化合物a3的合成:Synthesis of compound a3:

於250ml乾燥潔淨的三口瓶中加入12g的化合物a2以及90ml的二氯甲烷。在氮氣保護下攪拌前述混合物,並使用液氮降溫至0℃。控溫在0℃下,滴加1.4g的三氟化硼乙醚,並在滴加完畢後,仍控溫在0℃且持續反應30min。之後,自然升溫至室溫,持續反應4小時。以薄層層析法(thin layer chromatography,TLC)確認反應的完成點,並當證實反應完成後,將前述混合物加入矽藻土進行抽氣過濾。接著,對濾液進行減壓濃縮,以得到一乾燥物。將前述乾燥物溶解於1倍重的二氯甲烷溶解中,並加入1倍重的矽膠混合後再進行減壓濃縮,以得到含有矽膠的一乾燥物。接著,將前述乾燥物置於裝有3~4倍重的矽膠的管柱中進行層析處理(沖提液為石油醚:乙酸乙酯=20:1,再加入總體積1%的三乙胺)。最後,收集層析液並濃縮,以得到呈白色固體的化合物a3(理論產量:12g,實際產量:7g,產率:58%,mp:93.7℃~97.5℃)。12 g of compound a2 and 90 ml of dichloromethane were added to a 250 ml dry clean three-necked flask. The mixture was stirred under nitrogen and cooled to 0 °C using liquid nitrogen. Temperature control At 0 ° C, 1.4 g of boron trifluoride diethyl ether was added dropwise, and after the completion of the dropwise addition, the temperature was controlled at 0 ° C and the reaction was continued for 30 min. Thereafter, the temperature was naturally raised to room temperature, and the reaction was continued for 4 hours. The completion point of the reaction was confirmed by thin layer chromatography (TLC), and when it was confirmed that the reaction was completed, the above mixture was added to diatomaceous earth for suction filtration. Next, the filtrate was concentrated under reduced pressure to give a dried material. The dried product was dissolved in 1 part by weight of dichloromethane, and mixed with 1 time weight of yttrium gum, followed by concentration under reduced pressure to obtain a dried product containing guar gum. Next, the dried product was subjected to chromatography in a column containing 3 to 4 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 20:1, and then a total volume of 1% triethylamine was added. ). Finally, the chromatography solution was collected and concentrated to give Compound a3 (yield: 12 g, actual yield: 7 g, yield: 58%, mp: 93.7 ° C to 97.5 ° C) as a white solid.

化合物a4的合成:Synthesis of compound a4:

於500ml乾燥潔淨的三口瓶中加入40g的2,2,2-三氟乙醇,80g的三乙胺以及160ml的二氯甲烷。在氮氣保護下攪拌前述混合物,並降溫至-5℃~0℃後,分批加入75g的對甲苯磺醯氯。接著,自然升溫至室溫(20℃~25℃),並反應4小時。之後,向三口瓶中加入100ml的水攪拌5min後分液得水相及有機相。接著,用50ml的二氯甲烷提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次至近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,對濾液進行減壓濃縮後,加入2倍重的乙醇進行熱溶結晶,並將其放入冰箱冷凍4小時以上後取出以進行抽氣過濾。最後,使用少量凍乙醇淋洗,並重複前述結晶操作直至得到呈白色固體的化合物a4(理論產量:101g,實際產量:68g,產率:67.3%,純度(以氣相層析儀GC進行量測):99.976%)。40 g of 2,2,2-trifluoroethanol, 80 g of triethylamine and 160 ml of dichloromethane were placed in a 500 ml dry clean three-necked flask. The mixture was stirred under a nitrogen atmosphere, and after cooling to -5 ° C to 0 ° C, 75 g of p-toluenesulfonyl chloride was added in portions. Subsequently, the temperature was naturally raised to room temperature (20 ° C to 25 ° C), and reacted for 4 hours. Thereafter, 100 ml of water was added to the three-necked bottle and stirred for 5 minutes, and then the aqueous phase and the organic phase were separated. Next, the aqueous phase was extracted twice with 50 ml of dichloromethane, and the combined organic phases were washed twice with 50 ml of an aqueous solution of sodium chloride to near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure, and then hot-solved by adding 2 times by weight of ethanol, and placed in a refrigerator for 4 hours or more, and then taken out for suction filtration. Finally, it was rinsed with a small amount of frozen ethanol, and the above crystallization operation was repeated until a compound a4 was obtained as a white solid (theoretical yield: 101 g, actual yield: 68 g, yield: 67.3%, purity (measured by gas chromatography GC) Test): 99.976%).

化合物a5的合成:Synthesis of compound a5:

於1L潔淨的三口瓶中加入6g的氫化鈉(60%)以及70ml的N,N-二甲基甲醯胺(N,N-dimethyl formamide,DMF)。接著,在持續攪拌下降溫至-5℃~0℃後,滴加由120ml的DMF和30g的4-溴-2,6-二氟苯酚(4-bromo-2,6-difluorophenol)組成的溶液,並控溫在25℃以下。滴加完畢之後,在持續攪拌1小時下升溫至90℃~95℃後,滴加由200ml的DMF和40g的化合物a4組成的溶液,並升溫至110℃,且控溫在該溫度下反應6小時。之後,把前述反應液緩慢倒入裝有碎冰的燒杯中水解,加入25ml的鹽酸調節pH值為中性,再加入100ml的石油醚攪拌5min後進行分液得水相及有機相。接著,用50ml的石油醚提取水相兩次,以及用 100ml的氯化鈉水溶液洗滌合併後的有機相兩次至pH值接近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,將濾液進行減壓濃縮後,於室溫下進行矽膠管柱層析(2倍柱高的石油醚沖提兩次)。最後,收集層析液並濃縮後得到呈無色透明液體的化合物a5(理論產量:41.7g,實際產量:26.5g,產率:63.5%,純度(以氣相層析儀GC進行量測):96.8%)。To a 1 L clean three-necked flask was added 6 g of sodium hydride (60%) and 70 ml of N,N-dimethyl formamide (DMF). Then, after continuously stirring and lowering the temperature to -5 ° C to 0 ° C, a solution consisting of 120 ml of DMF and 30 g of 4-bromo-2,6-difluorophenol was added dropwise. And the temperature control is below 25 °C. After the completion of the dropwise addition, the temperature was raised to 90 ° C to 95 ° C under continuous stirring for 1 hour, and a solution consisting of 200 ml of DMF and 40 g of the compound a4 was added dropwise, and the temperature was raised to 110 ° C, and the temperature was controlled at this temperature. hour. Thereafter, the reaction solution was slowly poured into a beaker containing crushed ice to be hydrolyzed, 25 ml of hydrochloric acid was added to adjust the pH to neutrality, and then 100 ml of petroleum ether was added and stirred for 5 minutes, followed by liquid separation to obtain an aqueous phase and an organic phase. Next, extract the aqueous phase twice with 50 ml of petroleum ether, and use The combined organic phase was washed twice with 100 ml of an aqueous solution of sodium chloride until the pH was near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure, and then subjected to silica gel column chromatography (2 times column height of petroleum ether) twice at room temperature. Finally, the chromatographic solution was collected and concentrated to give the compound a5 as a colorless transparent liquid (theoretical yield: 41.7 g, actual yield: 26.5 g, yield: 63.5%, purity (measured by gas chromatograph GC): 96.8%).

