TWI608080B

TWI608080B - Liquid crystal compound, liquid crystal composition and liquid crystal display device having thereof

Info

Publication number: TWI608080B
Application number: TW103103614A
Authority: TW
Inventors: 游蕙如; 王俊智; 羅致遠
Original assignee: 達興材料股份有限公司
Priority date: 2014-01-29
Filing date: 2014-01-29
Publication date: 2017-12-11
Also published as: TW201529811A; CN104804748A

Description

液晶化合物、液晶組成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、液晶組成物以及液晶顯示元件，且特別是有關於一種具有高光學異向性、高澄清點、廣向列相溫度範圍以及較佳低溫儲存性的液晶化合物、液晶組成物以及包含液晶組成物之液晶顯示元件。 The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element, and more particularly to a liquid crystal compound having high optical anisotropy, high clear point, wide nematic phase temperature range, and preferably low temperature storage property, A liquid crystal composition and a liquid crystal display element including a liquid crystal composition.

液晶顯示元件(liquid crystal display device)為利用液晶光電變化之顯示元件，其具有體積小、重量輕、低電力消耗與顯示品質佳等優點，因此近年來已成為市場主流。 A liquid crystal display device is a display element that utilizes liquid crystal photoelectric change, and has advantages such as small size, light weight, low power consumption, and good display quality, and thus has become a mainstream in recent years.

液晶顯示元件中包含有液晶組成物，液晶組成物係包含一種以上之液晶化合物，為提升液晶顯示元件的性能，液晶化合物應具有以下特性：(1)化學性質與物理性質穩定；(2)具有較高的澄清點(向列相至液相的相變溫度)；(3)向列相的下限溫度較低；(4)與其他液晶化合物之相溶性優異；(5)具有較大之介電異向性；(6)具有相對高的光學異向性。 The liquid crystal display element includes a liquid crystal composition, and the liquid crystal composition contains one or more liquid crystal compounds. To improve the performance of the liquid crystal display element, the liquid crystal compound should have the following characteristics: (1) chemical and physical properties are stable; (2) Higher clearing point (phase transition temperature of nematic phase to liquid phase); (3) lower limit temperature of nematic phase is lower; (4) excellent compatibility with other liquid crystal compounds; (5) Electrical anisotropy; (6) has a relatively high optical anisotropy.

當液晶顯示元件中包含化學性質與物理性質穩定的液晶化合物，可提高電壓保持率。當使用具有較高澄清點及向列相下限溫度較低的液晶化合物，可擴寬向列相的溫度範圍，而使液晶顯示元件的使用溫度範圍變大，進而擴大液晶顯示元件的應用範圍。當使用與其他液晶化合物之相溶性優異的液晶化合物，可提升液晶組成物的性質。由於單一液晶化合物難以具備上述所有特點，因此液晶組成物通常包含一種以上之液晶化合物，當液晶化合物彼此間的相溶性越高，有利於液晶組成物的均勻性與穩定性。當使用具有較大之介電異向性的液晶化合物，有助於降低臨界電壓，臨界電壓較低可提升液晶顯示元件的對比度、顯示容量與響應速度。當使用具有較高的光學異向性的液晶化合物，有助於提升對比度。已知構成液晶顯示元件之單元厚度(d)與液晶組合物的光學異向性(△n)的乘積值為固定時，當光學異向性(△n)較大時，所使用的液晶顯示元件之單元厚度(d)可以較小。適當的乘積值取決於運作模式的種類，例如，以扭轉向列(Twisted nematic，TN)運作的液晶顯示元件，適當的乘積值約為0.45μm。由於響應速度與單元厚度的平方成反比，在維持固定乘積值與兼顧響應速度的情況下，可使用具有較高的光學異向性的液晶化合物。 When the liquid crystal display element contains a liquid crystal compound which is chemically and physically stable, the voltage holding ratio can be improved. When a liquid crystal compound having a relatively high clear point and a low nematic phase lower temperature is used, the temperature range of the nematic phase can be widened, and the use temperature range of the liquid crystal display element can be increased, thereby expanding the application range of the liquid crystal display element. When a liquid crystal compound excellent in compatibility with other liquid crystal compounds is used, the properties of the liquid crystal composition can be improved. Since it is difficult for a single liquid crystal compound to have all of the above characteristics, the liquid crystal composition usually contains one or more liquid crystal compounds, and the higher the compatibility of the liquid crystal compounds with each other, the uniformity and stability of the liquid crystal composition. When a liquid crystal compound having a large dielectric anisotropy is used, it contributes to lowering the threshold voltage, and a lower threshold voltage can improve the contrast, display capacity, and response speed of the liquid crystal display element. When a liquid crystal compound having a high optical anisotropy is used, it contributes to an improvement in contrast. It is known that when the product value of the unit thickness (d) constituting the liquid crystal display element and the optical anisotropy (Δn) of the liquid crystal composition is fixed, when the optical anisotropy (Δn) is large, the liquid crystal display used is used. The cell thickness (d) of the component can be small. The appropriate product value depends on the type of operation mode, for example, a liquid crystal display element operating in a twisted nematic (TN) with an appropriate product value of about 0.45 μm. Since the response speed is inversely proportional to the square of the cell thickness, a liquid crystal compound having a high optical anisotropy can be used while maintaining a fixed product value and a response speed.

如何改變液晶化合物的分子結構，使液晶化合物具備上述性質，以進一步改善液晶顯示元件的品質，係相關業者努力的目標。 How to change the molecular structure of the liquid crystal compound and to have the above properties of the liquid crystal compound to further improve the quality of the liquid crystal display element is a goal of the related art.

本發明之一目的是在提供一種液晶化合物，其具有高光學異向性、高澄清點與寬廣的向列相溫度範圍，藉此，有利於液晶化合物的保存及擴大其應用範圍。 SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal compound which has a high optical anisotropy, a high clearing point and a broad nematic phase temperature range, thereby facilitating the preservation of liquid crystal compounds and expanding the range of application thereof.

本發明之另一目的是在提供一種液晶組成物，其包含前述之液晶化合物，有利於低溫儲存，並有利於提升液晶顯示元件的成像品質及擴大其應用範圍。 Another object of the present invention is to provide a liquid crystal composition comprising the liquid crystal compound as described above, which is advantageous for low-temperature storage, and is advantageous for improving the image quality of the liquid crystal display element and expanding the range of application thereof.

本發明之再一目的是在提供一種液晶顯示元件，其包含前述之液晶組成物，故可具有較佳地成像品質及擴大其應用範圍。 Still another object of the present invention is to provide a liquid crystal display element comprising the liquid crystal composition described above, so that it can have better image quality and expand its application range.

依據本發明之一態樣之一實施方式是在提供一種液晶化合物，其具有如式(I)所示之一結構： One embodiment according to an aspect of the present invention provides a liquid crystal compound having a structure as shown in the formula (I):

式(I)中，R¹與R²係各自獨立為-H、-F、未經取代的碳數1至10的直鏈烷基或支鏈烷基、經鹵素取代的碳數1至10的直鏈烷基或支鏈烷基、未經取代的碳數2至10的直鏈烯基或支鏈烯基，或經鹵素取代的碳數2至10的直鏈烯基或支鏈烯基，R¹與R²中任意的-CH₂-可被-O-、-CO-、-COO-或-C≡C-取代，其前提是氧原子彼此不直接連接。 In the formula (I), R ¹ and R ² are each independently -H, -F, an unsubstituted linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms, and a halogen substituted carbon number of 1 to 10 Linear or branched alkyl, unsubstituted 2 to 10 linear alkenyl or branched alkenyl, or halogen substituted 2 to 10 linear alkenyl or branched alkene Any one of R ¹ and R ² -CH ₂ - may be substituted by -O-, -CO-, -COO- or -C≡C-, provided that the oxygen atoms are not directly bonded to each other.

A¹與A²係各自獨立為1,4-伸苯基、1,4-伸環己基、1,3-伸環戊基、2,5-伸四氫吡喃基或1,4-雙環[2.2.2]伸辛基，其中，1,4-伸苯基中任意一個或任意兩個不相鄰的-CH- 可被-N-取代，且1,4-伸苯基中任意一個氫原子可被氟原子取代，1,4-伸環己基中任意一個或任意兩個不相鄰的-CH₂-可被-O-或-S-取代，且1,4-伸環己基中任意一個氫原子可被氟原子取代。 The A ¹ and A ² systems are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentyl, 2,5-tetrahydropyranyl or 1,4-bicyclo [2.2.2] octyl group, wherein any one or any two of the 1,4-phenylene groups which are not adjacent may be substituted by -N-, and any one of 1,4-phenylene groups a hydrogen atom may be substituted with a fluorine atom, 1,4-cyclohexylene any one or any two non-adjacent -CH ₂ - may be substituted with -O- or -S-, and 1,4-cyclohexylene group Any one of the hydrogen atoms may be substituted by a fluorine atom.

A³為其中L為氫原子或氟原子。 A ³ is Wherein L is a hydrogen atom or a fluorine atom.

Z¹、Z²與Z³係各自獨立為單鍵、-O-、-CO-、-COO-、-C≡C-、-CH=CH-、-CH₂CH₂-、-CF₂CF₂-、-CF=CH-、-CH=CF-。m為1或2。n為0、1或2，且當Z¹為單鍵時，n≠0。 Z ¹ , Z ² and Z ³ are each independently a single bond, -O-, -CO-, -COO-, -C≡C-, -CH=CH-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CF=CH-, -CH=CF-. m is 1 or 2. n is 0, 1, or 2, and when Z ¹ is a single bond, n ≠ 0.

依據本發明之一態樣之另一實施方式是在提供一種液晶組成物，其包含前述之液晶化合物。 Another embodiment in accordance with an aspect of the present invention provides a liquid crystal composition comprising the liquid crystal compound described above.

依據本發明之一態樣之又一實施方式是在提供一種液晶顯示元件，其包含前述之液晶組成物。 According to still another embodiment of one aspect of the present invention, there is provided a liquid crystal display element comprising the liquid crystal composition described above.

第1圖係液晶化合物(I-2)之¹H-NMR光譜圖。 Fig. ^{1 is a 1} H-NMR spectrum chart of the liquid crystal compound (I-2).

第2圖係液晶化合物(I-1)之¹H-NMR光譜圖。 Fig. 2 is a ¹ H-NMR spectrum chart of the liquid crystal compound (I-1).

第3圖係液晶化合物(I-3)之¹H-NMR光譜圖。 Fig. 3 is a ¹ H-NMR spectrum chart of the liquid crystal compound (I-3).

第4圖係液晶化合物(I-4)之¹H-NMR光譜圖。 Fig. 4 is a ¹ H-NMR spectrum chart of the liquid crystal compound (I-4).

第5圖係液晶化合物(R-1)之¹H-NMR光譜圖。 Fig. 5 is a ¹ H-NMR spectrum chart of the liquid crystal compound (R-1).

第6圖係液晶化合物(R-2)之¹H-NMR光譜圖。 Fig. 6 is a ¹ H-NMR spectrum chart of the liquid crystal compound (R-2).

