TWI250200B - Liquid crystal compounds with optical activities having high helical twisting power, method for preparing the same, and liquid crystal composition containing the compounds - Google Patents

Abstract

The invention relates to the development of the optically active liquid crystal compounds having high helical twisting power. The liquid crystal compounds may be optically active ester derivatives of fluorine, phenanthrene, or dihydrophenanthrene. The method for preparing the liquid crystal compounds includes reacting alcohols with optical activities with acid derivatives of fluorine, phenanthrene, or dihydrophenanthrene to undergo esterification. The liquid crystal compounds possess a larger helical twisting power and highly soluble in nematic host, and the pitch of the liquid crystal compositions possess a lower temperature dependence.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal compound which can be used as a component of a liquid crystal composition, and particularly relates to an optically active high helical twisting force. ° [Prior Art] Reflective biliary liquid crystal display is a new type of display with high brightness, high contrast, power saving, wide viewing angle, no flicker and high reflectivity to reflect different wavelengths and wide viewing angle. The biggest advantage is that it saves energy. The average power consumption only requires a penetrating LCD panel μ 1/5G or less. An e-book made of cholesteric liquid crystal requires power only when turning pages (changing the liquid crystal texture), and it is not necessary to use power when the picture is still. At the same time, the cholesteric liquid crystal has a memory function, and as long as the page is turned to the desired page, the contents of the page can be continuously presented even if the plug or the battery is unplugged. Therefore, it is not suitable for outdoor billboards or handheld electronic products that require power saving. At present, most liquid crystal displays on the market are penetrating, and the liquid crystal display requires a polarizing film, a filter plate, a backlight module, etc., which is not only difficult to manufacture, but also light and thin. The cholesteric liquid crystal does not require a polarizing film and a filter because the liquid crystal molecules themselves have optical characteristics such as optical rotation, selective light scattering, and circular dichroism. At the same time, the cholesterol liquid crystal display is reflective, and it can directly use the ambient light source, and the brightness is high. Even in the outdoor sun, the picture is very clear. 'No need to add the f-light module, the overall reduction can be more than 30% of the liquid crystal display. manufacturing cost. A cholesteric liquid crystal can reflect light waves of a specific wavelength, and in particular, the reflection has a pitch p (the same as the 1250200 of the similar wavelength of the pitching ton) and passes through the other __ direction. The characteristics of the circular apolar light. Generally, the liquid crystal monomer polymerized into a condensed liquid crystal polymer reflects a wave width of about 40 to 50 nm, and the reflected wavelength is insufficient for use in a liquid crystal display. The larger the reflection wavelength, the reflection wavelength needs to cover 400~700 nm, so it is very important to improve the reflection wavelength of the cholesteric liquid crystal polymer to reflect a specific wavelength. According to the Bragg reflection rule, the cholesteric liquid crystal... Hquid crystal) has a relationship between the reflection center wavelength λ, the average refractive index of the film, and the pitch length P (pitch length) of the cholesteric liquid crystal arrangement.

λ = nave χ P The reflected wavelength Δ λ (reflection bandwidth) is related to the optical anisotropy Δ n (bn*efnngence, or birefringence, optical pitch) and the pitch p of the film. The relationship is as follows: Δ λ = Δ η χ Ρ that is, the reflection wavelength is related to the pitch ρ of the liquid crystal molecules and the optical anisotropy Δη, and the cholesteric liquid crystal is a mixture of optically active optically active molecules and non-optically active nematic liquid crystal formulations. The pitch size is controlled by the mixing ratio of the optically active molecule to the non-optically active nematic liquid crystal formulation. The relationship between the pitch of the molecule (Pitch, Ρ) and the nematic liquid crystal mixture can be expressed by the following simple formula: ΗΤΡ = (Ρχς)1 where P is the pitch of the liquid crystal molecules of the cholesterol, and C is the optically active molecule added to the liquid crystal mixture. The weight percent concentration, HTP is the Helical Twisting P0wer 'representing the rotational torsion ability of optically active molecules to make liquid crystal molecules'. The general optically active molecule has HTP < 10/z m_1. German liquid crystal expert H.-G. Kuball proposed in 1995 (c/^所· 5 1250200 2167) the height of helical twisting power (HTP), the type of optically active functional groups, intramolecular The number of chiral centers is closely related to the specfic rotation. In addition to the larger the optically active optical rotation and the greater the number of asymmetric centers, the larger the helical torsion force is, the more the molecules are added. Cyclic functional groups, and their asymmetry, to change their conformation, will also lead to a larger helical twisting force of optically active liquid crystal molecules. How to have a larger optical activity, more optical The number of chiral centers, Helical Twisting Power (HTP), and functional groups having a cyclic structure are introduced into an optically active liquid crystal molecule to improve the reflection wavelength of the cholesteric liquid crystal composition. An important subject of research. On the other hand, due to the special helical structure of optically active high helical torsion liquid crystal molecules, when this optically active liquid crystal molecule Addition to liquid crystal formulations, due to the special helical structure of optically active liquid crystal molecules, especially when the optical activity of high helical twisting force liquid crystal molecules gradually increases in weight (such as greater than l〇wt%), liquid crystal matrix (multilayer nematic) The liquid crystal) has poor solubility for the optically active liquid crystal molecules, so that when the cholesteric liquid crystal composition is formulated, the weight percentage concentration thereof is limited by the configuration of the optically active high helical twisting liquid crystal molecules. Accordingly, it is an object of the present invention to provide an optically active liquid crystal compound which is relatively easy to prepare and purify, and which has a high helical twisting force and a low temperature due to its optically active specific chemical structure. Dependence, very suitable for liquid crystal compositions of liquid crystal displays, especially cholesteric liquid crystal compositions. Another object of the present invention is to provide a method for preparing optically active liquid crystallized 1250200 compounds to obtain the present invention. A liquid crystal compound having an optically active high helical twisting force. A further object of the present invention is to provide a liquid crystal composition which can be used as a liquid crystal composition for a conventional transmissive display (TN, STN, TFT) and a reflective SSCT display. To achieve the above object, the optical device of the present invention A highly active helical twisting liquid crystal compound comprising an optically active organic ester compound as shown in formula (I):

