Compound containing phenanthrene structure, positive dielectric anisotropy liquid crystal composition containing phenanthrene compound and application of positive dielectric anisotropy liquid crystal composition

Abstract

The invention relates to a compound containing a phenanthrene structure, a positive dielectric anisotropy liquid crystal composition containing the phenanthrene compound and application of the positive dielectric anisotropy liquid crystal composition. The structure of the compound is shown in the formula I. The compound has high vertical dielectricity, the transmittance of the liquid crystal composition can be improved, the compound has low rotary viscosity and a large elastic coefficient, and the positive dielectric anisotropy liquid crystal composition can be applied to liquid crystal display devices. The response speed of the liquid crystal composition is favorably improved, and the liquid crystal composition has relatively high clearing point and optical anisotropy. The invention also provides a positive dielectric anisotropy liquid crystal composition containing the phenanthrene structure compound, and the liquid crystal composition has the characteristics of high transmittance, small rotary viscosity and fast response speed, has good high temperature resistance and ultraviolet irradiation resistance, and has strong stability under long-time high-brightness illumination. The liquid crystal composition is especially suitable for being used in the field of televisions. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of liquid crystal display technology, and more specifically to a compound containing a phenanthrene structure, a positive dielectric anisotropic liquid crystal composition containing the phenanthrene compound, and applications thereof in the field of liquid crystal display. Background Art

[0002] TFT-LCD (Thin Film Transistor Liquid Crystal Display) is the most mature technology in the field of flat panel display, and is widely used in display fields such as mobile phones, tablet computers, laptops, car displays, industrial control displays, and televisions. AMOLED (Active Matrix Organic Light Emitting Diode) display technology has also been continuously developing in recent years. With its high brightness, high contrast, bendability and flexibility, it has been widely used in small-size display devices such as smart phones and smart wearable devices, gradually replacing the application of TFT-LCD in small-size display devices. However, due to the technical difficulties such as service life and reliability of AMOLED technology, medium and large-size display devices such as computer monitors, car displays, and televisions are still dominated by TFT-LCD display devices. In order to compete with AMOLED, it is very important to improve the brightness, contrast and other performance of TFT-LCD display devices.

[0003] LCD display devices are divided into positive dielectric anisotropy and negative dielectric anisotropy according to the dielectric anisotropy of liquid crystal materials. The dielectric anisotropy is greater than zero for positive dielectric anisotropy, and the dielectric anisotropy is less than zero for negative dielectric anisotropy. In recent years, both negative dielectric anisotropy liquid crystal display materials and negative dielectric anisotropy liquid crystal display modes have become the research focus in the field of liquid crystal material technology. However, due to the inherent characteristics of negative dielectric anisotropy liquid crystal materials, negative dielectric anisotropy liquid crystal materials have slow response speed and poor reliability compared to positive dielectric anisotropy liquid crystal materials, and there is a higher risk of residual image defects. Therefore, in the field of television display, which has increasingly stringent requirements on response speed and residual image, positive dielectric anisotropy liquid crystal materials still have certain advantages and are a topic worthy of continuous research.

[0004] At present, high-resolution display screens have to face the problem of reduced panel aperture ratio, which leads to reduced display screen brightness. In order to obtain higher display brightness, it can be solved by increasing the brightness of the backlight or increasing the transmittance of the liquid crystal material. Mini LED backlight brightness is very high, and the brightness of a 4K resolution display screen is 1800nit. This requires that the liquid crystal material is not easy to age under long-term exposure to high-brightness backlight. However, the backlight is the component with the highest energy consumption in the TV. If the backlight can be used effectively, it can not only effectively save energy, but also increase the brightness of the display screen. Solving the problem of low display brightness and low contrast caused by reduced aperture ratio by increasing the transmittance of liquid crystal materials has become a two-pronged approach.