液晶化合物Liquid crystal compound

本發明之液晶化合物具有如式(I)所示之一結構： The liquid crystal compound of the present invention has a structure as shown in the formula (I):

A¹與A²係各自獨立為1,4-伸苯基、1,4-伸環己基、1,3-伸環戊基、2,5-伸四氫吡喃基或1,4-雙環[2.2.2]伸辛基，其中，1,4-伸苯基中任意一個或任意兩個不相鄰的-CH-可被-N-取代，且1,4-伸苯基中任意一個氫原子可被氟原子取代，1,4-伸環己基中任意一個或任意兩個不相鄰的-CH₂-可被-O-或-S-取代，且1,4-伸環己基中任意一個氫原子可被氟原子取代。 The A ¹ and A ² systems are each independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentyl, 2,5-tetrahydropyranyl or 1,4-bicyclo [2.2.2] octyl group, wherein any one or any two of the 1,4-phenylene groups which are not adjacent, -CH- may be substituted by -N-, and any one of 1,4-phenylene groups a hydrogen atom may be substituted with a fluorine atom, 1,4-cyclohexylene any one or any two non-adjacent -CH ₂ - may be substituted with -O- or -S-, and 1,4-cyclohexylene group Any one of the hydrogen atoms may be substituted by a fluorine atom.

依據本發明一實施方式，前述液晶化合物中，A¹與A²可各自獨立為1,4-伸苯基、1,4-伸環己基、1,3-伸環戊基或2,5-伸四氫吡喃基，其中，1,4-伸苯基中任意一個或任意兩個不相鄰的-CH-可被-N-取代，且1,4-伸苯基中任意一個氫原子可被氟原子取代，1,4-伸環己基中任意一個或任意兩個不相鄰的-CH₂-可被-O-或-S-取代，且1,4-伸環己基中任意一個氫原子可被氟原子取代，n可為1或2。 According to an embodiment of the present invention, in the liquid crystal compound, A ¹ and A ² may each independently be 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentyl or 2,5- a tetrahydropyranyl group in which any one or any two of the 1,4-phenylene groups which are not adjacent may be substituted by -N-, and any one of the 1,4-phenylene groups may have a hydrogen atom may be substituted with a fluorine atom, 1,4-cyclohexylene any one or any two non-adjacent -CH ₂ - may be substituted with -O- or -S-, 1,4-cyclohexylene and any one of The hydrogen atom may be substituted by a fluorine atom, and n may be 1 or 2.

依據本發明另一實施方式，前述液晶化合物中，A¹與A²可各自獨立為1,4-伸苯基、1,4-伸環己基或2,5-伸四氫吡喃基，且1,4-伸苯基中任意一個氫原子可被氟原子取代，1,4-伸環己基中任意一個或任意兩個不相鄰的-CH₂-可被-O-或-S-取代，且1,4-伸環己基中任意一個氫原子可被氟原子取代，Z¹、Z²與Z³可為單鍵，m可為1，n可為1。 According to another embodiment of the present invention, in the liquid crystal compound, A ¹ and A ² may each independently be a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,5-tetrahydropyranyl group, and a 1,4-phenylene arbitrary hydrogen atom may be substituted with a fluorine atom, 1,4-cyclohexylene any one or any two non-adjacent -CH ₂ - may be substituted with -O- or -S- And any one of the 1,4-cyclohexylene groups may be substituted by a fluorine atom, Z ¹ , Z ² and Z ³ may be a single bond, m may be 1, and n may be 1.

依據本發明再一實施方式，前述液晶化合物中，A¹與A²可為1,4-伸苯基，且1,4-伸苯基中任意一個氫原子可被氟原子取代，Z¹、Z²與Z³可為單鍵，m可為1，n可為1。 According to still another embodiment of the present invention, in the liquid crystal compound, A ¹ and A ² may be a 1,4-phenylene group, and any one of the 1,4-phenylene groups may be substituted by a fluorine atom, Z ¹ , Z ² and Z ³ may be a single bond, m may be 1, and n may be 1.

本發明之液晶化合物可具有但不限於如式(I-1)、式(I-2)、式(I-3)或式(I-4)所示之一結構： The liquid crystal compound of the present invention may have, but is not limited to, one of the structures shown in the formula (I-1), the formula (I-2), the formula (I-3) or the formula (I-4):

液晶組成物Liquid crystal composition

本發明之液晶組成物包含前述結構如式(I)之液晶化合物。 The liquid crystal composition of the present invention comprises the liquid crystal compound of the above formula (I).

前述之液晶組成物可更包含結構如式(II)、式(III)及式(IV)所示之化合物之至少一者：R³-A⁴-Z⁴-A⁵-R⁴ (II)， R⁵-A⁶-Z⁵-A⁷-Z⁶-A⁸-R⁶ (III)， R⁷-A⁹-Z⁷-A¹⁰-Z⁸-A¹¹-Z⁹-A¹²-R⁸ (IV)，其中，R³、R⁵與R⁷係各自獨立為碳數1至15的烷基或碳數2至15的烯基，R³、R⁵與R⁷中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且R³、R⁵與R⁷中任意一個或多個不相鄰的-CH₂-可被-O-、-S-、-CO-、-COO-、-O-CO-或-O-COO-取代。R⁴、R⁶與R⁸係各自獨立為氫、鹵素、碳數1至15的烷基或碳數2至15的烯基，R⁴、R⁶與R⁸中任意一個或多個-H可被-F、-CF₃或-CF₂H取代，且R⁴、R⁶與R⁸中任意一個或多個不相鄰的-CH₂-可被-O-、-S-、-CO-、-COO-、-O-CO-或-O-COO-取代。A⁴、A⁵、A⁶、A⁷、A⁸、A⁹、A¹⁰、A¹¹與A¹²係各自獨立為1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基或2,5-茚滿基，其中1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基與2,5-茚滿基中任意一個或多個氫原子可被氟原子取代。Z⁴、Z⁵、Z⁶、Z⁷、Z⁸與Z⁹係各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C₄H₈-、-CF₂-CF₂-、-C=C-、-C≡C-、-CF₂O-、-OCF₂-、-COO-或-O-CO-。前述之液晶組成物可更包含結構如式(II)、式(III)及式(IV)所示之化合物之至少一者，係指液晶組成物可僅包含結構如式(II)、式(III)及式(IV)所示之化合物之其中一種，亦可同時包含二種或者二種以上。 The liquid crystal composition may further comprise at least one of the compounds of the formula (II), the formula (III) and the formula (IV): R ³ -A ⁴ -Z ⁴ -A ⁵ -R ⁴ (II) , R ⁵ -A ⁶ -Z ⁵ -A ⁷ -Z ⁶ -A ⁸ -R ⁶ (III), R ⁷ -A ⁹ -Z ⁷ -A ¹⁰ -Z ⁸ -A ¹¹ -Z ⁹ -A ¹² -R ⁸ (IV), wherein R ³ , R ⁵ and R ⁷ are each independently an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and any one or more of R ³ , R ⁵ and R ⁷ -H can be substituted by -F, -CF ₃ , -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ³ , R ⁵ and R ⁷ can be -O-, -S- , -CO-, -COO-, -O-CO- or -O-COO-. R ⁴ , R ⁶ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and any one or more of R ⁴ , R ⁶ and R ⁸ -H Can be substituted by -F, -CF ₃ or -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ⁴ , R ⁶ and R ⁸ can be -O-, -S-, -CO -, -COO-, -O-CO- or -O-COO-. A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , A ¹¹ and A ¹² are each independently 1,4-cyclohexylene, 1,4-phenylene, 1,3- extending cyclopentyl or 2,5 indanyl, 1,4-cyclohexylene group wherein any one or more non-adjacent -CH ₂ - may be replaced by -O-, 1,4-cyclohexylene and Any one or more of the hydrogen atoms of the 1,4-phenylene group, the 1,3-cyclopentyl group and the 2,5-indanyl group may be substituted by a fluorine atom. Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ and Z ⁹ are each independently a single bond, a double bond, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₄ -, -C ₄ H ₈ -, -CF ₂ -CF ₂ -, -C=C-, -C≡C-, -CF ₂ O-, -OCF ₂ -, -COO- or -O-CO-. The liquid crystal composition may further comprise at least one of the compounds of the formula (II), the formula (III) and the formula (IV), and the liquid crystal composition may comprise only the structure of the formula (II), One of the compounds represented by III) and (IV) may be contained in combination of two or more kinds.

前述液晶組成物中，可更選擇性地包含添加劑，該添加劑可選自由表一所示之摻雜劑之其中一者或表二所示之安定劑之其中一者。 In the foregoing liquid crystal composition, an additive may be more selectively contained, and the additive may be selected from one of the dopants shown in Table 1 or one of the stabilizers shown in Table 2.

前述液晶組成物中，基於液晶組成物的含量為100 重量百分比，液晶組成物可包含0.1重量百分比至10重量百分比的結構如式(I)之液晶化合物，5重量百分比至50重量百分比的式(II)化合物，15重量百分比至50重量百分比的式(III)化合物以及1重量百分比至50重量百分比的式(IV)化合物。較佳地，基於液晶組成物的含量為100重量百分比，液晶組成物可包含0.1重量百分比至10重量百分比的結構如式(I)之液晶化合物，15重量百分比至50重量百分比的式(II)化合物，20重量百分比至50重量百分比的式(III)化合物以及1重量百分比至35重量百分比的式(IV)化合物。更佳地，基於液晶組成物的含量為100重量百分比，液晶組成物可包含0.1重量百分比至10重量百分比的結構如式(I)之液晶化合物，20重量百分比至50重量百分比的式(II)化合物，25重量百分比至50重量百分比的式(III)化合物以及10重量百分比至31重量百分比的式(IV)化合物。 In the liquid crystal composition described above, the content of the liquid crystal composition is 100. The weight percentage of the liquid crystal composition may include 0.1% by weight to 10% by weight of the liquid crystal compound of the formula (I), 5 parts by weight to 50% by weight of the compound of the formula (II), and 15 parts by weight to 50% by weight of the formula ( III) a compound and from 1% by weight to 50% by weight of a compound of formula (IV). Preferably, the liquid crystal composition may comprise 0.1% by weight to 10% by weight of the liquid crystal compound of the formula (I), and 15% by weight to 50% by weight of the formula (II), based on 100% by weight of the liquid crystal composition. The compound, 20% by weight to 50% by weight of the compound of the formula (III) and 1% by weight to 35% by weight of the compound of the formula (IV). More preferably, the liquid crystal composition may comprise 0.1% by weight to 10% by weight of the liquid crystal compound of the formula (I), and 20% by weight to 50% by weight of the formula (II), based on the content of the liquid crystal composition being 100% by weight. The compound, 25 parts by weight to 50% by weight of the compound of the formula (III) and 10% by weight to 31% by weight of the compound of the formula (IV).