A compound of the formula (1), wherein R1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, wherein the alkyl group The alkenyl group and the alkynyl group may be a linear alkyl group or a branched alkyl group, and R1 may be, for example, a hydrogen atom, -CH3, -C2H5 or -C3H7; R2 is a hydrogen atom or contains 1- The alkyl group of 12 carbon atoms may preferably be a linear alkyl group having 1 to 12 carbon atoms; A1 may be a methylene group, an ethylene group or an ethenylene group; A2 may be R", -OR" or -C02R", wherein R" is an alkyl group having 1 to 12 carbon atoms or a fluorine-containing alkyl group; and A3 may be a stretching group, a phenylene group, Diphenylene, stretched. dense. Pyrimidinediyl, naphthylene or anthrylene, and A3 is preferably methylene, ethylene, propylene, 1,2 _ phenyl, 1,3_phenyl, 1,4-phenyl, 2,2'-biphenyl, 2,3'-extended biphenyl, 2,4'-extended biphenyl , 3,3'-Exbiphenyl, 3,4'-Exbiphenyl, 4,4'-Exbiphenyl, 2,4-Exi-1250200 pyridyl, 2,5-exipyrimidyl, 4 , 5-pyrimidinyl, 4,6-exipyrimidinyl, 1,5-anthranyl, 1,6-anthranyl, 1,7-anthranyl, 1,8-anthranyl, 2,6 - anthranyl, 2,7-anthranyl, 1,5-anthracene, 1,6-extension, 1,7-extension, 1,8-extension, 2,6-extension Sulfhydryl, 2,7-extension base or 9,10-extension base. An optically active high helical twisting liquid crystal compound according to the present invention, wherein the organic ester compound having the structure of the formula (I) has hydrogen on one or more carbon atoms, optionally containing a fluorine atom or It is replaced by i. One of the features of the present invention is that the liquid crystal compound molecule contains a fluorene, a phenanthrene or a dihydrophenanthren ester compound as a core structure of the liquid crystal compound, and the reintroduction has a larger The optical structure of optically active optical rotation and high helical twisting force (HTP) is in a liquid crystal compound to obtain a liquid crystal compound having high helical twisting force and low temperature dependency. Therefore, when the optically active high helical twisting liquid crystal compound and the liquid crystal precursor are mixed into a liquid crystal composition, the probability of hydrogen bonding of the liquid crystal compound and the liquid crystal composition can be lowered, and the overall liquid crystal composition can be further reduced. Viscosity, and effectively promote the reduction of response time. The optically active high helical twisting liquid crystal compound of the present invention can be prepared by a simple chemical method, and a large amount of raw materials are easily obtained. The preparation method comprises the steps of: esterifying an organic acid compound having the formula (II) with an optically active alcohol having the formula (III),

Formula (II) 21250200 A2

R HO-CH- * Formula (III) wherein R, R2, A1, A2 and A3 have the same definitions as the compound (I), and the organic acid compound represented by the formula () is optically substituted with the formula (10). The antimony on the opposite side can be used as a fluorine atom or a cryptoside as needed. The present invention is a poetic composition formula (1) a method for preparing an optically active torsion liquid crystal compound having a reaction equation as shown in the formula (IV):

C〇2H + H〇-CH-a3-r2 *

H20, one of the features of the present invention is the use of a fluorene, phenamhrene or adiphenanthren acid derivative having a liquid crystal core structure and an optically active organic alcohol by a simple compounding step. A high helical twist liquid crystallized mouthpiece having an optically active functional group is obtained. The lipidation reaction step has the advantages that the synthesis process is easy to control, the reactivity is high, and the production 7 is easy to be purified. The lipidation reaction can easily introduce the optically active organic organic material into the liquid crystal molecules to form a desired one. Highly optically active helical torsion liquid crystal compound. The present invention is also directed to a liquid crystal composition of an optically active high helical twist liquid crystal 1250200 compound, characterized by comprising the compound of the above formula (1), the composition of which comprises: (a) at least one of the formula (1) An optically active organic ester compound,