[0005] Therefore, developing a compound that can simultaneously improve the response speed and transmittance of liquid crystal materials is an urgent problem to be solved. Summary of the invention

[0006] In order to solve one or more of the above technical defects, the present invention provides a compound containing a phenanthrene structure, which has a higher vertical dielectric constant, is beneficial to improving the transmittance of the liquid crystal composition, and has a lower rotational viscosity and a larger elastic coefficient, which is beneficial to improving the response speed of the liquid crystal composition, and also has a higher clearing point and optical anisotropy. The present invention also provides a positive dielectric anisotropic liquid crystal composition containing the phenanthrene structure compound, which has the characteristics of high transmittance, low rotational viscosity, and fast response speed, and has good resistance to high temperature and ultraviolet light, and has strong stability under long-term high-brightness light. The liquid crystal composition is particularly suitable for use in the field of television.

[0007] In order to achieve the above-mentioned beneficial technical effects, the present invention provides a compound containing a phenanthrene structure, wherein the above-mentioned compound is as shown in Formula I,

[0008]

[0009] in,

[0010] R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0011] R 2 represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms;

[0012] Z 1 Represents a single bond, -CH 2 -、-CH2 CH 2 -、-CH 2 O-;

[0013] express

[0014] The second object of the present invention is to provide a liquid crystal composition with positive dielectric anisotropy containing a phenanthrene structure compound, wherein the liquid crystal composition comprises one or more compounds of formula I and one or more compounds of formula II.

[0015]

[0016] in,

[0017] R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0018] R 2 represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms;

[0019] Z 1 Represents a single bond, -CH 2 -、-CH 2 CH 2 -、-CH 2 O-;

[0020] express

[0021] R 3 represents a chain alkyl group having 1 to 10 carbon atoms, and R 3 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0022] R 4 Indicates H or CH3;

[0023] express

[0024] express

[0025] The third object of the present invention is to provide a liquid crystal display element / liquid crystal display, which is mainly an active matrix display mode.

[0026] Effects of the Invention

[0027] The present invention provides a compound containing a phenanthrene structure, which has a high vertical dielectric constant, is beneficial to improving the transmittance of a liquid crystal composition, has a low rotational viscosity and a large elastic coefficient, is beneficial to improving the response speed of the liquid crystal composition, and also has a high clearing point and optical anisotropy. The present invention also provides a positive dielectric anisotropic liquid crystal composition containing the phenanthrene structure compound, which has the characteristics of high transmittance, low rotational viscosity, and fast response speed, and has good resistance to high temperature and ultraviolet light, and has strong stability under long-term high-brightness light. The liquid crystal composition is particularly suitable for use in the field of television. A liquid crystal display containing the compound or liquid crystal composition has the characteristics of high brightness, high contrast, fast response speed, no residual image, low energy consumption, and long service life. DETAILED DESCRIPTION

[0028] The present invention provides a compound containing a phenanthrene structure, wherein the compound is as shown in Formula I.

[0029]

[0030] in,

[0031] R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0032] R 2 represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms;

[0033] Z 1 Represents a single bond, -CH 2 -、-CH 2 CH 2 -、-CH 2 O-;

[0034] express

[0035] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-1 to I-5.

[0036]

[0037] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-1-1 to I-1-9.

[0038]

[0039]

[0040] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-2-1 to I-2-8.

[0041]

[0042]

[0043] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-3-1 to I-3-8.

[0044]

[0045]

[0046] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-4-1 to I-4-8.

[0047]

[0048] The liquid crystal compound of the present invention is preferably selected from the group consisting of compounds represented by the following formulas I-5-1 to I-5-8.

[0049]

[0050] The present invention provides a liquid crystal composition, which comprises one or more compounds represented by formula I and one or more compounds represented by formula II.

[0051]

[0052] in,

[0053] R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0054] R 2represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms;

[0055] Z 1 Represents a single bond, -CH 2 -、-CH 2 CH 2 -、-CH 2 O-;

[0056] express

[0057] R 3 represents a chain alkyl group having 1 to 10 carbon atoms, and R 3 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0058] R 4 Indicates H or CH 3 ;

[0059] express

[0060] express

[0061] The liquid crystal composition of the present invention is preferably a compound represented by the above formula I, R 1 represents a chain alkyl group having 1 to 10 carbon atoms; R 2 It represents an alkoxy group having 1 to 10 carbon atoms.