依據本發明一實施方式，前述液晶組成物中，R³、R⁵與R⁷可各自獨立為碳數1至7的烷基或碳數2至7的烯基，R³、R⁵與R⁷中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且R³、R⁵與R⁷中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代。R⁴、R⁶與R⁸可各自獨立為氫、鹵素、碳數1至7的烷基或碳數2至7的烯基，R⁴、R⁶與R⁸中任意一個或多個-H可被-F、-CF₃或-CF₂H取代，且R⁴、R⁶與R⁸中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代。A⁴、A⁵、A⁶、A⁷、A⁸、A⁹、A¹⁰、A¹¹與A¹²可各自獨立為1,4- 伸環己基、1,4-伸苯基或2,5-茚滿基，其中1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且1,4-伸環己基、1,4-伸苯基與2,5-茚滿基中任意一個或多個氫原子可被氟原子取代。Z⁴、Z⁵、Z⁶、Z⁷、Z⁸與Z⁹可各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C=C-、-C≡C-、-CF₂O-、-COO-或-O-CO-。 According to an embodiment of the present invention, in the liquid crystal composition, R ³ , R ⁵ and R ⁷ may each independently be an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and R ³ , R ⁵ and R. ^7, any one or more may be -H -F, -CF _3, -CF ₂ H substituent, and R ^3, R ⁵ and R ⁷ are any one or more nonadjacent -CH ₂ - may be - O-, -CO-, -COO-, -O-CO- or -O-COO-. R ⁴ , R ⁶ and R ⁸ may each independently be hydrogen, halogen, an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, or any one or more of R ⁴ , R ⁶ and R ⁸ -H It may be substituted by -F, -CF ₃ or -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ⁴ , R ⁶ and R ⁸ may be -O-, -CO-, -COO -, -O-CO- or -O-COO-. A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , A ¹¹ and A ¹² may each independently be 1,4-cyclohexylene, 1,4-phenylene or 2,5- Indane, wherein any one or more of the 1,4-cyclohexylene groups which are not adjacent, -CH ₂ - may be substituted by -O-, and 1,4-cyclohexylene, 1,4-phenylene and Any one or more of the hydrogen atoms in the 2,5-indanyl group may be substituted by a fluorine atom. Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ and Z ⁹ may each independently be a single bond, a double bond, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₄ -, -C=C- , -C≡C-, -CF ₂ O-, -COO- or -O-CO-.

依據本發明另一實施方式，前述液晶組成物中，式(II)化合物中的R³可為碳數1至7的烷基或碳數2至7的烯基，R⁴可為氫、鹵素、碳數1至7的烷基或碳數2至7的烯基，其中，R³與R⁴中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且R³與R⁴中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代。A⁴與A⁵可各自獨立為1,4-伸環己基或1,4-伸苯基，其中1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且1,4-伸環己基與1,4-伸苯基中任意一個或多個氫原子可被氟原子取代。Z⁴可為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C=C-、-C≡C-、-CF₂O-、-COO-或-O-CO-。例如，式(II)化合物可為但不限於結構如式(II-1)及式(II-6)所示之化合物： According to another embodiment of the present invention, in the liquid crystal composition, R ³ in the compound of the formula (II) may be an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and R ⁴ may be hydrogen or halogen. An alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, wherein any one or more of ^{-3 of} R ³ and R ⁴ may be substituted by -F, -CF ₃ or -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ³ and R ⁴ may be substituted by -O-, -CO-, -COO-, -O-CO- or -O-COO-. A ⁴ and A ⁵ each independently 1,4-cyclohexylene or 1,4-phenylene, 1,4-cyclohexylene group wherein any one or more non-adjacent -CH ₂ - may be - O-substituted, and any one or more of the hydrogen atoms of the 1,4-cyclohexylene group and the 1,4-phenylene group may be substituted by a fluorine atom. Z ⁴ may be a single bond, a double bond, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₄ -, -C=C-, -C≡C-, -CF ₂ O-, -COO- or -O-CO-. For example, the compound of formula (II) may be, but is not limited to, a compound of the formula (II-1) and formula (II-6):

上述式(II-1)至式(II-6)所示之化合物可單獨使用，亦可同時使用兩種以上。 The compounds represented by the above formula (II-1) to formula (II-6) may be used singly or in combination of two or more.

依據本發明再一實施方式，前述液晶組成物中，式(III)化合物中的R⁵可為碳數1至7的烷基或碳數2至7的烯基，R⁶可為氫、鹵素、碳數1至7的烷基或碳數2至7的烯基，其中，R⁵與R⁶中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且R⁵與R⁶中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代。A⁶、A⁷與A⁸可各自獨立為1,4-伸環己基、1,4-伸苯基或2,5-茚滿基，其中1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且1,4-伸環己基、1,4-伸苯基與2,5-茚滿基中任意一個或多個氫原子可被氟原子取代。Z⁵與Z⁶可各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C=C-、-C≡C-、-CF₂O-、-COO-或-O-CO-。例如，式(III)化合物可為但不限於結構如式(III-1)至式(III-25)所示之化合物： According to still another embodiment of the present invention, in the liquid crystal composition, R ⁵ in the compound of the formula (III) may be an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and R ⁶ may be hydrogen or halogen. An alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, wherein any one or more of ^{-5 of} R ⁵ and R ⁶ may be substituted by -F, -CF ₃ or -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ⁵ and R ⁶ may be substituted by -O-, -CO-, -COO-, -O-CO- or -O-COO-. A ⁶ , A ⁷ and A ⁸ may each independently be 1,4-cyclohexylene, 1,4-phenylene or 2,5-indanyl, wherein any one or more of 1,4-cyclohexylene groups Non-adjacent -CH ₂ - may be substituted by -O-, and any one or more hydrogen atoms of 1,4-cyclohexylene, 1,4-phenylene and 2,5-indanyl may be fluorine Atomic substitution. Z ⁵ and Z ⁶ may each independently be a single bond, a double bond, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₄ -, -C=C-, -C≡C-, -CF ₂ O- , -COO- or -O-CO-. For example, the compound of formula (III) may be, but is not limited to, a compound of the formula (III-1) to formula (III-25):

上述式(III-1)至式(III-25)所示之化合物可單獨使用，亦可同時使用兩種以上。 The compounds represented by the above formula (III-1) to formula (III-25) may be used singly or in combination of two or more.

依據本發明再一實施方式，前述液晶組成物中，式(IV)化合物中的R⁷可為碳數1至7的烷基或碳數2至7的烯基，R⁸可為氫、鹵素、碳數1至7的烷基或碳數2至7的烯基，其中，R⁷與R⁸中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且R⁷與R⁸中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代。A⁹、A¹⁰、A¹¹與A¹²可各自獨立為1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基或2,5-茚滿基，其中1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基或2,5-茚滿基中任意一個或多個氫原子可被氟原子取代。Z⁷、Z⁸與Z⁹可各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C=C-、-C≡C-、-CF₂O-、-COO-或-O-CO-。例如，式(IV)化合物可為但不限於結構如式(IV-1)至式(IV-8)所示之化合物： According to still another embodiment of the present invention, in the liquid crystal composition, R ⁷ in the compound of the formula (IV) may be an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and R ⁸ may be hydrogen or halogen. An alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, wherein any one or more of R ⁷ and R ⁸ may be substituted by -F, -CF ₃ or -CF ₂ H, and -CH ₂ - which is not adjacent to any one or more of R ⁷ and R ⁸ may be substituted by -O-, -CO-, -COO-, -O-CO- or -O-COO-. A ⁹ , A ¹⁰ , A ¹¹ and A ¹² may each independently be a 1,4-cyclohexylene group, a 1,4-phenylene group, a 1,3-cyclopentyl group or a 2,5-indanyl group, wherein Any one or more of the non-adjacent -CH ₂ - may be substituted by -O-, and 1,4-cyclohexylene, 1,4-phenylene, 1,3-extension ring Any one or more of the hydrogen atoms of the pentyl or 2,5-indanyl group may be substituted by a fluorine atom. Z ⁷ , Z ⁸ and Z ⁹ may each independently be a single bond, a double bond, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₄ -, -C=C-, -C≡C-, -CF ₂ O-, -COO- or -O-CO-. For example, the compound of formula (IV) may be, but is not limited to, a compound of the formula (IV-1) to formula (IV-8):

上述式(IV-1)至式(IV-8)所示之化合物可單獨使用，亦可同時使用兩種以上。 The compounds represented by the above formula (IV-1) to formula (IV-8) may be used singly or in combination of two or more.

液晶顯示元件Liquid crystal display element

本發明之液晶顯示元件包含前述之液晶組成物。關於液晶顯示元件的結構與製造方法係習用，在此不與贅述。 The liquid crystal display element of the present invention comprises the aforementioned liquid crystal composition. The structure and manufacturing method of the liquid crystal display element are conventional and will not be described here.

液晶化合物之製備方法Method for preparing liquid crystal compound <式(I-2)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (I-2)>

式(I-2)之液晶化合物可利用合成流程1所示之製備方法而得到： The liquid crystal compound of the formula (I-2) can be obtained by the production method shown in Synthesis Scheme 1:

合成流程1中化合物(i-2-1)的製備方法如下：將10克(35mmol)的1-溴-4-碘苯(1-bromo-4-iodobenzene)用無水四氫呋喃(dry THF)溶解後，置於乾燥250mL雙頸瓶中，在氮氣環境和低溫-78℃下，將17mL(42mmol)的正丁基鋰(n-BuLi)緩慢注射進雙頸瓶中，低溫下反應一小時後，再將5克(35mmol)的4-丙基環己基酮(4-propylcyclohexanone)緩慢注入，反應一小時。反應完全後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得8克化合物(i-2-1)，產率76%。 The compound (i-2-1) in the synthesis scheme 1 is prepared by dissolving 10 g (35 mmol) of 1-bromo-4-iodobenzene (1-bromo-4-iodobenzene) in anhydrous tetrahydrofuran (dry THF). Placed in a dry 250 mL double-necked flask, slowly inject 17 mL (42 mmol) of n-butyllithium (n-BuLi) into a double-necked flask under nitrogen atmosphere at a low temperature of -78 ° C, and react at low temperature for one hour. Further, 5 g (35 mmol) of 4-propylcyclohexanone was slowly injected and reacted for one hour. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and the organic layer was collected. After removing the solvent, the mixture was purified by column chromatography, and the extract was n-hexane. 8 g of compound (i-2-1) were obtained in a yield of 76%.

合成流程1中化合物(i-2-2)的製備方法如下：將8克(27mmol)化合物(i-2-1)置於250mL雙頸瓶中，加入0.5克硫酸氫鉀(KHSO₄)，在110℃下反應五小時。反應完成後，抽氣過濾除去固體，收集濾液，以減壓濃縮儀除去溶劑，以管柱層析法純化，沖提液為正己烷。得6克化合物(i-2-2)，產率80%。 The preparation of the compound (i-2-2) in the synthesis scheme 1 is as follows: 8 g (27 mmol) of the compound (i-2-1) is placed in a 250 mL double-necked flask, and 0.5 g of potassium hydrogen sulfate (KHSO ₄ ) is added. The reaction was carried out at 110 ° C for five hours. After completion of the reaction, the solid was removed by suction filtration, and the filtrate was collected, and the solvent was removed by a reduced pressure concentrator, and purified by column chromatography, and the extract was n-hexane. 6 g of compound (i-2-2) were obtained in a yield of 80%.