化合物a6的合成:Synthesis of compound a6:

於250ml乾燥潔淨的三口瓶中加入13g的鎂屑以及60ml的乙醚。接著,在氮氣保護下攪拌前述混合物,並加入少量溴乙烷以引發反應。接著,降溫至0℃~10℃,且控溫在該溫度下滴加由12g的化合物a5和30ml的乙醚組成的溶液。滴加完畢之後,仍控溫在0℃~10℃下持續反應1小時。接著,降溫至-70℃~-80℃,且控溫在該溫度下滴加15.6g的硼酸三異丙酯。滴加完畢後,自然升溫至-20℃之後,向三口瓶中加入20ml的稀鹽酸水溶液,攪拌5min後分液得水相及有機相。接著,用20ml的乙酸乙酯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。最後,將濾液進行減壓濃縮以得到呈淺紅色黏稠狀的化合物a6(理論產量:10.5g,實際產量:6.2g,產率:59%)。13 g of magnesium turnings and 60 ml of diethyl ether were added to a 250 ml dry clean three-necked flask. Next, the foregoing mixture was stirred under a nitrogen atmosphere, and a small amount of ethyl bromide was added to initiate the reaction. Subsequently, the temperature was lowered to 0 ° C to 10 ° C, and a temperature-controlled solution of 12 g of the compound a5 and 30 ml of diethyl ether was added dropwise at this temperature. After the completion of the dropwise addition, the temperature was continuously controlled at 0 ° C to 10 ° C for 1 hour. Subsequently, the temperature was lowered to -70 ° C to -80 ° C, and 15.6 g of triisopropyl borate was added dropwise at this temperature. After the completion of the dropwise addition, the temperature was naturally raised to -20 ° C, and then 20 ml of a dilute aqueous hydrochloric acid solution was added to the three-necked flask, and after stirring for 5 minutes, the aqueous phase and the organic phase were separated. Next, the aqueous phase was extracted twice with 20 ml of ethyl acetate, and the combined organic phases were washed twice with 50 ml of aqueous sodium chloride. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Finally, the filtrate was concentrated under reduced pressure to give Compound a6 (yield: 10.5 g, actual yield: 6.2 g, yield: 59%).

液晶化合物1-a-1(2toPU-O1CF3)的合成:Synthesis of liquid crystal compound 1-a-1 (2toPU-O1CF3):

於100ml乾燥潔淨的三口瓶中加入4g的化合物a3、3.8g的化合物a6、3.6g的碳酸鉀、0.1g的四(三苯基膦)鈀0.5g的四丁基溴化銨(tetrabutylammonium bromide,TBAB)、40ml的四 氫呋喃(tetrahydrofuran,THF)以及10ml的水。接著,攪拌前述混合物,並加熱迴流(70℃~80℃)4小時之後,向三口瓶中加入50ml的水,攪拌5min後進行分液得水相及有機相。接著,用30ml的甲苯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次至pH值接近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,對濾液進行減壓濃縮,以得到6.2g的乾燥物。將前述乾燥物溶解於1倍重的二氯甲烷中,並加入1倍重的矽膠混合後再進行減壓蒸餾,以得到含有矽膠的一乾燥物。接著,將前述乾燥物置於裝有3~4倍重的矽膠的管柱中進行層析處理(沖提液為石油醚:乙酸乙酯=20:1,再加入總體積1%的三乙胺)。最後,收集層析液並濃縮,以得到呈白色固體的液晶化合物1-a-1(2toPU-O1CF3)(理論產量:5.7g,實際產量:3.6g,產率:63.1%)。GCMS:m/z=430.2350[M+];1 H NMR(400MHz,CDCl3 ):δ(ppm)0.879(t,3H,J=8Hz),1.320(q,2H,J=8Hz),3.651(s,2H),4.105(s,6H),6.255(d,1H,J=12Hz),7.127(d,2H,J=8.8Hz),7.463(d,2H,J=8Hz),7.676(d,2H,J=8Hz)。4 g of compound a3, 3.8 g of compound a6, 3.6 g of potassium carbonate, 0.1 g of tetrakis(triphenylphosphine)palladium 0.5 g of tetrabutylammonium bromide were added to a 100 ml dry clean three-necked flask. TBAB), 40 ml of tetrahydrofuran (THF) and 10 ml of water. Next, the mixture was stirred and heated under reflux (70 ° C to 80 ° C) for 4 hours, and then 50 ml of water was added to the three-necked flask, and the mixture was stirred for 5 minutes, followed by liquid separation to obtain an aqueous phase and an organic phase. Next, the aqueous phase was extracted twice with 30 ml of toluene, and the combined organic phases were washed twice with 50 ml of an aqueous solution of sodium chloride until the pH was near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure to give 6.2 g of dried material. The dried product was dissolved in 1 time by weight of methylene chloride, and mixed with 1 time weight of yttrium gum, followed by distillation under reduced pressure to obtain a dried product containing guar gum. Next, the dried product was subjected to chromatography in a column containing 3 to 4 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 20:1, and then a total volume of 1% triethylamine was added. ). Finally, the chromatography liquid was collected and concentrated to give a liquid crystal compound 1-a-1 (2toPU-O1CF3) as a white solid (theoretical yield: 5.7 g, actual yield: 3.6 g, yield: 63.1%). GCMS: m/z = 430.2350 [M+]; 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 0.879 (t, 3H, J = 8 Hz), 1.320 (q, 2H, J = 8 Hz), 3.651 (s) , 2H), 4.105 (s, 6H), 6.255 (d, 1H, J = 12 Hz), 7.127 (d, 2H, J = 8.8 Hz), 7.463 (d, 2H, J = 8 Hz), 7.676 (d, 2H) , J = 8Hz).