Wherein R is a hydrogen atom, an alkyl group having M2 carbon atoms, a base having 丨_12 carbon atoms, a (tetra) group containing 丨12 carbon atoms, wherein the alkyl group, the alkenyl group and the alkynyl group are It is a linear or branched chain; R is a hydrogen atom or an alkyl group containing 1_丨2 carbon atoms; A is a methylene group, a stretching ethyl group... (3) illusion or ethylene Ethenylene; A2 is R'', _0R, or _c〇2R,, wherein R, is a burnt group containing a carbon atom or a fluorine-containing burn group; and 3 7 A is a stretch Methylene, phenylene, diphenylene, and a mouth. Pyrimidinediy(R), naphthylene or anthrylene, and the organic ester compound having the structure of the formula (1), one or more hydrogens on the carbon, may be fluorine atoms if necessary Or replaced by 13⁄4; and (b) liquid crystal, which is different from component (a). The liquid crystal composition of the optically active high helical twist liquid crystal compound of the present invention, wherein at least one of the components (a) has an optically active helical torsion liquid crystal compound as described in the above formula (), having a higher spiral Torsional force, in some preferred implementations of 12 1250200, its helical torsional force can be more than 46 彡. Therefore, in the case of a cholesteric liquid crystal composition having a reflection wavelength of 500 _nm, the amount of the liquid crystal compound of the component (8) may be added in the range of G lwt% to 3 Qwt%, preferably more preferably in the range of 1 wt% to 20 wt%. And the weight percentage is based on the total weight of the liquid crystal composition. Liquid of optically active high helical twist liquid crystal compound of the present invention

M': It has excellent high-helical twisting force, and its temperature dependence is low, and its address is still good. It can be used as one of the liquid crystal components required for liquid crystal displays. It is suitable for making liquid crystal display devices, especially suitable for Display, super-twist (four) type (STN) display, color) Which talker and thin-film transistor type (TFT) display active high spiral torsion liquid crystal combination:, first = biliary = crystal polarizer, reflector Or a color filter or a color filter. Film formation as a polarizing plate. Further, this day is too bright, and I am using the example of the model.

/ Zhu Yue The method, features and advantages of the invention, the scope of the invention, and the use of the U-face to limit the contents of the invention should be based on the scope of the attached patent. [Embodiment] Synthesis of liquid crystal compound (4) Transistor liquid crystal compound, the details of which are detailed in 1. Test method: Pitch and spiral _ force Η ρ test part: 13 1250200 About measuring the pitch measurement, use Olympus MX50 optical polarizing microscope volume. The measurement method is that the synthesized new optically active molecule is mixed into the ZLI-1132 provided by Merck Company at a concentration of 1 wt%, and is filled into the wedge-shaped liquid crystal cell by capillary action to measure the pitch and standardize. Scale (0.01mm) to determine the unit scale length in the microscope. Remove the standard scale (0.01mm) and place it on the microscope stage. Focus on the eyepiece and measure the distance between the two LCD defect lines to get the pitch. . We can repeat this step to observe the values obtained three times and then average the pitch. The pitch value obtained through the above steps is again brought into the formula HTPsCPxc)·1, and the HTP value can be obtained by conversion. Synthesis of liquid crystal compound: [Example 1] Synthesis of liquid crystal compound 1

(R)-l-phenylethyl fluorene-2-carboxylate 1.5 g (7.14 mmol) of fluorene-2-carboxylic acid and 0.87 g (7.14 mm〇l) under nitrogen system )-(+)-l-phenylethanol ((R)-(+)-l-phenylethanol) was placed in a reaction flask, and 1.62 g (7-85 mmol) of N,N'-dicyclohexylcarbodiimide ( N,N'-dicyclohexyl carbodimide, DCC) and 0_44 g (3.57 mmol) N,N-(dimethyl amino)-pyridine (DMAP) with 200 mL of hexane Methane (CH2C12) was used as a solvent and stirred at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and then filtered, and then filtered, ethyl acetate (EA), and then washed with water and diluted aqueous hydrochloric acid 1250200 2-3 times After removing the water with magnesium sulfate, filtering and drying, and then purifying by column chromatography (ethyl acetate / n-hexane = 1 : 10) to give a white solid 1.24 g, yield 55%. α]=-120.99. Using an optical polarizing microscope to measure the pitch value (pitch length, Ρ) is 8.92 μιη, and then taking the pitch value obtained in the above step into the formula HTP-^Pxc)·1, the helical torsion force HTP = 11.2201^1 can be obtained. . [Example 2] Synthesis of liquid crystal compound 2

(R)-1 -(1 -naphthyl)ethyl fluorene-2-carboxylate 1.70 g (8.09 mmol) of fluorene-2-carboxylic acid and 1.40 g (8.09 mmol) under a nitrogen system (R)-(+)-1-(1-naphthyl)ethyl alcohol ((R)_(+)-l-(l-naphthyl)ethanol) was placed in a reaction flask, and 1.84 g (8.90 mmol) was added. N,N'-dicyclohexylcarbodiimide (DCC) and 0.5 g (4_05 mmol) of N,N-dimethylamino D ratio N (N-N-dimethylamino) -pyridine, DMAP), and stirred with 200 mL of dichloromethane (CH2C12) at room temperature: 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and dilute aqueous hydrochloric acid 2-3 times to sulfuric acid Magnesium was dehydrated, filtered, and dried, then purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to yield white solids, 1.68 g, yield 57%, [α] = -177.07. The 15 1250200 is measured by an optical polarizing microscope with a pitch length (P) of 3.78 μm, and the pitch value obtained in the above step is further brought into the formula HTP=(Pxc)_1 to obtain a helical torsion force ΗΤΡ=26· 46μηι-1. [Example 3] Synthesis of liquid crystal compound 3