合成流程1中化合物(i-2-3)的製備方法如下：將0.5克(1.7mmol)化合物(i-2-2)置於100mL雙頸瓶中，在氮氣環境下，以無水四氫呋喃溶解後，在0℃下用針筒緩慢注入3.6mL、1M之BH₃/THF(BH₃溶解於四氫呋喃中，BH₃的含量為3.6mmol)，在0℃下反應一小時，待反應回到室溫後反應一小時，用針筒緩慢注入2mL乙醇後，加熱迴流反應三十分鐘，用針筒緩慢注入3M、2mL氫氧化鈉水溶液，再注入30wt%、1mL H₂O₂，持續加熱迴流兩小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，先以正己烷將未反應的化合物(i-2-2)沖出，再用乙酸乙酯將產物，即化合物(i-2-3)沖出。 The preparation method of the compound (i-2-3) in the synthesis scheme 1 is as follows: 0.5 g (1.7 mmol) of the compound (i-2-2) is placed in a 100 mL double-necked flask, and dissolved in anhydrous tetrahydrofuran under a nitrogen atmosphere. 3.6 mL, 1 M BH ₃ /THF (BH ₃ dissolved in tetrahydrofuran, BH ₃ content: 3.6 mmol) was slowly injected into the syringe at 0 ° C, and reacted at 0 ° C for one hour until the reaction was returned to room temperature. After the reaction for one hour, slowly inject 2 mL of ethanol with a syringe, heat and reflux for 30 minutes, slowly inject 3M, 2 mL of sodium hydroxide aqueous solution with a syringe, and then inject 30 wt%, 1 mL of H ₂ O ₂ , and continue to heat and reflux for two hours. . After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water. The organic layer was collected, and the solvent was removed, and then purified by column chromatography, and the unreacted compound (i-2- 2) After punching out, the product, i.e., compound (i-2-3), was washed out with ethyl acetate.

合成流程1中化合物(i-2-4)的製備方法如下：將化合物(i-2-3)用二氯甲烷溶解，緩慢加入溶解於二氯甲烷的0.5克氯鉻酸吡啶鹽(Pyridinium Chlorochromate，PPC)，加熱迴流反應14小時。反應完成後，以二氯甲烷和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，先以正己烷將未反應的化合物(i-2-3)沖出，再用沖提液比例為乙酸乙酯：正己烷為1：10將產物，即化合物(i-2-4)沖出。 The preparation of the compound (i-2-4) in the synthesis scheme 1 is as follows: the compound (i-2-3) is dissolved in dichloromethane, and 0.5 g of pyridinium chloride (Pyridinium Chlorochromate) dissolved in dichloromethane is slowly added. , PPC), heated to reflux for 14 hours. After completion of the reaction, the organic layer was extracted with dichloromethane and distilled water, and after removing the solvent, it was purified by column chromatography, and the unreacted compound (i-2-3) was first flushed out with n-hexane, and then washed. The liquid extraction ratio is B Ethyl acetate: The product, i.e., compound (i-2-4), was washed out at 1:10 n-hexane.

合成流程1中化合物(i-2-6)的製備方法如下：將0.9克(3mmol)的化合物(i-2-4)、0.78克(3mmol)的化合物(i-2-5)、1.26克(9mmol)的碳酸鉀(K₂CO₃)和0.5毫升的界面活性劑氯化甲基三辛基銨(Aliquat 336)置入250mL雙頸瓶中，以50毫升甲苯(Toluene)和10毫升蒸餾水溶解後，在氮氣環境下，加入0.1克(0.09mmol)的四(三苯基膦)鈀(Tetrakis(triphenylphosphine)palladium(0)，Pd(PPh₃)₄)，在90℃下，反應14小時。反應完成後，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得1.1克化合物(i-2-6)，產率84%。 The preparation of the compound (i-2-6) in the synthesis scheme 1 is as follows: 0.9 g (3 mmol) of the compound (i-2-4), 0.78 g (3 mmol) of the compound (i-2-5), 1.26 g. (9 mmol) potassium carbonate (K ₂ CO ₃ ) and 0.5 ml of surfactant methyl trioctyl ammonium chloride (Aliquat 336) were placed in a 250 mL two-necked flask with 50 ml of toluene and 10 ml of distilled water. After dissolution, 0.1 g (0.09 mmol) of tetrakis(triphenylphosphine)palladium (0), Pd(PPh ₃ ) ₄ ) was added under a nitrogen atmosphere, and the reaction was carried out at 90 ° C for 14 hours. . After completion of the reaction, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed and purified by column chromatography. 1.1 g of compound (i-2-6) was obtained in a yield of 84%.

合成流程1中化合物(i-2-7)的製備方法如下：將1.1克(2.5mmol)的化合物(i-2-6)溶解於二氯甲烷中，在氮氣環境下，緩慢滴入二乙胺基三氟化硫(Diethylaminosulfur trifluoride，DAST)，在50℃下加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和5%氫氧化鉀水溶液萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.8克化合物(i-2-7)，產率71%。 The preparation method of the compound (i-2-7) in the synthesis scheme 1 is as follows: 1.1 g (2.5 mmol) of the compound (i-2-6) is dissolved in dichloromethane, and slowly dropped into the diethyl group under a nitrogen atmosphere. Diethylaminosulfur trifluoride (DAST) was heated under reflux at 50 ° C for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and 5% aqueous potassium hydroxide, and the organic layer was collected, and the solvent was removed and purified by column chromatography to give n-hexane. 0.8 g of the compound (i-2-7) was obtained in a yield of 71%.

反應方程式1中化合物(I-2)的製備方法如下：將0.8克(1.7mmol)的化合物(i-2-7)溶解於四氫呋喃中，加入0.45克(4mmol)的叔丁醇鉀(potassium tert-butaoxide，t-BuOK)，加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷，得0.2克的式(I-2)的液晶化合物，產率27%。請參照第1圖，其係液晶化合物(I-2)之¹H-NMR光譜圖，由第1圖可確認液晶化合物(I-2)的結構無誤。 The preparation of the compound (I-2) in the reaction formula 1 is as follows: 0.8 g (1.7 mmol) of the compound (i-2-7) is dissolved in tetrahydrofuran, and 0.45 g (4 mmol) of potassium tert-butoxide (potassium tert) is added. -butaoxide, t-BuOK), heated to reflux for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water. The organic layer was collected, and the solvent was removed, and then purified by column chromatography, and the extract was n-hexane to obtain 0.2 g of the formula (I). -2) Liquid crystal compound, yield 27%. Referring to Fig. 1, which is a ¹ H-NMR spectrum of the liquid crystal compound (I-2), it can be confirmed from Fig. 1 that the structure of the liquid crystal compound (I-2) is correct.

<式(I-1)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (I-1)>

式(I-1)之液晶化合物與式(I-2)之液晶化合物之製備方法差異在於製備化合物(i-2-6)時，將其中的0.78克(3mmol)的化合物(i-2-5)置換為0.75克(3mmol)的化合物(i-1-5)，其他製備方法皆與式(I-2)之液晶化合物相同。化合物(i-1-5)結構如下：請參照第2圖，其係液晶化合物(I-1)之¹H-NMR光譜圖，由第2圖可確認液晶化合物(I-1)的結構無誤。 The difference between the liquid crystal compound of the formula (I-1) and the liquid crystal compound of the formula (I-2) is that 0.78 g (3 mmol) of the compound (i-2-) is prepared when the compound (i-2-6) is prepared. 5) The compound (i-1-5) was replaced with 0.75 g (3 mmol), and the other preparation methods were the same as those of the liquid crystal compound of the formula (I-2). The structure of the compound (i-1-5) is as follows: Referring to Fig. 2, which is a ¹ H-NMR spectrum of the liquid crystal compound (I-1), it can be confirmed from Fig. 2 that the structure of the liquid crystal compound (I-1) is correct.

<式(I-3)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (I-3)>

式(I-3)之液晶化合物與式(I-2)之液晶化合物之製備方法差異在於製備化合物(i-2-6)時，將其中的0.78克(3mmol)的化合物(i-2-5)置換為0.78克(3mmol)的化合物(i-3-5)，其他製備方法皆與式(I-2)之液晶化合物相同。化合物(i-3-5)結構如下：請參照第3圖，其係液晶化合物(I-3)之¹H-NMR光譜圖，由第3圖可確認液晶化合物(I-3)的結構無誤。 The difference between the liquid crystal compound of the formula (I-3) and the liquid crystal compound of the formula (I-2) is that 0.78 g (3 mmol) of the compound (i-2-) is prepared when the compound (i-2-6) is prepared. 5) The compound (i-3-5) was replaced with 0.78 g (3 mmol), and the other preparation methods were the same as those of the liquid crystal compound of the formula (I-2). The structure of the compound (i-3-5) is as follows: Referring to Fig. 3, which is a ¹ H-NMR spectrum of the liquid crystal compound (I-3), it can be confirmed from Fig. 3 that the structure of the liquid crystal compound (I-3) is correct.

<式(I-4)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (I-4)>

式(I-4)之液晶化合物可利用合成流程2所示之製備方法而得到： The liquid crystal compound of the formula (I-4) can be obtained by the production method shown in Synthesis Scheme 2:

合成流程2中化合物(i-4-1)的製備方法如下：將15克(78.9mmol)的4-溴-2-氟苯胺(4-bromo-2-fluorobenzenamine)溶解於150mL的三乙胺(triethylamine，Et₃N)，在冰浴下緩慢滴加入15mL(236.8mmol)的乙醯氯(acetyl chloride)，在冰浴下反應1小時，反應完全後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去大部分溶劑後，加入正己烷洗去不純物，抽氣過濾收集固體。得淡黃色固體的化合物(i-4-1)13.7克，產率74.8%。 The preparation of the compound (i-4-1) in the synthesis scheme 2 is as follows: 15 g (78.9 mmol) of 4-bromo-2-fluorobenzenamine is dissolved in 150 mL of triethylamine ( Triethylamine, Et ₃ N), 15 mL (236.8 mmol) of acetyl chloride was slowly added dropwise in an ice bath, and reacted for 1 hour in an ice bath. After the reaction was completed, the solvent was removed by a reduced pressure concentrator to acetic acid. After extracting the ethyl ester and distilled water, the organic layer was collected, and most of the solvent was removed. Then, n-hexane was added and the impurities were removed, and the solid was collected by suction filtration. The compound (i-4-1) was obtained as a pale yellow solid (13.7 g, yield: 74.8%).

合成流程2中化合物(i-4-2)的製備方法如下：將10克(43.0mmol)化合物(i-4-1)用無水四氫呋喃溶解後，置於乾燥250mL雙頸瓶中，在氮氣環境和低溫下，將3.5mL、2.5M正丁基鋰(86.1mmol)緩慢注射進雙頸瓶中，低溫下反應一小時後，再將6.6克(47.3mmol)的4-丙基環己基酮(4-propylcyclohexanone)緩慢注入，反應一小時。反應完全後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為乙酸乙酯與正己烷混合液，比例為1：3，除去未反應的化合物(i-4-1)後，改變沖提液為乙酸乙酯，將得到深褐色液體，直接進行下一步驟。 The preparation method of the compound (i-4-2) in the synthesis scheme 2 is as follows: 10 g (43.0 mmol) of the compound (i-4-1) is dissolved in anhydrous tetrahydrofuran, and placed in a dry 250 mL double-necked flask under a nitrogen atmosphere. And at a low temperature, 3.5 mL, 2.5 M n-butyllithium (86.1 mmol) was slowly injected into a two-necked flask, and after reacting for one hour at a low temperature, 6.6 g (47.3 mmol) of 4-propylcyclohexyl ketone ( 4-propylcyclohexanone) was slowly injected and reacted for one hour. After the reaction was completed, the solvent was removed under a reduced pressure concentrator and extracted with ethyl acetate and distilled water. The organic layer was collected, and the solvent was removed, and then purified by column chromatography. The extract was a mixture of ethyl acetate and n-hexane in a ratio of 1:3, and the unreacted compound (i-4-1) was removed and changed. The extract was ethyl acetate which gave a dark brown liquid which was taken directly to the next step.