合成例2Synthesis Example 2

製備液晶化合物1-a-2(2toPU-O2F)的合成方法如下所示。A method for synthesizing the liquid crystal compound 1-a-2 (2toPU-O2F) is shown below.

於100ml乾燥潔淨的三口瓶中加入5g的二異丙胺以及20ml的THF。接著,在氮氣保護下攪拌前述混合物,並降溫至 -10℃~0℃。控溫在-10℃~0℃下,滴加13ml的正丁基鋰。滴加完畢後,仍控溫在-10℃~0℃並持續反應1小時,以得到於後續步驟中使用的LDA試劑。另外,於另一100ml乾燥潔淨的三口瓶中加入3.6g的液晶化合物1-a-1以及20ml的THF。接著,在氮氣保護下攪拌前述混合物,並降溫至-70℃~-80℃後,滴加前述所得的LDA試劑。滴加完畢後,控溫在-70℃~-80℃下並持續反應2小時之後,向三口瓶中加入20ml的水,攪拌5min後進行分液得水相及有機相。接著,用20ml的乙酸乙酯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,對濾液進行減壓濃縮,以得到一乾燥物。將前述乾燥物溶解於1倍重的二氯甲烷中,並加入1倍重的矽膠混合後再進行減壓蒸餾,以得到含有矽膠的一乾燥物。接著,將前述乾燥物置於裝有4~5倍重的矽膠的管柱中進行層析處理(沖提液為石油醚:乙酸乙酯=20:1,再加入總體積1%的三乙胺)。最後,收集層析液並濃縮,以得到呈白色固體的液晶化合物1-a-2(2toPU-O2F)(實際產量:2.7g,產率:75%,mp:169.16℃~169.94℃)。GCMS:m/z=410.4606[M]+1 H NMR(400MHz,CDCl3 ):δ(ppm)0.879(t,3H,J=8Hz),1.320(q,2H,J=8Hz),4.105(s,6H),6.255(d,1H,J=12Hz),7.127(d,2H,J=8.8Hz),7.463(d,2H,J=8Hz),7.676(d,2H,J=8Hz)。5 g of diisopropylamine and 20 ml of THF were added to a 100 ml dry clean three-necked flask. Next, the mixture was stirred under a nitrogen atmosphere and cooled to -10 ° C to 0 ° C. The temperature was controlled at -10 ° C ~ 0 ° C, 13 ml of n-butyl lithium was added dropwise. After the completion of the dropwise addition, the temperature was controlled at -10 ° C to 0 ° C and the reaction was continued for 1 hour to obtain the LDA reagent used in the subsequent step. Separately, 3.6 g of the liquid crystal compound 1-a-1 and 20 ml of THF were placed in another 100 ml of a dry clean three-necked flask. Next, the mixture was stirred under a nitrogen atmosphere, and after cooling to -70 ° C to -80 ° C, the LDA reagent obtained above was added dropwise. After the completion of the dropwise addition, the temperature was controlled at -70 ° C to -80 ° C for 2 hours, and then 20 ml of water was added to the three-necked flask, and after stirring for 5 minutes, the aqueous phase and the organic phase were separated. Next, the aqueous phase was extracted twice with 20 ml of ethyl acetate, and the combined organic phases were washed twice with 50 ml of aqueous sodium chloride. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure to give a dried material. The dried product was dissolved in 1 time by weight of methylene chloride, and mixed with 1 time weight of yttrium gum, followed by distillation under reduced pressure to obtain a dried product containing guar gum. Next, the dried product was subjected to chromatography in a column packed with 4 to 5 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 20:1, and then a total volume of 1% triethylamine was added. ). Finally, the chromatography liquid was collected and concentrated to give a liquid crystal compound 1-a-2 (2toPU-O2F) as a white solid (actual yield: 2.7 g, yield: 75%, mp: 169.16 ° C to 169.94 ° C). GCMS: m/z = 410.4606 [M] + ; 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 0.879 (t, 3H, J = 8 Hz), 1.320 (q, 2H, J = 8 Hz), 4.105 ( s, 6H), 6.255 (d, 1H, J = 12 Hz), 7.127 (d, 2H, J = 8.8 Hz), 7.463 (d, 2H, J = 8 Hz), 7.766 (d, 2H, J = 8 Hz).

合成例3Synthesis Example 3

製備液晶化合物1-b-1(2toUQU-O1CF3)的合成方法如下 所示。The synthesis method of preparing liquid crystal compound 1-b-1 (2toUQU-O1CF3) is as follows Shown.

化合物b1的合成:Synthesis of compound b1:

於2L乾燥潔淨的三口瓶中加入28.8g的鎂屑、50ml的THF以及少量的3,5-二氟溴苯,攪拌引發後滴加由193g的3,5-二氟溴苯和600ml的THF組成的溶液,並維持迴流(78℃左右)。滴加完畢後,持續迴流反應1小時。接著,在氮氣保護下降至室溫後再加入300ml的THF,並繼續降溫至-40℃~-50℃。在溫度維持在-40℃~-50℃的情況下,通入二氧化碳氣體,通氣至不再升溫後(大約1小時),再保持通氣30min後停止通氣,並自然回溫至-20℃。之後,將反應液緩慢倒入裝有碎冰以及鹽酸的燒杯中進行酸化水解,並在攪拌5min後進行分液得水相及有機相。接著,用100ml的乙酸乙酯提取水相兩次,以及用100ml的氯化鈉水溶液洗滌合併後的有機相兩次。之後,對前述有機相用30g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,對濾液進行減壓濃縮後,加入2倍重的石油醚以及1倍重的甲苯進行熱溶結晶。結晶完成 後進行抽氣過濾,並使用少量凍石油醚淋洗,以得到呈淺黃色固體的化合物b1(理論產量:158g,實際產量:93g,產率:58.8%,mp:121.11℃~121.96℃)。28.8g of magnesium turnings, 50ml of THF and a small amount of 3,5-difluorobromobenzene were added to a 2L dry clean three-necked flask. After stirring, 193 g of 3,5-difluorobromobenzene and 600 ml of THF were added dropwise. The solution is composed and maintained at reflux (about 78 ° C). After the completion of the dropwise addition, the reflux reaction was continued for 1 hour. Next, after the nitrogen protection was lowered to room temperature, 300 ml of THF was further added, and the temperature was further lowered to -40 ° C to -50 ° C. When the temperature is maintained at -40 ° C ~ -50 ° C, carbon dioxide gas is introduced, after the air is no longer heated (about 1 hour), and then ventilated for 30 minutes, the ventilation is stopped, and the temperature is naturally returned to -20 ° C. Thereafter, the reaction solution was slowly poured into a beaker containing crushed ice and hydrochloric acid for acid hydrolysis, and after stirring for 5 minutes, liquid separation and an organic phase were obtained. Next, the aqueous phase was extracted twice with 100 ml of ethyl acetate, and the combined organic phases were washed twice with 100 ml of aqueous sodium chloride. Thereafter, the organic phase was dried with 30 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure, and then 2 times by weight of petroleum ether and 1 time by weight of toluene were added for hot solution crystallization. Crystallization completed After suction filtration, it was rinsed with a small amount of frozen petroleum ether to give compound b1 as a pale yellow solid (theoretical yield: 158 g, actual yield: 93 g, yield: 58.8%, mp: 121.11 ° C to 121.96 ° C).

化合物b2的合成:Synthesis of compound b2:

於1L乾燥潔淨的三口瓶中加入70g的3,5-二氟苯甲酸、105g的氯化亞碸、250ml的甲苯以及幾滴DMF後開始攪拌,並加熱迴流4小時。之後,停止加熱,並降溫至不迴流。接著,將反應液進行減壓蒸餾以得到呈淺紅色液體的化合物b2(理論產量:78.5g,實際產量:68g,產率:86.6%)。70 g of 3,5-difluorobenzoic acid, 105 g of hydrazine chloride, 250 ml of toluene and a few drops of DMF were added to a 1 L dry clean three-necked flask, and stirring was started, followed by heating under reflux for 4 hours. After that, the heating is stopped and the temperature is lowered to no reflux. Next, the reaction liquid was subjected to distillation under reduced pressure to give Compound b2 (yield: 78.5 g, actual yield: 68 g, yield: 86.6%).

化合物b4的合成:Synthesis of compound b4:

於1L乾燥潔淨的三口瓶中加入43g的化合物b3(合成方法請參照前述化合物a1,於此不再贅述)、70g的吡啶以及200ml的二氯甲烷。接著,在氮氣保護下攪拌前述混合物,並降溫至0℃~5℃。控溫在0℃~5℃下,滴加由68g的化合物b2以及100ml的二氯甲烷組成的溶液。滴加完畢後,自然升溫並攪拌過夜。之後,向三口瓶中加入100ml的水並攪拌5min後進行分液得水相及有機相。接著,用100ml的二氯甲烷提取水相兩次,以及用100ml的氯化鈉水溶液洗滌合併後的有機相兩次至pH值接近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,將濾液進行矽膠管柱層析(沖提液為石油醚:乙酸乙酯=9:1)收集層析液並濃縮後,以得到呈淺黃色液體的化合物a4(理論產量:94.8g,實際產量:58g,產率:61.2%,純度(以氣相層析儀GC進行量測):95.799%)。43 g of the compound b3 was added to a 1 L dry clean three-necked flask (for the synthesis, please refer to the aforementioned compound a1, which will not be described again), 70 g of pyridine and 200 ml of dichloromethane. Next, the mixture was stirred under a nitrogen atmosphere and cooled to 0 ° C to 5 ° C. A solution consisting of 68 g of compound b2 and 100 ml of dichloromethane was added dropwise at a temperature controlled from 0 ° C to 5 ° C. After the addition was completed, the temperature was naturally raised and stirred overnight. Thereafter, 100 ml of water was added to the three-necked flask and stirred for 5 minutes, followed by liquid separation to obtain an aqueous phase and an organic phase. Next, the aqueous phase was extracted twice with 100 ml of dichloromethane, and the combined organic phases were washed twice with 100 ml of an aqueous solution of sodium chloride until the pH was near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was subjected to a gel column chromatography (the extract was petroleum ether: ethyl acetate = 9:1). The chromatographic solution was collected and concentrated to give compound a4 as a pale yellow liquid (theoretical yield: 94.8 g, Actual yield: 58 g, yield: 61.2%, purity (measured by gas chromatograph GC): 95.799%).

化合物b5的合成:Synthesis of compound b5:

於500ml乾燥潔淨的三口瓶中加入27g的化合物b4以及300ml的二氯甲烷。接著,在氮氣保護下攪拌前述混合物,並使用液氮降溫至0℃。控溫在0℃下,滴加3.7g的三氟化硼乙醚,並在滴加完畢後,仍控溫在0℃下且持續反應30min。之後,自然升溫至室溫,持續反應4小時。以TLC確認反應的完成點,並當證實反應完成後,將前述混合物加入10.6g的三乙胺並攪拌1小時。之後,加入矽藻土進行抽氣過濾。接著,對濾液進行減壓濃縮後進行矽膠管柱層析(沖提液為2倍柱高的石油醚以及2倍柱高的乙酸乙酯)。繼之,收集層析液並濃縮後使用2倍量的乙醇進行再結晶,並將其放入冰箱冷凍6小時以上後取出以進行抽氣過濾。最後,使用少量凍乙醇淋洗以得到呈白色固體的化合物b5(理論產量:27g,實際產量:16.8g,產率:62.2%,純度(以氣相層析儀GC進行量測):99.031%)。Into a 500 ml dry clean three-necked flask, 27 g of compound b4 and 300 ml of dichloromethane were added. Next, the mixture was stirred under a nitrogen atmosphere and cooled to 0 ° C using liquid nitrogen. Temperature control At 0 ° C, 3.7 g of boron trifluoride etherate was added dropwise, and after the completion of the dropwise addition, the temperature was controlled at 0 ° C and the reaction was continued for 30 min. Thereafter, the temperature was naturally raised to room temperature, and the reaction was continued for 4 hours. The completion point of the reaction was confirmed by TLC, and when it was confirmed that the reaction was completed, the mixture was added to 10.6 g of triethylamine and stirred for 1 hour. Thereafter, the diatomaceous earth was added for suction filtration. Next, the filtrate was concentrated under reduced pressure, and then subjected to a gel column chromatography (the extract was 2 times column height of petroleum ether and 2 times column height of ethyl acetate). Subsequently, the chromatography solution was collected, concentrated, and recrystallized using a 2-fold amount of ethanol, and placed in a refrigerator for 6 hours or more, and then taken out for suction filtration. Finally, a small amount of frozen ethanol was used for rinsing to give compound b5 as a white solid (theoretical yield: 27 g, actual yield: 16.8 g, yield: 62.2%, purity (measured by gas chromatograph GC): 99.031% ).