(R)-l-(2-naphthyl)ethyl frluorene-2-carboxylate

Under a nitrogen system, 1.75 g (8.32 mmol) of fluorene-2-carboxylic acid and 1.45 g (8.42 111111〇1) (foot) _(+)-1_(2_naphthyl) Base alcohol ((foot)-(+)-1_(2-1^01^]1}4)61:]1&11〇1) placed in the reaction flask, and then added 1.91 g (9.27 mmol) N, N '_N-N-dicyclohexyl carbodimide (DCC) and 0.5 g (4.05 mmol) of N,N-dimethylamino-pyridine DMAP) was scrambled at room temperature for 1 hour with 200 mL of dichloromethane (CH2C12) as solvent. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature. After filtration, the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and diluted aqueous The water was filtered, dried, and purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to yield white solid 1.72 g, yield 57%, [α]=-200 · 34. The pitch length (Ρ) is measured by an optical polarizing microscope of 4·5 Ιμιη, and the pitch value obtained in the above step is further brought into the formula ΗΤΡ2 (Pxc)_1 to obtain the helical twisting force. 16 1250200 [Example 4] Synthesis of liquid crystal compound 4

(R)-l-phenylethyl 9? 10-dihydrophenanthrene-2-carboxylate Under a nitrogen system, 0.5 g (2.23 mmol) of 9,10-dihydrophenanthrene-2-carboxylic acid (9? 10-dihydrophenanthrene-2-carboxylic acid) And 0.27 g (2.21 mmol) of (R)-(+)-l-phenylethanol ((R)-(+)-l-phenylethanol) was placed in a reaction flask, and then 0.47 g (2.28 mmol) of N, N was added. '-N-N-dicyclohexyl carbodimide (DCC) and 0.12 g (0.98 111111〇1)]^,1^_dimethylamino[1°°定(]^,1^ -((^11^11)^1&11^11〇)-port 714 (11116, DMAP), and stirred with 100 mL of dichloromethane (CH2C12) as a solvent at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature. After filtration, the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and diluted aqueous The water was filtered, dried, and purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to afford white solid 46 g, yield 63%, [α] = -104·56. Measuring the pitch value using an optical polarizing microscope (pitch lengt h, Ρ) is 6·54μηι, and the pitch value obtained in the above step is further brought into the formula HTP=(Pxc)-1, and the helical twisting force HTP=15.28011" can be obtained. [Example 5] Synthesis of liquid crystal compound 5 17 1250200

(R)-l-(l-naphthyl)ethyl 9?l〇-dihydrophenanthrene-2-carboxylate Under a nitrogen system, 5 g (2.23 mmol) of 9,10-dihydrophenanthrene-2-carboxylic acid (9, 10-dihydrophenanthrene-2-carboxylic acid) with 0.38 g (2.21 mmol) of (R)-(+)-l-(l-naphthyl)ethyl alcohol ((R)-(+)-l-(l-naphthyl )ethanol) placed in a reaction flask, followed by 〇·5g (2.42 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) and 0.12 g (0.98 111111〇1) )1^,1^-dimethylamino port ratio is determined by (1^,!^-((^11161:]171&111111〇)-0>^(111^, DMAP), and 1〇〇mL Dichloromethane (CH2C12) was used as a solvent and stirred at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA). After extraction, the organic layer was washed with water and a dilute aqueous solution of hydrochloric acid 2-3 times, water was removed with magnesium sulfate, filtered, dried, and then subjected to column chromatography (ethyl acetate / hexane = 1 · · 1 〇) Purification and separation gave 0.44 g of a white solid, yield 52%, [?] = -178.68. The pitch length (Ρ) measured by the optical polarizing microscope is 3.38 μιη. 'The pitch value obtained in the above step is further brought into the formula HTP-^Pxc)-1, and the helical twisting force HTP=29 can be obtained. 6] Synthesis of liquid crystal compound 6 18 1250200

(R)-l-(2-naphthyl)ethyl 9?10-dihydrophenanthrene-2-carboxylate Under a nitrogen system, 0.5 g (2.23 mmol) of 9,10-dihydrophenanthenecarboxylic acid (9,10-dihydrophenanthrene) -2-carboxylic acid) with 0.38 g (2·21 mmol) of (R)-(+)-l-(2-naphthyl)ethyl alcohol ((R)-(+)-l-(2-naphthyl) Ethanol) was placed in a reaction flask, and 0.55 g (2.42 mmol) of N,N,-dicyclohexyl carbodimide (DCC) and 0-12 g (0-98 mmol) N were added. N-dimethylamino-pyridine (DMAP) was stirred at room temperature for 1 hour with 100 mL of dichloromethane (CH2C12) as a solvent. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature. After filtration, the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and diluted aqueous The water was filtered, and then dried and then purified by column chromatography (ethyl acetate / hexane = 1 : 1 〇) to give a white solid, 0.47 g, yield 56%, [α] =- 177·96. Using a optical polarizing microscope to measure the pitch value (pitch length, Ρ) is 3·89 μιη, and then taking the pitch value obtained in the above step into the formula HTP=(Pxc)-1, the helical torsion force HTP= 25.690111-1 can be obtained. . [Example 7] Synthesis of liquid crystal compound 7 19 1250200