合成流程2中化合物(i-4-3)的製備方法如下：將上一步驟得到的化合物(i-4-2)置於250mL雙頸瓶中，加入3克的硫酸氫鉀(KHSO₄)，在110℃下反應五小時。反應完成後，抽氣過濾除去固體，收集濾液，以減壓濃縮儀除去溶劑，再以管柱層析法純化，沖提液為乙酸乙酯與正己烷混合液，比例為1：3。得2.5克化合物(i-4-3)，產率21%。 The preparation method of the compound (i-4-3) in the synthesis scheme 2 is as follows: the compound (i-4-2) obtained in the previous step is placed in a 250 mL double-necked flask, and 3 g of potassium hydrogen sulfate (KHSO ₄ ) is added. The reaction was carried out at 110 ° C for five hours. After completion of the reaction, the solid was removed by suction filtration, and the filtrate was collected, and the solvent was removed by a reduced pressure concentrator, and then purified by column chromatography. The extract was a mixture of ethyl acetate and n-hexane in a ratio of 1:3. 2.5 g of compound (i-4-3) were obtained in a yield of 21%.

合成流程2中化合物(i-4-4)的製備方法如下：將2.5克(9mmol)的化合物(i-4-3)溶解於乙醇(EtOH)中，緩慢加入鹽酸，加熱迴流3小時，反應完成後，讓反應回到室溫，緩慢加入氫氧化鈉水溶液直到反應呈中性或是弱鹼，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，得2克深褐色液體，產率95%。 The compound (i-4-4) in the synthesis scheme 2 is prepared by dissolving 2.5 g (9 mmol) of the compound (i-4-3) in ethanol (EtOH), slowly adding hydrochloric acid, and heating under reflux for 3 hours. After completion, the reaction was returned to room temperature, and an aqueous sodium hydroxide solution was slowly added until the reaction was neutral or weak. The solvent was removed under a reduced pressure concentrator, extracted with ethyl acetate and distilled water, and the organic layer was collected. 2 g of dark brown liquid was obtained with a yield of 95%.

合成流程2中化合物(i-4-5)的製備方法如下：將1.27克(5.46mmol)的化合物(i-4-4)溶解於30mL四氫呋喃中，緩慢滴加入25mL鹽酸，在0℃時，緩慢滴加入溶於蒸餾水中的0.75克(10.9mmol)的亞硝酸鈉，在0℃下反應1小時後，在0℃下緩慢滴加入溶於蒸餾水中的1.8克(10.9mmol)的碘化鉀，反應1小時後，在室溫下加入5mL飽和硫代硫酸鈉水溶液，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得透明液體0.64克，產率35%。 The preparation method of the compound (i-4-5) in the synthesis scheme 2 is as follows: 1.27 g (5.46 mmol) of the compound (i-4-4) is dissolved in 30 mL of tetrahydrofuran, and 25 mL of hydrochloric acid is slowly added dropwise at 0 ° C. 0.75 g (10.9 mmol) of sodium nitrite dissolved in distilled water was slowly added dropwise, and after reacting at 0 ° C for 1 hour, 1.8 g (10.9 mmol) of potassium iodide dissolved in distilled water was slowly added dropwise at 0 ° C to react. After 1 hour, 5 mL of a saturated aqueous solution of sodium thiosulfate was added at room temperature, and the solvent was removed under a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed by column chromatography. Purified, the extract was n-hexane. A clear liquid of 0.64 g was obtained with a yield of 35%.

合成流程2中化合物(i-4-6)的製備方法如下：將1.8克(5.2mmol)化合物(i-4-5)置於50mL雙頸瓶中，在氮氣環境下，以無水四氫呋喃溶解後，在0℃下用針筒緩慢注入30mL、1M的BH₃/THF，在室溫下反應3小時，用針筒緩慢注入3M、10mL氫氧化鈉水溶液，再注入30wt%、7mL H₂O₂，持續加熱迴流14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，先以正己烷將未反應的化合物(i-4-5)沖出，再用乙酸乙酯將產物沖出。得黃色液體，直接進行下一步驟。 The preparation method of the compound (i-4-6) in the synthesis scheme 2 is as follows: 1.8 g (5.2 mmol) of the compound (i-4-5) is placed in a 50 mL double-necked flask, and dissolved in anhydrous tetrahydrofuran under a nitrogen atmosphere. Slowly inject 30 mL, 1 M BH ₃ /THF with a syringe at 0 ° C, react at room temperature for 3 hours, slowly inject 3M, 10 mL aqueous sodium hydroxide solution with a syringe, and inject 30 wt%, 7 mL H ₂ O ₂ , heating and refluxing for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water. The organic layer was collected, and the solvent was removed, and then purified by column chromatography, and the unreacted compound (i-4- 5) The product was washed out and the product was washed out with ethyl acetate. A yellow liquid is obtained and the next step is carried out directly.

合成流程2中化合物(i-4-7)的製備方法如下：將化合物(i-4-6)用20mL二氯甲烷溶解，緩慢加入溶解於二氯甲烷的2克的氯鉻酸吡啶鹽(Pyridinium Chlorochromate，PPC)，加熱迴流反應5小時。反應完成後，以矽藻土(Celite)進行快速管柱層析法純化，以二氯甲烷和乙酸乙酯做為沖提液。以減壓濃縮儀除去溶劑，得到褐色液體，直接進行下一步驟。 The compound (i-4-7) in the synthesis scheme 2 is prepared by dissolving the compound (i-4-6) in 20 mL of dichloromethane, and slowly adding 2 g of pyridinium chlorochromate dissolved in dichloromethane ( Pyridinium Chlorochromate (PPC), heated to reflux for 5 hours. After completion of the reaction, purification was carried out by flash column chromatography using Celite, using dichloromethane and ethyl acetate as the extract. The solvent was removed under a reduced pressure concentrator to give a brown liquid which was taken directly to the next step.

合成流程2中化合物(i-4-8)的製備方法如下：將化合物(i-4-7)溶解於二氯甲烷中，在氮氣環境下，緩慢滴入2mL的二乙胺基三氟化硫(Diethylaminosulfur trifluoride，DAST)，在50℃下加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和5%氫氧化鉀水溶液萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.3克化合物(i-4-8)，產率15%。 The preparation method of the compound (i-4-8) in the synthesis scheme 2 is as follows: the compound (i-4-7) is dissolved in dichloromethane, and 2 mL of diethylamine trifluoride is slowly added dropwise under a nitrogen atmosphere. Diethylaminosulfur trifluoride (DAST) was heated under reflux at 50 ° C for 14 hours. After the completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and 5% aqueous potassium hydroxide, and then the organic layer was collected, and the solvent was removed and purified by column chromatography. The solution is n-hexane. 0.3 g of the compound (i-4-8) was obtained in a yield of 15%.

合成流程2中化合物(I-4)的製備方法如下：將0.3克(0.82mmol)的化合物(i-4-8)溶解於三乙胺(Et₃N)中，除氧氣(degas)後，在氮氣環境下，加入0.01克碘化銅(0.033mmol)和0.03克(0.016mmol)的四(三苯基膦)鈀(Tetrakis(triphenylphosphine)palladium(0)，Pd(PPh₃)₄)，最後再加入0.13克(0.91mmol)的1-乙炔基-4-丙基苯(l-ethynyl-4-propylbenzene)，在90℃下，反應14小時。反應完成後，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.03克最終產物，產率9%。請參照第4圖，其係液晶化合物(I-4)之¹H-NMR光譜圖，由第4圖可確認液晶化合物(I-4)的結構無誤。 The preparation of the compound (I-4) in the synthesis scheme 2 is as follows: 0.3 g (0.82 mmol) of the compound (i-4-8) is dissolved in triethylamine (Et ₃ N), after degassing (degas), Under a nitrogen atmosphere, 0.01 g of copper iodide (0.033 mmol) and 0.03 g (0.016 mmol) of tetrakis(triphenylphosphine)palladium (0), Pd(PPh ₃ ) ₄ ) were added. Further, 0.13 g (0.91 mmol) of 1-ethynyl-4-propylbenzene was added, and the reaction was carried out at 90 ° C for 14 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed and purified by column chromatography. 0.03 g of the final product was obtained in a yield of 9%. Referring to Fig. 4, which is a ¹ H-NMR spectrum of the liquid crystal compound (I-4), it can be confirmed from Fig. 4 that the structure of the liquid crystal compound (I-4) is correct.

<比較例之液晶化合物><Comparative Example Liquid Crystal Compound>

比較例之液晶化合物為結構如式(R-1)及式(R-2)所示之液晶化合物： The liquid crystal compound of the comparative example is a liquid crystal compound represented by the formula (R-1) and the formula (R-2):

<式(R-1)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (R-1)>

式(R-1)之液晶化合物可利用合成流程3所示之製備方法而得到： The liquid crystal compound of the formula (R-1) can be obtained by the production method shown in Synthesis Scheme 3:

合成流程3中化合物(r-1-1)的製備方法如下：將20克(100.4mmol)的對溴丙苯(1-bromo-4-propylbenzene)用無水四氫呋喃溶解後，置於乾燥的500mL雙頸瓶中，在氮氣環境和低溫下，將52mL、2.5M(130mmol)的正丁基鋰緩慢注射進雙頸瓶中，低溫下反應一小時後，再將25mL(100mmol)的2-異丙氧基-4,4,5,5-四甲基-1,3,2-二氧雜硼烷 (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane)緩慢注入，反應一小時。反應完全後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷，除去未反應的對溴丙苯後，改變沖提液為乙酸乙酯，將得到15.32克淺黃色液體，產率62%。 The preparation method of the compound (r-1-1) in the synthesis scheme 3 is as follows: 20 g (100.4 mmol) of 1-bromo-4-propylbenzene is dissolved in anhydrous tetrahydrofuran, and then placed in a dry 500 mL double. In a flask, 52 mL, 2.5 M (130 mmol) of n-butyllithium was slowly injected into a double-necked flask under nitrogen atmosphere and low temperature. After reacting at low temperature for one hour, 25 mL (100 mmol) of 2-isopropyl was further added. Oxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) was slowly injected and reacted for one hour. After the reaction was completed, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and then the organic layer was collected. After removing the solvent, the solvent was purified by column chromatography, and the extract was n-hexane to remove unreacted bromopropyl bromide. After benzene, changing the extract to ethyl acetate gave 15.32 g of a pale yellow liquid with a yield of 62%.