化合物b6的合成方法:Synthesis method of compound b6:

於500ml乾燥潔淨的三口瓶中加入15.4g的化合物b5以及160ml的THF。接著,在氮氣保護下攪拌前述混合物,並降溫至-70℃~-80℃後,滴加32ml的正丁基鋰。滴加完畢後,在-70℃~-80℃下持續反應1小時,並滴加38.6g的二氟二溴甲烷溶液(55.5%)。滴加完畢後,自然升溫至-30℃,並把反應液緩慢倒入裝有水燒杯中進行水解,再加入50ml的乙酸乙酯攪拌5min後進行分液得水相及有機相。接著,用50ml的乙酸乙酯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次pH值接近中性。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,將濾液進行矽膠管柱層析(沖提液為石 油醚:乙酸乙酯=95:5),收集層析液並濃縮以得到呈淺紅色液體的化合物b6(理論產量:23g,實際產量:22g,產率:95.6%)。To a 500 ml dry clean three-necked flask was added 15.4 g of compound b5 and 160 ml of THF. Next, the mixture was stirred under a nitrogen atmosphere, and after cooling to -70 ° C to -80 ° C, 32 ml of n-butyllithium was added dropwise. After completion of the dropwise addition, the reaction was continued at -70 ° C to -80 ° C for 1 hour, and 38.6 g of a difluorodibromomethane solution (55.5%) was added dropwise. After the completion of the dropwise addition, the temperature was naturally raised to -30 ° C, and the reaction liquid was slowly poured into a water-containing beaker for hydrolysis, and then 50 ml of ethyl acetate was added and stirred for 5 minutes, and then the liquid phase and the organic phase were separated. Next, the aqueous phase was extracted twice with 50 ml of ethyl acetate, and the combined organic phases were washed with 50 ml of an aqueous sodium chloride solution and the pH was nearly neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate is subjected to gel column chromatography (the extract is stone) Oleic ether: ethyl acetate = 95:5), chromatography was collected and concentrated to give compound b6 (yield: 23 g, actual yield: 22 g, yield: 95.6%).

液晶化合物1-b-1(2toUQU-O1CF3)的合成:Synthesis of liquid crystal compound 1-b-1 (2toUQU-O1CF3):

於500ml乾燥潔淨的三口瓶中加入150ml的水後開始攪拌且加熱升溫至50℃。接著,於三口瓶中加入9.6g的1-三氟乙氧基2,6-二氟苯酚、12g的碳酸鉀以及3.4g的TBAB後再升溫至80℃,並加入22.5g的化合物b6。之後,將溫度再次升溫至100℃左右並進行迴流,持續反應6小時後,接著將溫度降至室溫,並向三口瓶中加入50ml的乙酸乙酯,攪拌5min後分液得水相及有機相。接著,用20ml的乙酸乙酯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,將濾液進行減壓濃縮後,於裝有3~4倍重的矽膠的管柱中進行層析處理(沖提液為石油醚:乙酸乙酯=3:1,再加入總體積1%的三乙胺)。繼之,收集層析液並濃縮後使用2倍量的乙醇進行再結晶,並將其放入冰箱冷凍6小時以上後取出以進行抽氣過濾。最後,使用少量凍乙醇淋洗以得到呈白色固體的液晶化合物1-b-1(2toUQU-O1CF3)(理論產量:17.4g,實際產量:11.6g,產率:66.6%,純度(以氣相層析儀GC進行量測):98.9%,mp:93.12℃~94.31℃)。GCMS:m/z=532.2276[M]+1 H NMR(400MHz,CDCl3 ):δ(ppm)0.864(t,3H,J=8Hz),1.328(q,2H,J=8Hz),3.618(q,2H,J=11.2Hz),4.027(s,6H),6.868(d,2H,J=8Hz),7.655(d,2H,J=8Hz)。After adding 150 ml of water to a 500 ml dry clean three-necked flask, stirring was started and the temperature was raised to 50 ° C by heating. Next, 9.6 g of 1-trifluoroethoxy 2,6-difluorophenol, 12 g of potassium carbonate, and 3.4 g of TBAB were added to the three-necked flask, and the mixture was further heated to 80 ° C, and 22.5 g of the compound b6 was added. After that, the temperature was again raised to about 100 ° C and refluxed. After the reaction was continued for 6 hours, the temperature was then lowered to room temperature, and 50 ml of ethyl acetate was added to the three-necked flask. After stirring for 5 minutes, the aqueous phase was separated and organic. phase. Next, the aqueous phase was extracted twice with 20 ml of ethyl acetate, and the combined organic phases were washed twice with 50 ml of aqueous sodium chloride. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure, and then subjected to chromatography in a column containing 3 to 4 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 3:1, and then added to the total volume of 1%). Triethylamine). Subsequently, the chromatography solution was collected, concentrated, and recrystallized using a 2-fold amount of ethanol, and placed in a refrigerator for 6 hours or more, and then taken out for suction filtration. Finally, it was rinsed with a small amount of cold ethanol to obtain a liquid crystal compound 1-b-1 (2toUQU-O1CF3) as a white solid (theoretical yield: 17.4 g, actual yield: 11.6 g, yield: 66.6%, purity (in the gas phase) Chromatography GC for measurement): 98.9%, mp: 93.12 ° C ~ 94.31 ° C). GCMS: m/z = 532.2276 [M] + ; 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 0.864 (t, 3H, J = 8 Hz), 1.328 (q, 2H, J = 8 Hz), 3.618 ( q, 2H, J = 11.2 Hz), 4.027 (s, 6H), 6.868 (d, 2H, J = 8 Hz), 7.655 (d, 2H, J = 8 Hz).