(R)-l-phenylethyl 25-ethyl-9?10-dihydro-phenanthrene-2-carboxylate Under a nitrogen system, 0.5 g (1.98111111〇1) 2'-ethyl-9,10-dihydrophenanthrene-2 -2'-ethyl-9,10-dihydrophenanthrene-2-carboxylic acid and 0.24 g (1.98 mmol) of (R)-(+)-1-phenylethanol ((R)-(+)_l-phenylethanol) In the reaction flask, 〇·45 g (2·18 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) and 0.12 g (〇e98 mmol) of N,N were added. N,N-(dimethylamino)-pyridine (DMAP) was stirred with 100 mL of dioxane (CH2C12) as a solvent at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and dilute aqueous hydrochloric acid 2-3 times to sulfuric acid Magnesium was dehydrated, filtered, and dried, then purified by column chromatography (ethyl acetate / hexanes = 1 : 10) to give a white solid, 0.47 g, yield 67%, [α] = -106.19. The pitch length (Ρ) is measured by an optical polarizing microscope (Pitch length, Ρ) is 5·13 μιη, and the pitch value obtained in the above step is further brought into the formula HTP = (Pxc)·1, and the helical torsion force ΗΤΡ二19.48#111 can be obtained. -1. [Example 8] Synthesis of liquid crystal compound 8 20 1250200

(R)-l-(l-naphthyl)ethyl 2,-ethyl-9,10-Dihydro-phenanthrene-2-carboxyat Under a nitrogen system '0.5 g (1.98111111〇1) 2'-ethyl-9,10 - 2'-ethyl-9,10-dihydrophenanthrene-2-carboxylic acid with 0.34 g (1_98 mmol) of (R)_(+) small (1-naphthyl)ethyl alcohol (( R)_(+)-l-(l_naphthyl)ethanol) was placed in the reaction flask, followed by the addition of 〇·45 g (2.18 mmol) of N,N,_dicyclohexylcarbodiimide (N,N,-Dicycl〇) Hexyl carbodimide (DCC) and 0.12 g (〇·98 mmol) of N,N-(dimethylamino)-pyridine (DMAP), and burned with 100 mL of dioxin ( CH^Cl2) was used as a bathing agent' to disturb for 1 hour at the temperature. After the above-mentioned retort is heated and refluxed for 24 hours, the reaction is cooled to room temperature, filtered, and the mash is drained, extracted with ethyl acetate (EA), and then the organic layer is washed 2-3 times with water and a diluted aqueous solution of hydrochloric acid. The water was removed by magnesium sulfate, filtered, and dried, and then purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to give a white solid. [α] = -145.45. The pitch length (Ρ) was measured by an optical polarizing microscope (3, 33 μm), and the pitch value obtained in the above step was again introduced into the formula ΗΤΡ2 (Pxc)-1 to obtain the helical torsion force. [Example 9] Synthesis of liquid crystal compound 9 21 1250200

(R)-l-(2-Naphthyl)ethyl 2?-ethyl-9? 10-Dihydro-phenanthrene-2-carboxylate Under a nitrogen system, 0.5 g (1.98111111〇1) 2'-ethyl-9,10 -2'-ethyl-9,10-dihydrophenanthrene-2-carboxylic acid and 〇·34 g (1.98 mmol) of (R)-(+)-l-(2-naphthyl) Ethyl alcohol ((R)-(+)-l-(2-naphthyl)ethanol) was placed in a reaction flask, and 0.45 g (2_18 mmol) of N,N'-dicyclohexylcarbodiimide (N5N') was added. -Dicyclohexyl carbodimide, DCC) and 0. 12 g (〇.98 mmol) of N,N-dimethylamino-pyridine (DMAP) in 100 mL of dichloromethane (CHWl2) As a solvent, it was stirred at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and dilute aqueous hydrochloric acid 2-3 times to sulfuric acid Magnesium was dehydrated, filtered, and dried, then purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to give white solid (0.49 g, yield 61%, [α] = -180.77. The pitch value (Ρ) is measured by an optical polarizing microscope (Pitch length, Ρ) is 2.87 μηι, and the pitch value obtained in the above step is further brought into the formula ΗΤΡ2 (Pxc)-1 to obtain the helical torsion force Ητρ^^μπΓ1. [Example 10] Synthesis of liquid crystal compound 10 1250200

(R)-phenanthrene-2-carboxylic acid 1 -naphthalen -2-yl-ethyl ester 0.4 g (1.80 mmol) of phenanthrene-2-carboxylic acid and 0.35 under a nitrogen system (2.00 mmol) (R)_(+)_l_(2-naphthyl)ethanol ((R)-(+)_l-(2-naphthyl)ethanol) was placed in a reaction flask, and 0.45 g was added ( 2.18 mmol) N,N'-dicyclohexylcarbodiimide (DCC) and 0.10 g (0.82 mmol) of N,N-dimethylaminopyridine (N,N- (dimethyl amino)-pyridine, DMAP), and 50 mL of dichloromethane (CH2C12) as a solvent, and stirred at room temperature for 1 hour. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and dilute aqueous hydrochloric acid 2-3 times to sulfuric acid Magnesium was dehydrated, filtered, dried, and purified by column chromatography (ethyl acetate / n-hexane = &lt The pitch length (P) was measured by an optical polarizing microscope to be 4.63 μηι, and the pitch value obtained in the above step was further brought into the formula HTP=(Pxc)_1 to obtain a helical torsion force HTP=21.60 μιτΓ1. [Example 11] Synthesis of liquid crystal compound 11 23 1250200