合成流程3中化合物(r-1-2)的製備方法如下：將15克(60mmol)的化合物(r-1-1)、11.5克(12.6mmol)的4-溴-2-氟苯胺、7.3克(37.7mmol)的氫氧化鈉和0.5毫升的界面活性劑氯化甲基三辛基銨置入500mL的雙頸瓶中，以150mL的甲苯和30mL的蒸餾水溶解後，在氮氣環境下，加入0.05克(0.05mmol)的四(三苯基膦)鈀，在90℃下，反應5小時。反應完成後，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得5.7克白色固體，產率42%。 The preparation of the compound (r-1-2) in the synthesis scheme 3 is as follows: 15 g (60 mmol) of the compound (r-1-1), 11.5 g (12.6 mmol) of 4-bromo-2-fluoroaniline, 7.3 Glucose (37.7mmol) of sodium hydroxide and 0.5ml of surfactant methyltrioctylammonium chloride were placed in a 500mL double-necked flask, dissolved in 150mL of toluene and 30mL of distilled water, and then added under nitrogen atmosphere. 0.05 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium was reacted at 90 ° C for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed and purified by column chromatography. 5.7 g of a white solid were obtained in a yield of 42%.

合成流程3中化合物(r-1-3)的製備方法如下：將5克(22mmol)化合物(r-1-2)溶解於30mL的四氫呋喃中，緩慢滴加入15mL的鹽酸，在0℃時，緩慢滴加入溶於蒸餾水中的3.1克(44mmol)亞硝酸鈉，在0℃下反應1小時後，在0℃下緩慢滴加入溶於蒸餾水中的7.5克(44mmol)碘化鉀，反應1小時後，在室溫下加入5mL的飽和硫代硫酸鈉水溶液，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得透明液體5.3克，產率70%。 The preparation method of the compound (r-1-3) in the synthesis scheme 3 is as follows: 5 g (22 mmol) of the compound (r-1-2) is dissolved in 30 mL of tetrahydrofuran, and 15 mL of hydrochloric acid is slowly added dropwise at 0 ° C. 3.1 g (44 mmol) of sodium nitrite dissolved in distilled water was slowly added dropwise, and after reacting at 0 ° C for 1 hour, 7.5 g (44 mmol) of potassium iodide dissolved in distilled water was slowly added dropwise at 0 ° C, and after reacting for 1 hour, 5 mL of a saturated aqueous solution of sodium thiosulfate was added at room temperature, and the solvent was removed under a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed, and then purified by column chromatography. Hexane. A clear liquid of 5.3 g was obtained with a yield of 70%.

合成流程3中化合物(r-1-4)的製備方法如下：將3克(8.8mmol)化合物(r-1-3)用無水四氫呋喃溶解後，置於乾燥的250mL雙頸瓶中，在氮氣環境和低溫下，將5.3mL、2.5M(13.2mmol)的正丁基鋰緩慢注射進雙頸瓶中，低溫下反應一小時後，再將1.2克(8.8mmol)的4-丙基環己基酮緩慢注入，反應一小時。反應完全後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷，除去未反應的化合物(r-1-3)後，改變沖提液為乙酸乙酯，將得到深褐色液體2.1克，直接進行下一步驟。 The preparation of the compound (r-1-4) in the synthesis scheme 3 is as follows: 3 g (8.8 mmol) of the compound (r-1-3) is dissolved in anhydrous tetrahydrofuran, and placed in a dry 250 mL double-necked flask under nitrogen. 5.3 mL, 2.5 M (13.2 mmol) of n-butyllithium were slowly injected into a double-necked flask at ambient temperature and low temperature. After reacting for one hour at low temperature, 1.2 g (8.8 mmol) of 4-propylcyclohexyl was further added. The ketone was slowly injected and reacted for one hour. After the reaction was completed, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water. The organic layer was collected, and the solvent was removed, and then purified by column chromatography, and the extract was n-hexane to remove unreacted compound (r After -1-3), changing the extract to ethyl acetate gave 2.1 g of a dark brown liquid and proceed directly to the next step.

合成流程3中化合物(r-1-5)的製備方法如下：將上一步驟得到的化合物(r-1-4)置於250mL的雙頸瓶中，加入3克的KHSO4，在110℃下反應五小時。反應完成後，抽氣過濾除去固體，收集濾液，以減壓濃縮儀除去溶劑，以管柱層析法純化，沖提液為正己烷。得1.4克的化合物(r-1-5)，產率47%。 The preparation method of the compound (r-1-5) in the synthesis scheme 3 is as follows: the compound (r-1-4) obtained in the previous step is placed in a 250 mL double-necked flask, and 3 g of KHSO4 is added at 110 ° C. Reaction for five hours. After completion of the reaction, the solid was removed by suction filtration, and the filtrate was collected, and the solvent was removed by a reduced pressure concentrator, and purified by column chromatography, and the extract was n-hexane. 1.4 g of compound (r-1-5) were obtained in a yield of 47%.

合成流程3中化合物(r-1-6)的製備方法如下：將1.4克(4.2mmol)的化合物(r-1-5)置於50mL的雙頸瓶中，在氮氣環境下，以無水四氫呋喃溶解後，在0℃下用針筒緩慢注入10mL、1M的BH₃/THF，在室溫下反應3小時，用針筒緩慢注入3M、6mL的氫氧化鈉水溶液，再注入30wt%、3mL的H₂O₂，持續加熱迴流14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，先以正己烷將未反應的化合物(r-1-5)沖出，再用乙酸乙酯將產物沖出。得黃色液體，直接進行下一步驟。 The preparation of the compound (r-1-6) in the synthesis scheme 3 is as follows: 1.4 g (4.2 mmol) of the compound (r-1-5) is placed in a 50 mL double-necked flask under anhydrous nitrogen in the presence of anhydrous tetrahydrofuran. After dissolving, slowly inject 10 mL of 1 M BH ₃ /THF with a syringe at 0 ° C, react at room temperature for 3 hours, slowly inject 3 M, 6 mL of sodium hydroxide aqueous solution with a syringe, and inject 30 wt%, 3 mL. H ₂ O _{2 was} continuously heated to reflux for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed, and then purified by column chromatography, and the unreacted compound (r-1- 5) The product was washed out and the product was washed out with ethyl acetate. A yellow liquid is obtained and the next step is carried out directly.

合成流程3中化合物(r-1-7)的製備方法如下：將化合物(r-1-6)用20mL的二氯甲烷溶解，緩慢加入溶解於二氯甲烷的2克氯鉻酸吡啶鹽，加熱迴流反應5小時。反應完成後，以矽藻土進行快速管柱層析法純化，以二氯甲烷和乙酸乙酯做為沖提液。以減壓濃縮儀除去溶劑，得到褐色液體，直接進行下一步驟。 The compound (r-1-7) in the synthesis scheme 3 is prepared by dissolving the compound (r-1-6) in 20 mL of dichloromethane, and slowly adding 2 g of pyridinium chlorochromate dissolved in dichloromethane. The reaction was heated to reflux for 5 hours. After completion of the reaction, purification was carried out by rapid column chromatography using diatomaceous earth, using dichloromethane and ethyl acetate as the extract. The solvent was removed under a reduced pressure concentrator to give a brown liquid which was taken directly to the next step.

合成流程3中化合物(r-1-8)的製備方法如下：將化合物(r-1-7)溶解於二氯甲烷中，在氮氣環境下，緩慢滴入2mL的DAST，在50℃下加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和5wt%氫氧化鉀水溶液萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.2克的化合物(r-1-8)，產率12%。 The preparation method of the compound (r-1-8) in the synthesis scheme 3 is as follows: the compound (r-1-7) is dissolved in dichloromethane, and 2 mL of DAST is slowly dropped under a nitrogen atmosphere, and heated at 50 ° C. The reaction was refluxed for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and a 5 wt% aqueous solution of potassium hydroxide. The organic layer was collected, and the solvent was removed and purified by column chromatography to give n-hexane. 0.2 g of the compound (r-1-8) was obtained in a yield of 12%.

合成流程3中化合物(R-1)的製備方法如下：將0.2克(1.7mmol)化合物(r-1-8)溶解於四氫呋喃中，加入0.1克叔丁醇鉀，加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.1克化合物(R-1)，產率53%。請參照第5圖，其係液晶化合物(R-1)之¹H-NMR光譜圖，由第5圖可確認液晶化合物(R-1)的結構無誤。 The compound (R-1) in the synthesis scheme 3 was prepared by dissolving 0.2 g (1.7 mmol) of the compound (r-1-8) in tetrahydrofuran, adding 0.1 g of potassium t-butoxide, and heating to reflux for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and distilled water, and the organic layer was collected. After removing the solvent, it was purified by column chromatography, and the extract was n-hexane. 0.1 g of the compound (R-1) was obtained in a yield of 53%. Referring to Fig. 5, which is a ¹ H-NMR spectrum of the liquid crystal compound (R-1), it can be confirmed from Fig. 5 that the structure of the liquid crystal compound (R-1) is correct.

<式(R-2)之液晶化合物之製備方法><Preparation method of liquid crystal compound of formula (R-2)>

式(R-2)之液晶化合物可利用合成流程4所示之製備方法而得到： The liquid crystal compound of the formula (R-2) can be obtained by the production method shown in Synthesis Scheme 4:

合成流程4中化合物(i-2-1)至(i-2-4)的製備方法與合成流程1中化合物(i-2-1)至(i-2-4)的製備方法相同，在此不予贅述。 The preparation method of the compounds (i-2-1) to (i-2-4) in the synthesis scheme 4 is the same as the preparation method of the compounds (i-2-1) to (i-2-4) in the synthesis scheme 1, This will not be repeated.

合成流程4中化合物(r-2-6)的製備方法如下：將0.51克(1.7mmol)的化合物(i-2-4)、0.49克(1.7mmol)的化合物(r-2-5)、0.71克碳酸鉀(5.1mmol)和0.5毫升介面活性劑氯化甲基三辛基銨置入250mL的雙頸瓶中，以50mL的甲苯和10mL的蒸餾水溶解後，在氮氣環境下，加入0.1克(0.09mmol)的四(三苯基膦)鈀，在90℃下，反應14小時。反應完成後，以乙酸乙酯和蒸餾水萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.5克化合物(r-2-6)，產率64%。 The preparation of the compound (r-2-6) in the synthesis scheme 4 is as follows: 0.51 g (1.7 mmol) of the compound (i-2-4), 0.49 g (1.7 mmol) Compound (r-2-5), 0.71 g potassium carbonate (5.1 mmol) and 0.5 ml of the surfactant methyltrioctylamine chloride were placed in a 250 mL two-necked flask and dissolved in 50 mL of toluene and 10 mL of distilled water. Thereafter, 0.1 g (0.09 mmol) of tetrakis(triphenylphosphine)palladium was added under a nitrogen atmosphere, and the reaction was carried out at 90 ° C for 14 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was collected, and the solvent was removed and purified by column chromatography. 0.5 g of compound (r-2-6) was obtained in a yield of 64%.

合成流程4中化合物(R-2)的製備方法如下：將0.5克(1mmol)的化合物(r-2-6)溶解於二氯甲烷中，在氮氣環境下，緩慢滴入DAST，在50℃下加熱迴流反應14小時。反應完成後，以減壓濃縮儀除去溶劑，以乙酸乙酯和5%氫氧化鉀水溶液萃取後收集有機層，除去溶劑後，以管柱層析法純化，沖提液為正己烷。得0.3克化合物(R-2)，產率62%。請參照第6圖，其係液晶化合物(R-2)之¹H-NMR光譜圖，由第6圖可確認液晶化合物(R-2)的結構無誤。 The preparation method of the compound (R-2) in the synthesis scheme 4 is as follows: 0.5 g (1 mmol) of the compound (r-2-6) is dissolved in dichloromethane, and DAST is slowly dropped under a nitrogen atmosphere at 50 ° C. The reaction was heated under reflux for 14 hours. After completion of the reaction, the solvent was removed by a reduced pressure concentrator, and extracted with ethyl acetate and 5% aqueous potassium hydroxide, and the organic layer was collected, and the solvent was removed and purified by column chromatography to give n-hexane. 0.3 g of the compound (R-2) was obtained in a yield of 62%. Referring to Fig. 6, which is a ¹ H-NMR spectrum of the liquid crystal compound (R-2), it can be confirmed from Fig. 6 that the structure of the liquid crystal compound (R-2) is correct.