合成例4Synthesis Example 4

製備液晶化合物1-b-2(2toUQU-O2F)的合成方法如下所示。The synthesis method for preparing the liquid crystal compound 1-b-2 (2toUQU-O2F) is shown below.

於250ml乾燥潔淨的三口瓶中加入20g的二異丙胺以及100ml的THF。接著,在氮氣保護下攪拌前述混合物,並降溫至-10℃~0℃。控溫在-10℃~0℃下,滴加53ml的正丁基鋰,且在滴加完畢後,仍控溫在-10℃~0℃下持續反應1小時,以得到於後續步驟中使用的LDA試劑。另外,於另一500ml乾燥潔淨的三口瓶中加入7g的液晶化合物1-b-1以及100ml的THF。接著,在氮氣保護下攪拌前述混合物,並降溫至-70℃~-80℃後,滴加前述所得的LDA試劑。控溫在-70℃~-80℃下並持續反應2小時之後,向三口瓶中加入20ml的水,攪拌5min後進行分液得水相及有機相。接著,用20ml的乙酸乙酯提取水相兩次,以及用50ml的氯化鈉水溶液洗滌合併後的有機相兩次。之後,對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著,對濾液進行減壓濃縮後,於裝有4~5倍重的矽膠的管柱中進行層析處理(沖提液為石油醚:乙酸乙酯=3:1,再加入總體積1%的三乙胺)。最後,收集層析液並濃縮後使用2倍量的乙醇進行再結晶,以得到呈白色固體的1-b-2液晶化合物(2toUQU-O2F)(理論產量:6.7g,實際產量:5g,產率:74.6%,純度(以氣相層析儀GC進行量測):98.9%,mp:66.69℃~67.53℃)。GCMS:m/z= 512.1960[M]+1 H NMR(400MHz,CDCl3 ):δ(ppm)0.868(t,3H,J=8Hz),1.330(q,2H,J=8Hz),4.429(s,6H),6.173(d,1H,J=12Hz),6.873(d,2H,J=8Hz),7.571(d,2H,J=8Hz)。20 g of diisopropylamine and 100 ml of THF were added to a 250 ml dry clean three-necked flask. Next, the mixture was stirred under a nitrogen atmosphere and cooled to -10 ° C to 0 ° C. Control temperature at -10 ° C ~ 0 ° C, add 53ml of n-butyl lithium, and after the completion of the addition, still control the temperature at -10 ° C ~ 0 ° C for 1 hour, in order to get used in the next step LDA reagent. Separately, 7 g of the liquid crystal compound 1-b-1 and 100 ml of THF were placed in another 500 ml dry clean three-necked flask. Next, the mixture was stirred under a nitrogen atmosphere, and after cooling to -70 ° C to -80 ° C, the LDA reagent obtained above was added dropwise. After the temperature was controlled at -70 ° C to -80 ° C for 2 hours, 20 ml of water was added to the three-necked flask, and after stirring for 5 minutes, the aqueous phase and the organic phase were separated. Next, the aqueous phase was extracted twice with 20 ml of ethyl acetate, and the combined organic phases were washed twice with 50 ml of aqueous sodium chloride. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was concentrated under reduced pressure, and then subjected to chromatography in a column packed with 4 to 5 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 3:1, and then added to the total volume of 1%). Triethylamine). Finally, the chromatographic solution was collected, concentrated, and recrystallized using twice the amount of ethanol to obtain a 1-b-2 liquid crystal compound (2toUQU-O2F) as a white solid (theoretical yield: 6.7 g, actual yield: 5 g, yield Rate: 74.6%, purity (measured by gas chromatograph GC): 98.9%, mp: 66.69 ° C ~ 67.53 ° C). GCMS: m/z = 512.1960 [M] + ; 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 0.868 (t, 3H, J = 8 Hz), 1.330 (q, 2H, J = 8 Hz), 4.429 ( s, 6H), 6.173 (d, 1H, J = 12 Hz), 6.873 (d, 2H, J = 8 Hz), 7.571 (d, 2H, J = 8 Hz).

以上,雖然僅透過合成例1至合成例4說明液晶化合物1-a-1、1-a-2、1-b-1及1-b-2的合成方法,但此領域技術人員根據上述合成例1至合成例4所揭露的內容即可理解液晶化合物1-a-3、1-b-3、1-c-1、1-d-1及液晶化合物3的合成方法。As described above, the synthesis methods of the liquid crystal compounds 1-a-1, 1-a-2, 1-b-1, and 1-b-2 are described only by the synthesis examples 1 to 4, but those skilled in the art have synthesized according to the above. The synthesis of the liquid crystal compounds 1-a-3, 1-b-3, 1-c-1, 1-d-1 and liquid crystal compound 3 can be understood from the contents disclosed in the examples 1 to 4.

〈液晶組合物的製備及性質測試〉<Preparation and Properties Test of Liquid Crystal Composition> 實施例1至實施例9與比較例Example 1 to Example 9 and Comparative Example

以表二所示的比例(重量百分比),將液晶化合物1-a-1至液晶化合物1-a-3、液晶化合物1-b-1至液晶化合物1-b-3、液晶化合物1-c-1、液晶化合物1-d-1及液晶化合物3分別與母液(由重量比例為1:1:1的2CCGF、3CCGF及5CCGF組成)進行混合,藉此製備實施例1至實施例8的液晶組合物以及比較例的液晶組合物;另依表四所示之成分及各成份比例製備出實施例9。Liquid crystal compound 1-a-1 to liquid crystal compound 1-a-3, liquid crystal compound 1-b-1 to liquid crystal compound 1-b-3, liquid crystal compound 1-c in the ratio (% by weight) shown in Table 2 -1, liquid crystal compound 1-d-1 and liquid crystal compound 3 were mixed with a mother liquid (composed of 2CCGF, 3CCGF and 5CCGF in a weight ratio of 1:1:1), respectively, thereby preparing liquid crystals of Examples 1 to 8. The liquid crystal composition of the composition and the comparative example; Example 9 was prepared according to the components shown in Table 4 and the ratio of each component.