(R)-(-)2?2?2-trifluoro-1-(9-anthryl)ethyl-25-ethyl-9,10-dihydrop henanthrene-2-carboxylate Under a nitrogen system, 0.23 g (0.91111111〇1) 2'_Ethyl-9,10-dihydrophenanthrene-2-carboxylic acid and 0.25 g (0·91 mmol) (R)- (-)- 2,2,2-trifluoro-1-(9-fluorenyl)ethyl alcohol ((R)-(-)-2,2,2-trifluoro-l_(9-anthryl)ethanol) In the reaction flask, 0.45 g (2.18 mmol) of N,N'-Dicyclohexylcarbodiimide (DCC) and 0.10 g (0.82 mmol) of N,N-dimethyl were added. The amino group D was occluded (N, N-(dimethyl amino)-pyridine, DMAP), and stirred at room temperature for 1 hour with 50 mL of dichloromethane (CH2C12) as a solvent. After the reaction flask was heated to reflux for 24 hours, the reaction was cooled to room temperature, filtered, and the filtrate was evaporated to ethyl acetate (EA), and then the organic layer was washed with water and dilute aqueous hydrochloric acid 2-3 times to sulfuric acid Magnesium was dehydrated, filtered, dried, and purified by column chromatography (ethyl acetate / n-hexane = 1 : 10) to afford 0.22 g of white solid. The pitch length (P) was measured by an optical polarizing microscope (Pitch length, P) to be 2.14 μηι, and the pitch value obtained in the above step was further brought into the formula HTP^CPxcV1 to obtain a helical torsion force ΗΤΡ=46·66 μιη-1. The results of the measurement of the pitch value Ρ and the helical torsion force of the liquid crystal compound obtained in accordance with the formula (I) obtained in Examples 1 to 11 are as shown in Table 1 24 1250200: Pitch (P) Spiral torsion force (ΗΤΡ) Liquid crystal compound 1 8.92μηι η.22μπιι Liquid crystal compound 2 4.09μιη 24.46μιη'1 Liquid crystal compound 3 4.51μηη 22.16μηι"1 Liquid crystal compound 4 6.54μιη 15·28μηι-1 Liquid crystal compound 5 3.38μιη 29.55μιη"1 Liquid crystal compound 6 3.89 Μπι 25.69μιη"1 Liquid Crystal Compound 7 5.13μηι ΙΜδμιη-1 Liquid Crystal Compound 8 3.33μιη 30.05μηι"1 Liquid Crystal Compound 9 2.87μηι 34.77μιη'1 Liquid Crystal Compound 10 4.63μπι 21·60μιη] Liquid Crystal Compound 11 2.14μηι 46.66μιη"1 Table 1 New cholesterol liquid crystal formula formulation: We will prepare the liquid crystal compound for further mutual solubility test. The selected liquid crystal is a commercial liquid crystal ZLI-5100-100 or ZLI-5200-100 supplied by Merck as a nematic liquid crystal precursor, and we synthesize liquid crystal compound 5, liquid crystal compound 8 and liquid crystal compound 9 into the blending. The compounding process and results are as shown in the following examples. [Example 12] Liquid crystal composition (A) The liquid crystal compound 5 obtained in Example 5 was mixed into a commercial ZLI-5100-100 nematic liquid crystal precursor supplied by Merck, so that the formulated cholesterol 25 2550200 alcohol liquid crystal formulation was prepared. The reflection wavelength was 568-48 nm, and the relationship between the liquid crystal compound 5 and the ZLI-5100-100 nematic liquid crystal precursor weight concentration ratio was i2 84%. [Example 13] Liquid crystal composition (B) The liquid crystal compound 8 obtained in Example 8 was mixed into a commercial ZLI-5 100-1 〇〇 nematic liquid crystal precursor supplied by Merck, so that the formulated cholesterol liquid crystal formulation was reflected. The wavelength was 568_48 nm, and the relationship between the liquid crystal compound § and the ZLI-5100-100 nematic liquid crystal precursor weight concentration ratio was 丨3 〇〇%. [Example 14] Liquid crystal composition (C) The liquid crystal compound 9 obtained in Example 9 was mixed into a commercial ZLI-5100-100 nematic liquid crystal precursor supplied by Merck Co., Ltd., so that the formulated cholesterol liquid crystal formulation had a reflection wavelength of 588_48 nm. At this time, the relationship between the liquid crystal compound 9 and the ZLI-5100-100 nematic liquid crystal precursor weight concentration ratio was i丨·36%. [Example 15] Liquid crystal composition (D) The liquid crystal compound 11 obtained in Example 11 was mixed into a commercial ZLI-5200-100 nematic liquid crystal precursor supplied by Merck, so that the formulated cholesterol liquid crystal formulation had a reflection wavelength of 552.00. At this time, the relationship between the liquid crystal compound 11 and the ZLI-5200-100 nematic liquid crystal precursor weight concentration ratio was 5.59 Å/〇. [Comparative Example 1] 26 1250200 Liquid crystal composition (D) The liquid crystal compound S-811 (nematic liquid crystal was added by the company 'Merck Co., Ltd., product number s_8ii, HTp value is ^ The knife is inserted into the ZLI_51〇〇_1〇〇 nematic liquid crystal matrix provided by Merck, so that the formulated cholesterol liquid crystal formula reflects at a wavelength of 585.47 nm. At this time, the liquid crystal compounds S_8U and zli_5i〇〇_i〇〇 The relationship between the ratio of the weight of the nematic liquid to the mother's body weight is 34.5% (based on the total weight of the liquid crystal composition). The temperature dependence test was carried out by adding the ratio of the liquid crystal compound obtained in the above Examples 3, 8 and 9 to the commercially available s_8U nematic liquid crystal additive Fwd wt% in zu_5! 〇 (m 〇〇 nematic liquid crystal precursor) And completely miscible, sequentially obtaining liquid crystal compositions e, FG and ruthenium, respectively, by using capillary action to make the above liquid crystal compositions e, F, G and ruthenium filled in a human wedge-shaped liquid crystal cell, and measuring at different temperatures The liquid helium and the pitch of the a objects EF, G, and Η are observed in dependence on the pitch value and the temperature. The results are shown in Fig. 1. As can be seen from Fig. 1, the optical device of the present invention A liquid crystal compound having a high activity of a helical twisting force has a lower temperature dependency than when it is added to a nematic liquid crystal, and a liquid crystal composition suitable for an LCD can be obtained. Compared with the prior art, the invention has the following advantages: The liquid crystal compound of the invention has a high helical twisting force (HTP value can be greater than the above) due to its optically active structure with high optical rotation (partial) invention The liquid crystal compound has a helical twisting force of up to 27 1250200 ΜΠ1 or more, a large super-turning force, a force and a spiral twist of the compound of day and night, and the pitch dependence of the pitch on the temperature is low. In the case of the invention, the anti-left two, in addition, the invention is similar to the η ^ liquid crystal molecules in the molecular material, phenanthrene and phenanthrene. The part of the new optically active molecule is structured to have a low temperature dependence with the nematic liquid crystal. Furthermore, the liquid crystal compound of the present invention is also a very important feature of the present invention. Moreover, since the liquid crystal material of the present invention has a high helical twisting force, the liquid crystal compound can be reduced in the entire liquid helium and the use of the five materials, thereby achieving the effective control of the direction of twisting of the liquid crystal molecules and the requirements of the LCD panel. Further, it is possible to reduce the price of the entire liquid crystal composition and even the panel. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the scope of the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