液晶化合物之評價方法Evaluation method of liquid crystal compound

(一)相變化溫度(Phase Transfer Temperature，PT，單位為℃)：使用差示掃描量熱儀(DSC)系統，將液晶化合物置於鋁盤上精秤0.5mg至40mg，藉由液晶化合物因相變化而出現的吸熱峰及放熱峰的起始點來確定相變化溫度。相變化的表示方式為：結晶相標示為C，近晶相標示為S，向列相標示為N，液相標示為I。相變化溫度的表示方式，如「C63N138I」表示由結晶相至向列相的相變溫度 (T_C)為63℃，由向列相至液相的相變溫度(T_NI)為138℃，又例如「C107N>250I」表示由結晶相至向列相的相變溫度(T_C)為107℃，由向列相至液相的相變溫度(T_NI)大於250℃(超過儀器的偵測範圍)。 (1) Phase Transfer Temperature (PT, unit: °C): Using a differential scanning calorimeter (DSC) system, the liquid crystal compound is placed on an aluminum plate with a fine scale of 0.5 mg to 40 mg, by liquid crystal compound The endothermic peak appearing in phase change and the starting point of the exothermic peak determine the phase change temperature. The phase change is expressed as: crystalline phase labeled C, smectic phase labeled S, nematic phase labeled N, and liquid phase labeled I. The phase change temperature is expressed as "C63N138I", which means that the phase transition temperature (T _C ) from the crystal phase to the nematic phase is 63 ° C, and the phase transition temperature (T _NI ) from the nematic phase to the liquid phase is 138 ° C. For another example, "C107N>250I" means that the phase transition temperature (T _C ) from the crystal phase to the nematic phase is 107 ° C, and the phase transition temperature (T _NI ) from the nematic phase to the liquid phase is greater than 250 ° C (more than the instrument's detection) Measuring range).

(二)向列相的溫度範圍(△T，單位為℃)：將相變化溫度的測量所得的結果，代入以下公式計算：△T=T_NI-T_C，即可得到向列相的溫度範圍，當△T數值越大，表示向列相的溫度範圍越寬廣。 (2) Temperature range of the nematic phase (ΔT, unit is °C): Calculate the result of the phase change temperature and substitute the following formula: △T=T _NI -T _C to obtain the temperature of the nematic phase Range, when the value of ΔT is larger, the wider the temperature range indicating the nematic phase.

(三)光學異向性(△n)：以單方向擦拭主稜鏡的表面，在主稜鏡上滴加少量液晶化合物，於25℃下，使用波長589nm的濾光光片，以目鏡上安裝有偏光板的阿貝折射儀進行測定。當偏光方向與擦拭方向平行時，測定折射率為n ∥；當偏光方向與擦拭方向垂直時，測定折射率為n ⊥。光學異向性(△n)由n ∥與n ⊥的差值而得，以大於、等於0.2為優，小於0.2且大於、等於0.1為佳，以小於0.1為差。 (3) Optical anisotropy (△n): Wipe the surface of the main crucible in a single direction, add a small amount of liquid crystal compound on the main crucible, and use a filter with a wavelength of 589 nm at 25 ° C on the eyepiece. The Abbe refractometer equipped with a polarizing plate was measured. When the polarizing direction is parallel to the wiping direction, the refractive index is measured as n ∥; when the polarizing direction is perpendicular to the wiping direction, the refractive index is measured as n ⊥. The optical anisotropy (Δn) is obtained by the difference between n ∥ and n , , preferably greater than or equal to 0.2, less than 0.2 and greater than or equal to 0.1, and less than 0.1.

液晶化合物之評價結果Evaluation results of liquid crystal compounds

將前述液晶化合物之製備方法中所得到之本發明之液晶化合物(I-1)~液晶化合物(I-4)，以及比較例之液晶化合物(R-1)與液晶化合物(R-2)，進行相變化溫度、向列相的溫度範圍以及光學異向性等測量，並將結果記載於表三。 The liquid crystal compound (I-1) to liquid crystal compound (I-4) of the present invention obtained in the method for producing a liquid crystal compound, and the liquid crystal compound (R-1) of the comparative example and the liquid crystal compound (R-2), The phase change temperature, the temperature range of the nematic phase, and the optical anisotropy were measured, and the results are shown in Table 3.

由表三之結果可知，比較例液晶化合物(R-1)的向列相的溫度範圍狹窄且光學異向性不佳，比較例液晶化合物(R-2)的向列相的溫度範圍雖然寬廣，但光學異向性不佳，而本發明之液晶化合物(I-1)~液晶化合物(I-4)不僅具有優良的光學異向性，且兼具寬廣的向列相的溫度範圍，故有利於擴大應用範圍，此外，本發明之液晶化合物的向列相至液相的相變溫度普遍較高，亦即具有較高的澄清點，其中，液晶化合物(I-4)的向列相的下限溫度為47℃，更有利於低溫儲存。 As is clear from the results of Table 3, the temperature range of the nematic phase of the liquid crystal compound (R-1) of the comparative example was narrow and the optical anisotropy was poor, and the temperature range of the nematic phase of the liquid crystal compound (R-2) of the comparative example was broad. However, the optical anisotropy is not good, and the liquid crystal compound (I-1) to liquid crystal compound (I-4) of the present invention not only has excellent optical anisotropy, but also has a wide temperature range of a nematic phase, so It is advantageous to expand the range of application. Further, the phase transition temperature of the nematic phase to the liquid phase of the liquid crystalline compound of the present invention is generally higher, that is, has a higher clearing point, wherein the nematic phase of the liquid crystal compound (I-4) The lower limit temperature is 47 ° C, which is more conducive to low temperature storage.

液晶組成物之評價方法Method for evaluating liquid crystal composition

(一)由向列相至液相的相變溫度(T_NI，澄清點)：使用差示掃描量熱儀(DSC)系統，將液晶組成物置於鋁盤上精秤0.5mg至40mg，藉由液晶組成物因相變化而出現的吸熱峰及放熱峰的起始點來確定相變化溫度。 (1) Phase transition temperature from the nematic phase to the liquid phase (T _NI , clarification point): Using a differential scanning calorimeter (DSC) system, the liquid crystal composition is placed on an aluminum pan with a scale of 0.5 mg to 40 mg. The phase change temperature is determined from the endothermic peak of the liquid crystal composition due to the phase change and the starting point of the exothermic peak.

(二)介電係數異方性(△ε)：將液晶化合物裝入間隔平均為8μm的TN液晶盒中，於溫度25℃下，對該TN液晶盒施加10V的電壓(1KHz，正弦波)，在平行於液晶分子長軸方向所測得的平均介電常數為ε ∥，垂直於液晶分子長軸所測得的平均介電常數為ε ⊥，介電異方性(△ε)為ε ∥與ε ⊥之間的差值，一般TN型液晶顯示器採用平行配向技術，為了實現低電壓驅動，以大於、等於8為優，小於8且大於、等於3為佳。 (2) Dielectric coefficient anisotropy (Δ ε ): A liquid crystal compound was placed in a TN liquid crystal cell having an average interval of 8 μm, and a voltage of 10 V (1 kHz, sine wave) was applied to the TN liquid crystal cell at a temperature of 25 ° C. The average dielectric constant measured parallel to the long axis of the liquid crystal molecule is ε ∥ , and the average dielectric constant measured perpendicular to the long axis of the liquid crystal molecule is ε ⊥ , and the dielectric anisotropy ( Δ ε ) is ε The difference between ∥ and ε ,, generally TN type liquid crystal display adopts parallel alignment technology, in order to achieve low voltage driving, it is better than greater than, equal to 8, less than 8 and greater than or equal to 3.

(三)光學異向性(△n)：以單方向擦拭主稜鏡的表面，在主稜鏡上滴加少量液晶組成物，於25℃下，使用波長589nm的濾光光片，以目鏡上安裝有偏光板的阿貝折射儀進行測定。當偏光方向與擦拭方向平行時，測定折射率為n ∥；當偏光方向與擦拭方向垂直時，測定折射率為n ⊥。光學異向性(△n)由計算n ∥與n ⊥的差值而得，以大於、等於0.2為優，小於0.2且大於、等於0.1為佳，以小於0.1為差。 (3) Optical anisotropy (△n): Wipe the surface of the main crucible in a single direction, add a small amount of liquid crystal composition on the main crucible, and use a filter with a wavelength of 589 nm at 25 ° C to the eyepiece. The Abbe refractometer on which the polarizing plate was mounted was measured. When the polarizing direction is parallel to the wiping direction, the refractive index is measured as n ∥; when the polarizing direction is perpendicular to the wiping direction, the refractive index is measured as n ⊥. The optical anisotropy (Δn) is obtained by calculating the difference between n ∥ and n , , preferably greater than or equal to 0.2, less than 0.2 and greater than or equal to 0.1, and less than 0.1.

(四)低溫儲存(Low Temperature Storage，LTS，單位為小時)：將0.3mL的液晶組成物置於容量為7mL的樣品瓶中，以-30℃冷藏後析出或固化的時間。 (4) Low Temperature Storage (LTS, in hours): A time when 0.3 mL of the liquid crystal composition was placed in a sample bottle having a capacity of 7 mL and stored at -30 ° C for precipitation or solidification.

液晶組成物之實施例與比較例Embodiments and Comparative Examples of Liquid Crystal Composition

製備實施例1~8的液晶組成物以及比較例1’~6’的液晶組成物。實施例1~8的液晶組成物以及比較例1’~6’的液晶組成物的成份列於表四至表六。 The liquid crystal compositions of Examples 1 to 8 and the liquid crystal compositions of Comparative Examples 1' to 6' were prepared. The compositions of the liquid crystal compositions of Examples 1 to 8 and the liquid crystal compositions of Comparative Examples 1' to 6' are shown in Tables 4 to 6.

將實施例1~8的液晶組成物以及比較例1’~6’的液晶組成物進行由向列相至液相的相變溫度、介電係數異方性、光學異向性、低溫儲存等性質量測，並將結果記錄於表七A與表七B中。 The liquid crystal compositions of Examples 1 to 8 and the liquid crystal compositions of Comparative Examples 1' to 6' were subjected to a phase transition temperature, a dielectric anisotropy, an optical anisotropy, a low temperature storage, and the like from a nematic phase to a liquid phase. The quality was measured and the results were recorded in Tables 7A and 7B.