〈性質測試〉<Property Test>

接著,對實施例1至實施例9的液晶組合物及比較例的液晶組合物分別進行澄清點(Tni)、介電常數異向性(△ε)、轉動黏度(γ1)、光學異向性(△n)的測量,其中實施例1至實施例8的測量結果記載在表二中、實施例9的測量結果記載在表四中;液晶化合物的性質由實施例1至實施例8的推得並記載在表三 中。液晶化合物及液晶組合物的前述性質分別是透過以下方法進行測定。Next, the liquid crystal composition of Examples 1 to 9 and the liquid crystal composition of the comparative example were respectively subjected to a clearing point (Tni), a dielectric anisotropy (Δε), a rotational viscosity (γ1), and an optical anisotropy. The measurement of (Δn), wherein the measurement results of Examples 1 to 8 are described in Table 2, and the measurement results of Example 9 are shown in Table 4; the properties of the liquid crystal compound are derived from Examples 1 to 8. And recorded in Table 3 in. The above properties of the liquid crystal compound and the liquid crystal composition were measured by the following methods, respectively.

澄清點(Tni,單位:℃):Clarification point (Tni, unit: °C):

使用差示掃描量熱儀(DSC;廠商:TA;型號:Q200),將液晶化合物或液晶組合物置於鋁盤中精秤0.5mg至10mg,並在鋁盤壓錠後以DSC進行相變溫度測試,即藉由液晶化合物或液晶組合物因相變化而出現的吸熱峰及放熱峰的起始點來得到相變化溫度。由於液晶化合物或液晶組合物為向列相(nematic phase),因此由室溫升溫的圖譜上會出現向列相轉變為液相的吸熱峰,可讀出澄清點的溫度。Using a differential scanning calorimeter (DSC; manufacturer: TA; model: Q200), the liquid crystal compound or liquid crystal composition was placed in an aluminum pan with a scale of 0.5 mg to 10 mg, and the phase change temperature test was performed by DSC after the aluminum pan was pressed. That is, the phase change temperature is obtained by the endothermic peak of the liquid crystal compound or the liquid crystal composition due to the phase change and the starting point of the exothermic peak. Since the liquid crystal compound or the liquid crystal composition is a nematic phase, an endothermic peak which changes from a nematic phase to a liquid phase appears on the spectrum which is raised from room temperature, and the temperature of the clearing point can be read.

介電常數異向性(△ε):Dielectric anisotropy (△ε):

將待測液晶組合物裝入液晶盒中,於溫度25℃下,對該液晶盒施加0V至20V的電壓,並量測得電容對電壓的曲線(C-V curve)。在C-V curve中,高電壓區及低電壓區皆會呈現水平,在低電壓區讀取電容C⊥、在高電壓區讀取電容C∥,並可藉公式由C⊥、C∥換算為ε⊥、ε∥,介電常數異向性(△ε)=ε∥-ε⊥。The liquid crystal composition to be tested was placed in a liquid crystal cell, and a voltage of 0 V to 20 V was applied to the liquid crystal cell at a temperature of 25 ° C, and a capacitance-to-voltage curve (C-V curve) was measured. In the CV curve, both the high voltage region and the low voltage region will be horizontal. The capacitor C⊥ is read in the low voltage region and the capacitor C∥ is read in the high voltage region, and can be converted to C by C⊥ and C∥ by the formula. ⊥, ε∥, dielectric anisotropy (Δε) = ε ∥ - ε ⊥.

另外,在獲得各個液晶組合物的△ε後,藉由母液的已知△ε,並透過外插方式得出對應的待測液晶化合物的△ε。Further, after Δε of each liquid crystal composition is obtained, the corresponding Δε of the liquid crystal compound to be tested is obtained by the known Δε of the mother liquid and by extrapolation.

光學異向性(△n):Optical anisotropy (△n):

利用一目鏡上安裝有偏光板的阿貝(Abbe)折射儀(廠商:ATAGO;型號:DR-M2)對各個液晶組合物進行量測。首先,在阿貝折射儀的主稜鏡表面以單方向刷上配向液,並以無塵布沿同一方向擦拭配向,接著在主稜鏡上滴加少量待測的液晶組合物,在測試溫度25℃,使用波長為589nm的濾光片進行光學異向 性的測量。當偏光方向與擦拭方向平行時,測得的折射率為n∥;當偏光方向與擦拭方向垂直時,測得的折射率為n⊥;光學異向性(△n)=n∥-n⊥。Each liquid crystal composition was measured by an Abbe refractometer (manufacturer: ATAGO; model: DR-M2) on which a polarizing plate was attached to one eyepiece. First, the alignment liquid is brushed in a single direction on the main surface of the Abbe refractometer, and the alignment is wiped in the same direction with a dust-free cloth, and then a small amount of the liquid crystal composition to be tested is dropped on the main crucible at the test temperature. Optical anisotropy at 25 ° C using a filter with a wavelength of 589 nm Sexual measurement. When the polarizing direction is parallel to the wiping direction, the measured refractive index is n∥; when the polarizing direction is perpendicular to the wiping direction, the measured refractive index is n⊥; optical anisotropy (Δn)=n∥-n⊥ .

另外,在獲得各個液晶組合物所測得的△n後,藉由母液的已知△n,並透過外插方式得出對應的待測液晶化合物的△n。Further, after obtaining Δn measured by each liquid crystal composition, the corresponding Δn of the liquid crystal compound to be tested is obtained by the known Δn of the mother liquid and by extrapolation.

轉動黏度(γ1,單位:mPa.s):Rotational viscosity (γ1, unit: mPa.s):

如前述測得介電常數異向性(△ε)之後,軟體即可由△ε值進行轉動黏度(γ1)的換算。After the dielectric anisotropy (Δε) is measured as described above, the soft body can be converted from the rotational viscosity (γ1) by the Δε value.

另外,在獲得各個液晶組合物所測得的γ1後,藉由母液的已知γ1,並透過外插方式得出對應的待測液晶化合物的γ1。Further, after obtaining γ1 measured by each liquid crystal composition, the corresponding γ1 of the liquid crystal compound to be tested is obtained by the known γ1 of the mother liquid and by extrapolation.