28 1250200 [Simple description of the drawing] Fig. 1 is a graph showing the dependence of the pitch and temperature of the liquid crystal compositions E, F, G and Η. [Symbol description] No 0

29

Claims (1)

1250200 Pickup, patent application scope: 1. An optically active High Helix Twisting Power (HTP) liquid crystal compound, including optically active as shown in formula (1) R1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, wherein the alkyl group, the alkenyl group and The alkynyl group is linear or branched; R2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; A1 is a methylene group, an ethylene group or an ethylene group. Ethenylene; A2 is R", -OR" or -C02R", wherein R, is a burnt group containing 1 to 12 carbon atoms or a fluorine-containing burnt group; and A is a stretch-base, stretch a phenylene, a diphenylene, a pyrimidinediyl, a napllthylene or an anthrylene, and the organic cool compound having the structure of the formula (1) The hydrogen on one or more carbons may be replaced by a fluorine atom or a halogen as needed. 2. The optically active high helical twisting liquid crystal compound according to claim 1, wherein R1 is hydrogen Atom, _CH3, -C2H5 or -C3H7 ο 3·The optically active high-spiral twist as described in claim 1 A liquid crystal compound wherein R 2 is a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms of 30 1250200. 4. The optically active high helical twisting liquid crystal compound as described in the scope of claim 2, Wherein A3 is a methylene, an ethylene or a pr〇pylene. The soil 5 has an optically active high helical torsion force as described in the scope of the patent application. a liquid crystal compound, wherein the A3 is a u-extension base, a u-phenylene group or an M-phenylene group. 6. The optically active high helical twisting liquid crystal compound according to the invention of claim 2, wherein A3 is 2, 2, biphenyl, 2,3,_biphenyl, 2,4'-biphenyl, 3,3,_biphenyl, 3,4,_diphenyl Or a 4,4, biphenyl group. 7. The optically active high helical twisting liquid crystal compound according to claim 1, wherein the A3 is 2,4-pyrimidinyl, 2, Pyrimidine group, 4,5-extended pyrimidinyl group or 4,6-extended pyrimidinyl group. 8. Optically active high helical twisting liquid crystal as described in the scope of claim 2 a compound wherein the A3 is 1,5-anthranyl, anthracene, 6-naphthyl, anthracene, 7-naphthyl, 1,8-naphthyl, 2,6-anthranyl or 2,7-extension Naphthyl. 9. The optically active high helical twisting liquid crystal compound according to claim 1, wherein the A3 is 丨, 5 蒽 蒽, 丨, 6 蒽 蒽, 丨, 7 · Stretching base, 1,8-stretching base, 2,6_stretching base, 2,7_stretching base or 9,1〇_stretching ^ ° ~ 10 · as claimed in item 1 The liquid crystal compound having an optically active high helical twisting force has a helical twisting force of not less than 1. η· A method for preparing an optically active high helical twist liquid crystal compound, comprising the steps of: an organic acid compound having the formula (π) and an optically active alcohol having 31 1250200 represented by the formula (111) Esterification reaction, * Formula (III) Wherein R is a hydrogen atom, a stilbene group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having a U2 carbon atom, wherein the alkyl group, an alkyl group and an alkyl group are burned. The fast-based system is linear or branched; R2 is a hydrogen atom or a burnt group containing 1 to 12 carbon atoms; A1 is a methyiene, ethyl (ethylen illusion or vinyl) (ethenylene); A2 is R", -OR" or -C〇2R", wherein R, is an alkyl group containing a carbon atom or a fluorine-containing alkyl group; A3 is a methyl group, a phenylene group, a diphenylene group, a pyrimidinediyi group, a naPhthylene group or an anthrylene group, and the The organic acid compound represented by the formula and the hydrogen having one or more carbons of the optically active alcohol represented by the formula (111) may be optionally substituted by a fluorine atom or a letter. '' 12. A method for preparing an optically active rhombohedral twisted liquid crystal compound as described in the scope of claim 5, R 1 Sun - ° 八丁你马氧原子, _CH3, 32 1250200 -C2H5 or It is _c3H7. η·如巾 The high optical activity of the preparation described in item n of the patent range: : Method for ugly liquid crystal compound' wherein r2 is a hydrogen atom or a linear alkyl group having 1 to 12 deuterium atoms. The method for preparing an optically active "high-twisting liquid crystal compound" as described in the patent scope of the invention, wherein the t A3 system is methyl methene, the ethyl group (10) is (four) or the propyl group is extended. (Shuai is called. 