由實施例1與比較例3’以及實施例3與比較例6’的性質量測結果可知，藉由液晶化合物(I-1)或液晶化合物(I-2)比液晶化合物(R-1)多了一個苯環，除了可提高液晶組成物的光學異向性，及由向列相至液相的相變溫度變高(亦即具有較高澄清點)，並可提升液晶組成物於低溫的儲存能力。 From the results of the qualitative measurement of Example 1 and Comparative Example 3' and Example 3 and Comparative Example 6', it is understood that the liquid crystal compound (I-1) or the liquid crystal compound (I-2) is a liquid crystal compound (R-1). Adding a benzene ring, in addition to improving the optical anisotropy of the liquid crystal composition, and the phase transition temperature from the nematic phase to the liquid phase becomes higher (that is, having a higher clearing point), and the liquid crystal composition can be raised at a low temperature. Storage capacity.

在組成成份較接近的實施例1、實施例2與比較例1’~比較例3’的性質量測結果可知，藉由於液晶組成物中添加本發明之液晶化合物(I-1)或液晶化合物(I-4)，可有效提升向列相組成物於低溫的儲存能力。 It is understood that the liquid crystal compound (I-1) or the liquid crystal compound of the present invention is added to the liquid crystal composition by the measurement results of the properties of the first embodiment, the second embodiment, and the comparative example 1' to the comparative example 3'. (I-4), which can effectively improve the storage capacity of the nematic phase composition at low temperatures.

在組成成份較接近的實施例3與比較例4’~比較例6’的性質量測結果可知，藉由於液晶組成物中添加本發明之液晶化合物(I-2)，除了可提升光學異向性、介電係數異方性、由向列相至液相的相變溫度，並可有效提升向列相組成物於低溫的儲存能力。 In the results of the measurement of the quality of the third embodiment and the comparative example 4' to the comparative example 6' which are relatively close in composition, it is understood that the addition of the liquid crystal compound (I-2) of the present invention to the liquid crystal composition can enhance the optical anisotropy. The anisotropy of the dielectric coefficient, the phase transition temperature from the nematic phase to the liquid phase, and the storage capacity of the nematic phase composition at low temperatures can be effectively improved.

此外，本發明之液晶組成物的由向列相至液相的相變溫度、介電係數異方性、光學異向性、低溫儲存等性質皆為優或佳，當應用於液晶顯示元件，可提升液晶顯示元件的成像品質。 Further, in the liquid crystal composition of the present invention, the phase transition temperature, the dielectric anisotropy, the optical anisotropy, the low temperature storage, and the like from the nematic phase to the liquid phase are excellent or preferable, and when applied to a liquid crystal display element, The image quality of the liquid crystal display element can be improved.

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，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

Claims

一種液晶化合物，其具有如式(I-1)、式(I-2)或式(I-3)所示之一結構： A liquid crystal compound having a structure represented by the formula (I-1), the formula (I-2) or the formula (I-3):

一種液晶組成物，其包含如請求項1所述之液晶化合物。 A liquid crystal composition comprising the liquid crystal compound according to claim 1.

如請求項2所述之液晶組成物，其更包含結構如式(II)、式(III)及式(IV)所示之化合物之至少一者：R³-A⁴-Z⁴-A⁵-R⁴ (II)；R⁵-A⁶-Z⁵-A⁷-Z⁶-A⁸-R⁶ (III)；R⁷-A⁹-Z⁷-A¹⁰-Z⁸-A¹¹-Z⁹-A¹²-R⁸ (IV)；其中，該R³、該R⁵與該R⁷係各自獨立為碳數1至15的烷基或碳數2至15的烯基，該R³、該R⁵與該R⁷中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且該R³、該R⁵ 與該R⁷中任意一個或多個不相鄰的-CH₂-可被-O-、-S-、-CO-、-COO-、-O-CO-或-O-COO-取代；該R⁴、該R⁶與該R⁸係各自獨立為氫、鹵素、碳數1至15的烷基或碳數2至15的烯基，該R⁴、該R⁶與該R⁸中任意一個或多個-H可被-F、-CF₃或-CF₂H取代，且該R⁴、該R⁶與該R⁸中任意一個或多個不相鄰的-CH₂-可被-O-、-S-、-CO-、-COO-、-O-CO-或-O-COO-取代；該A⁴、該A⁵、該A⁶、該A⁷、該A⁸、該A⁹、該A¹⁰、該A¹¹與該A¹²係各自獨立為1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基或2,5-茚滿基，其中該1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且該1,4-伸環己基、該1,4-伸苯基、該1,3-伸環戊基與該2,5-茚滿基中任意一個或多個氫原子係可被氟原子取代；以及該Z⁴、該Z⁵、該Z⁶、該Z⁷、該Z⁸與該Z⁹係各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C₄H₈-、-CF₂-CF₂-、-C=C-、-C≡C-、-CF₂O-、-OCF₂-、-COO-或-O-CO-。 The liquid crystal composition according to claim 2, further comprising at least one of the compounds of the formula (II), the formula (III) and the formula (IV): R ³ -A ⁴ -Z ⁴ -A ⁵ -R ⁴ (II); R ⁵ -A ⁶ -Z ⁵ -A ⁷ -Z ⁶ -A ⁸ -R ⁶ (III); R ⁷ -A ⁹ -Z ⁷ -A ¹⁰ -Z ⁸ -A ¹¹ -Z ⁹ -A ¹² -R ⁸ (IV); wherein R ³ , the R ⁵ and the R ⁷ are each independently an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, the R ³ , Any one or more of the R ⁵ and the R ⁷ may be substituted by -F, -CF ₃ , -CF ₂ H, and the R ³ , the R ⁵ and the R ⁷ are not in phase with any one or more of the R ⁷ The adjacent -CH ₂ - may be substituted by -O-, -S-, -CO-, -COO-, -O-CO- or -O-COO-; the R ⁴ , the R ⁶ and the R ⁸ are each Independently being hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, the R ⁴ , the R ⁶ and any one or more of the R ⁸ may be -F, -CF ₃ or -CF ₂ H substituted, and the R ⁴ , the R ⁶ and any one or more of the R ⁸ non-adjacent -CH ₂ - may be -O-, -S-, -CO-, -COO -, -O-CO- or -O-COO-substituted; the A ⁴ , the A ⁵ , the A ⁶ , the A ⁷ , the A ⁸ , the A ⁹ , the A ¹⁰ , the A ¹¹ and the A ¹² Each is independently 1,4- Cyclohexylene, 1,4-phenylene, 1,3-cyclopentyl or 2,5-extending indanyl, wherein the 1,4-cyclohexylene any one or more non-adjacent -CH ₂ - may be substituted by -O-, and the 1,4-cyclohexylene group, the 1,4-phenylene group, the 1,3-cyclopentyl group and any one or more of the 2,5-indanyl group a hydrogen atom system may be substituted by a fluorine atom; and the Z ⁴ , the Z ⁵ , the Z ⁶ , the Z ⁷ , the Z ⁸ and the Z ⁹ system are each independently a single bond, a double bond, a —CH ₂ O—, _{_{-OCH 2 -, - C 2 H}} 4 -, - C 4 H 8 -, - CF 2 -CF 2 -, - C = C -, - C≡C -, - CF 2 O -, - OCF 2 -, -COO- or -O-CO-.

如請求項3所述之液晶組成物，其包含結構如式(II)、式(III)和式(IV)所示之化合物。 The liquid crystal composition according to claim 3, which comprises a compound represented by the formula (II), the formula (III) and the formula (IV).

如請求項4所述之液晶組成物，基於該液晶組成物的含量為100重量百分比，該液晶組成物包含：0.1重量百分比至10重量百分比的該液晶化合物；5重量百分比至50重量百分比的該式(II)化合物； 15重量百分比至50重量百分比的該式(III)化合物；以及1重量百分比至50重量百分比的該式(IV)化合物。 The liquid crystal composition according to claim 4, wherein the liquid crystal composition contains: 0.1% by weight to 10% by weight of the liquid crystal compound; and 5 parts by weight to 50% by weight based on the liquid crystal composition. a compound of formula (II); 15% by weight to 50% by weight of the compound of the formula (III); and 1% by weight to 50% by weight of the compound of the formula (IV).

如請求項3所述之液晶組成物，其中該R³、該R⁵與該R⁷係各自獨立為碳數1至7的烷基或碳數2至7的烯基，該R³、該R⁵與該R⁷中任意一個或多個-H可被-F、-CF₃、-CF₂H取代，且該R³、該R⁵與該R⁷中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代；該R⁴、該R⁶與該R⁸係各自獨立為氫、鹵素、碳數1至7的烷基或碳數2至7的烯基，該R⁴、該R⁶與該R⁸中任意一個或多個-H可被-F、-CF₃或-CF₂H取代，且該R⁴、該R⁶與該R⁸中任意一個或多個不相鄰的-CH₂-可被-O-、-CO-、-COO-、-O-CO-或-O-COO-取代；該A⁴、該A⁵、該A⁶、該A⁷、該A⁸、該A⁹、該A¹⁰、該A¹¹與該A¹²係各自獨立為1,4-伸環己基、1,4-伸苯基、1,3-伸環戊基或2,5-茚滿基，其中該1,4-伸環己基中任意一個或多個不相鄰的-CH₂-可被-O-取代，且該1,4-伸環己基、該1,4-伸苯基與該2,5-茚滿基中任意一個或多個氫原子係可被氟原子取代；以及該Z⁴、該Z⁵、該Z⁶、該Z⁷、該Z⁸與該Z⁹係各自獨立為單鍵、雙鍵、-CH₂O-、-OCH₂-、-C₂H₄-、-C=C-、-C≡C-、-CF₂O-、-COO-或-O-CO-。 The liquid crystal composition according to claim 3, wherein the R ³ , the R ⁵ and the R ⁷ are each independently an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and the R ³ , Any one or more of R ⁵ and R ⁷ may be substituted by -F, -CF ₃ , -CF ₂ H, and the R ³ , the R ⁵ and any one or more of the R ⁷ are not adjacent -CH ₂ - may be substituted by -O-, -CO-, -COO-, -O-CO- or -O-COO-; the R ⁴ , the R ⁶ and the R ⁸ are each independently hydrogen, halogen An alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, wherein R ⁴ , any one or more of R ⁶ and R ⁸ may be -F, -CF ₃ or -CF ₂ H is substituted, and the R ⁴ , the R ⁶ and the -CH ₂ - which are not adjacent to any one or more of the R ⁸ may be -O-, -CO-, -COO-, -O-CO- or - O-COO-substituted; the A ⁴ , the A ⁵ , the A ⁶ , the A ⁷ , the A ⁸ , the A ⁹ , the A ¹⁰ , the A ¹¹ and the A ¹² are each independently 1,4-stretched Cyclohexyl, 1,4-phenylene, 1,3-cyclopentyl or 2,5-indanyl, wherein any one or more of the 1,4-cyclohexylene groups are not adjacent -CH ₂ - may be substituted by -O-, and the 1,4-cyclohexylene group, the 1,4-phenylene group and the 2,5-indanyl group or Based hydrogen atoms may be substituted with a fluorine atom; and Z ^4, the Z ^5, the Z ^6, the Z ^7, Z ⁸ ₂ O- which the line Z ⁹ are each independently a single bond, double bond, -CH, -OCH ₂ -, -C ₂ H ₄ -, -C=C-, -C≡C-, -CF ₂ O-, -COO- or -O-CO-.

一種液晶顯示元件，包含如請求項2至6中任一項所述之液晶組成物。 A liquid crystal display element comprising the liquid crystal composition according to any one of claims 2 to 6.