由上述表三可知,液晶化合物1-a-1至1-d-1具有符合業界需求的介電常數異向性(範圍為19.2~49.8),因此可預期地,採用符合本發明式1的液晶化合物的液晶顯示元件可擁有省電的特性。另外,與比較例的液晶化合物3相比,液晶化合物1-a-1至1-d-1具有低的轉動黏度,藉此,可預期地,液晶顯示元件若採用符合本發明式1的液晶化合物能縮短應答時間,且應答速度能夠加快。另外,與比較例的液晶化合物3相比,液晶化合物1-a-1至1-d-1具有高的澄清點,這表示可預期地,符合本發明式1的液晶化合物能夠應用在較廣的溫度範圍內,藉此提升液晶顯示元件的應用價值。As can be seen from the above Table 3, the liquid crystal compounds 1-a-1 to 1-d-1 have dielectric anisotropy in accordance with the industrial requirements (range 19.2 to 49.8), and thus it is expected to adopt the formula 1 according to the present invention. The liquid crystal display element of the liquid crystal compound can have power saving characteristics. In addition, the liquid crystal compounds 1-a-1 to 1-d-1 have a low rotational viscosity as compared with the liquid crystal compound 3 of the comparative example, whereby it is expected that the liquid crystal display element employs the liquid crystal according to the formula 1 of the present invention. Compounds can reduce response time and response speed can be increased. In addition, the liquid crystal compounds 1-a-1 to 1-d-1 have a high clearing point as compared with the liquid crystal compound 3 of the comparative example, which indicates that it is expected that the liquid crystal compound according to the formula 1 of the present invention can be applied to a wider range. In the temperature range, thereby enhancing the application value of the liquid crystal display element.

雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (8)

一種液晶化合物,由式1表示: ,其中 R1 為一個或不相鄰的多個-CH2 -經-O-取代且碳數為2至10的烯基,或碳數為2至10的醚基,其中,R1 上的一或多個氫原子可被氟原子取代;R2 為碳數為1至10的烷基;A1 、A2 、A3 及A4 獨立地為1,4-伸環己基或1,4-伸苯基,其中A1 到A4 上的一或多個氫原子可被鹵素取代;Z1 、Z2 及Z3 獨立地為單鍵、-C2 H4 -、-COO-、-OCO-、-CF2 O-、-OCF2 -、-C≡C-或-CH=CH-;以及n、m獨立地為1或0。A liquid crystal compound represented by Formula 1: And wherein R 1 is a plurality of -CH 2 -substituted or O-substituted alkenyl groups having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms, wherein R 1 is One or more hydrogen atoms may be substituted by a fluorine atom; R 2 is an alkyl group having 1 to 10 carbon atoms; A 1 , A 2 , A 3 and A 4 are independently 1,4-cyclohexylene or 1,4 a phenyl group in which one or more hydrogen atoms on A 1 to A 4 may be substituted by halogen; Z 1 , Z 2 and Z 3 are independently a single bond, -C 2 H 4 -, -COO-, - OCO-, -CF 2 O-, -OCF 2 -, -C≡C- or -CH=CH-; and n, m are independently 1 or 0. 如申請專利範圍第1項所述的液晶化合物,其中R1 為-OCHCF2 或-OCF2 CFCF2The liquid crystalline compound according to claim 1, wherein R 1 is -OCHCF 2 or -OCF 2 CFCF 2 . 如申請專利範圍第1項所述的液晶化合物,其中A1 、A2 、 A3 及A4 獨立地選自由所組成的族群。The liquid crystalline compound according to claim 1, wherein A 1 , A 2 , A 3 and A 4 are independently selected from the group consisting of , and The group of people formed. 如申請專利範圍第1項所述的液晶化合物,其中Z1 、Z2 及Z3 獨立地選自由單鍵及-CF2 O-所組成的族群。The liquid crystalline compound according to claim 1, wherein Z 1 , Z 2 and Z 3 are independently selected from the group consisting of a single bond and -CF 2 O-. 如申請專利範圍第1項所述的液晶化合物,其選自由以下式1-a至式1-d表示的化合物所組成的族群: ,以及,其中 R1 為一個或不相鄰的多個-CH2 -經-O-取代且碳數為2至10的烯基,或碳數為2至10的醚基,其中,R1 上的一或多個氫原子可被氟原子取代;以及R2 為碳數為1至10的烷基。The liquid crystal compound according to claim 1, which is selected from the group consisting of compounds represented by the following formula 1-a to formula 1-d: ,as well as And wherein R 1 is a plurality of -CH 2 -substituted or O-substituted alkenyl groups having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms, wherein R 1 is One or more hydrogen atoms may be substituted by a fluorine atom; and R 2 is an alkyl group having a carbon number of 1 to 10. 一種液晶組合物,包括如申請專利範圍第1項至第5項中任一項所述的液晶化合物。 A liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 5. 如申請專利範圍第6項所述的液晶組合物,更包括選自由式2所表示之化合物中的至少一者: ,其中 R3 為碳數為1至10的烷基或碳數為2至10的烯基,且在前述烷基或烯基中,一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代;R4 為鹵素、碳數為1至10的烷基或碳數為2至10的烯基,且於前述烷基或烯基中,一或多個氫原子可被氟原子取代,一個或不相鄰的多個-CH2 -可被-O-取代; A5 、A6 及A7 獨立地為1,4-伸環己基或1,4-伸苯基,其中A5 到A7 上的一或多個氫原子可被鹵素取代;Z4 及Z5 獨立地為單鍵、-C2 H4 -、-COO-、-OCO-、-CF2 O-、-OCF2 -、-C≡C-或-CH=CH-;以及o為1或0。The liquid crystal composition according to claim 6, further comprising at least one selected from the group consisting of compounds represented by Formula 2: Wherein R 3 is an alkyl group having a carbon number of 1 to 10 or an alkenyl group having a carbon number of 2 to 10, and in the aforementioned alkyl or alkenyl group, one or more hydrogen atoms may be substituted by a fluorine atom, one or not The adjacent plurality of -CH 2 - may be substituted by -O-; R 4 is a halogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and is in the aforementioned alkyl or alkenyl group. One or more hydrogen atoms may be substituted by a fluorine atom, and one or a plurality of adjacent -CH 2 - may be substituted by -O-; A 5 , A 6 and A 7 are independently 1,4-cyclohexylene Or 1,4-phenylene, wherein one or more hydrogen atoms on A 5 to A 7 may be substituted by halogen; Z 4 and Z 5 are independently a single bond, -C 2 H 4 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- or -CH=CH-; and o is 1 or 0. 一種液晶顯示元件,包括如申請專利範圍第1項至第5項中任一項所述的液晶化合物。 A liquid crystal display element comprising the liquid crystal compound according to any one of claims 1 to 5.
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