15. If you want to prepare an optically active high-power liquid crystal compound, the A3 system is 1,2_phenylene, 1,3_ stretching base or It is a K-phenylene group. 16. A method for preparing an optically active liquid 2 compound, wherein the a3 system is 2, 2, a biphenyl group, and a: Biphenyl, 2,4,-biphenyl, 3,3,_biphenyl or 4,4, biphenyl. The highest activity of the preparation activity described in item U of the patent scope: A method for transducing a liquid crystal compound, wherein the a3 is 2,4 heptyl, 'extended pyridine, 4,5-exipyrimidyl or 4,6-exipyrimidinyl. Spirulina as claimed in the patent (4) U A method for preparing an optically active high-stretching liquid crystal compound, wherein the A3 is 1,5-anthranyl, 1,6-, 7-naphthyl, l8·naphthyl, 2,6-anthranyl Or 2,7-stretching naphthyl. 蝉η Μ如U利*围The preparation of the item U has an optically active high == night crystal method, wherein the eight 3 series is 1,5_the onion base, and the W is the 9 1 soil 〇#二伸恩基,1,8_伸蒽 base , 2,6_extension base, 2,7·extension base or 疋9,1〇_extension base. 2〇·-liquid crystal composition, comprising: (4) at least as shown in formula (1) The optically active (10) compound 33 1250200, R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkylene group having 1 to 12 stone anions, and an alkynyl group having 1 to 12 carbon atoms, wherein the alkyl group and the alkylene group And alkynyl groups are linear or branched; R2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; A is a methylene group, an ethylene group or an ethenylene; A2 is R,, and -OR , or /0〇2ΪΙ,,, wherein R, is an alkyl group or a fluorine-containing alkyl group having M2 carbon atoms; The A system is a methylene, a phenylene, a diphenylene, a pyrimidinediyl, a naphthylene or an anthrylene, and An organic ester compound having the formula (I), wherein one or more hydrogens on the carbon may be substituted by a fluorine atom or an imine; and (b) a liquid crystal, and the component (a) different. The liquid crystal composition according to claim 2, wherein Ri is a hydrogen atom, _CH3, -C2H5 or -C3H7. The liquid crystal composition according to claim 20, wherein R2 is a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms. The liquid crystal composition according to claim 20, wherein the A3 is a methyl group, an ethylene group or a propyl group 34 1250200 (propylene) 〇 24 · as claimed The liquid crystal composition according to Item 2, wherein A3 is hydrazine, 2-extended base, 1,3-phenylene or 1,4-phenylene. The liquid crystal composition according to claim 20, wherein A3 is 2, 2, biphenyl, 2,3, -biphenyl, 2,4,-diphenyl, 3 , 3, - biphenyl, 3, 4, - biphenyl or 4, 4, _ biphenyl. The liquid crystal composition according to claim 20, wherein the A3 is 2,4_stretched. A dense sigma group, a 2,5-an extended pyrimidinyl group, a 4,5-extended pyrimidinyl group or a 4,6-extended pyrimidinyl group. The liquid crystal composition according to claim 20, wherein Α3 is f丨,5·anthranyl, anthracene, 6-anthranyl, 1,7-anthranyl, 1,8-extension Naphthyl, 2,6. anthranyl or 2,7-anthranyl. The liquid crystal composition of claim 2, wherein A3 is 丨,5, fluorenyl, fluorene, 6-extension, 1,7-extension, 1,8- Extrusion base, 2,6-extension base, 2,7_extension base or 9,1〇_extension base. The liquid crystal composition according to claim 20, wherein the nightingale is a twisted nematic (TN) liquid crystal, a super twisted nematic (STN) liquid crystal, and a color super twisted nematic (SSTN) Liquid crystal or thin film transistor type (tft) liquid crystal. A liquid crystal composition which can be formed on a polarizing plate or a color light-receiving sheet, and an optically active organic ester compound represented by the formula (I): Wherein R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 丨-; 35 1250200 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, wherein the alkyl group, Alkenyl and alkynyl are linear or branched; R2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; A1 is a methylene group and an ethylene group. Or ethenylene; A2 is R", -OR" or -C02R", where R" is a burning group containing 1-12 carbon atoms; and A3 is stretching:!: complete , phenylene, diphenylene, pyrimidinediyl, naphthylene or anthrylene, and having the structure of formula (I) The organic ester compound may have a hydrogen on one or more carbons, optionally substituted by a fluorine atom or a halogen. 36