[0062] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula I is selected from the group consisting of the compounds represented by the following formulas I-1 to I-5,

[0063]

[0064]

[0065] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the above formula I is 5-20%.

[0066] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of compounds represented by the following formulas II-1 to II-28,

[0067]

[0068]

[0069]

[0070] Among them, R 3 It represents an alkyl group having 1 to 5 carbon atoms.

[0071] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the aforementioned formula II is 5-15%.

[0072] The liquid crystal composition of the present invention, preferably, further comprises one or more compounds represented by formula III,

[0073]

[0074] in,

[0075] R 5 , R 6 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

[0076] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula III is selected from the group consisting of compounds represented by the following formulae III-1 to III-12,

[0077]

[0078] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the aforementioned formula III is 45-55%.

[0079] The liquid crystal composition of the present invention, preferably, further comprises one or more compounds represented by formula IV,

[0080]

[0081] in,

[0082] R 7 , R 8 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms;

[0083] express

[0084] Z 2 Represents a single bond or -CH 2 CH 2 -;

[0085] p represents 1 or 2; when p represents 2, Can be the same or different.

[0086] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV is selected from the group consisting of compounds represented by the following formulae IV-1 to IV-7,

[0087]

[0088] in,

[0089] R 7 , R 8 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

[0090] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the aforementioned formula IV is 5-20%.

[0091] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-1 is selected from the group consisting of compounds represented by the following formulae IV-1-1 to IV-1-9,

[0092]

[0093] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-2 is selected from the group consisting of compounds represented by the following formulae IV-2-1 to IV-2-15,

[0094]

[0095] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-3 is selected from the group consisting of compounds represented by the following formulae IV-3-1 to IV-3-16,

[0096]

[0097]

[0098] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-4 is selected from the group consisting of compounds represented by the following formulae IV-4-1 to IV-4-16,

[0099]

[0100] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-5 is selected from the group consisting of compounds represented by the following formulae IV-5-1 to IV-5-16,

[0101]

[0102] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-6 is selected from the group consisting of compounds represented by the following formulae IV-6-1 to IV-6-11,

[0103]

[0104]

[0105] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula IV-7 is selected from the group consisting of compounds represented by the following formulae IV-7-1 to IV-7-8,

[0106]

[0107] The liquid crystal composition of the present invention, preferably, further comprises one or more compounds represented by formula V,

[0108]

[0109] in,

[0110] R 9 , R 10 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;

[0111] express

[0112] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula V is selected from the group consisting of the compounds represented by the following formulas V-1 to V-2,

[0113]

[0114] in,

[0115] R 9 , R 10 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0116] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula V-1 is selected from the group consisting of the compounds represented by the following formulas V-1-1 to V-1-7,

[0117]

[0118] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula V-2 is selected from the group consisting of the compounds represented by the following formulas V-2-1 to V-2-10,

[0119]

[0120] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the aforementioned formula V is 1-25%.

[0121] The liquid crystal composition of the present invention, preferably, further comprises one or more compounds represented by formula VI,

[0122]

[0123] in,

[0124] R 11 represents a chain alkyl group having 1 to 10 carbon atoms, and R 11 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene;

[0125] Z 3 Represents a single bond or -CH 2 CH 2 -;

[0126] q represents 0 or 1.

[0127] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula VI is selected from the group consisting of compounds represented by the following formulae VI-1 to VI-3,

[0128]

[0129] in,

[0130] R 11 It represents a chain alkyl group having 1 to 10 carbon atoms.

[0131] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the above formula VI is 1-10%.

[0132] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula VI-1 is selected from the group consisting of compounds represented by the following formulae VI-1-1 to VI-1-4,

[0133]

[0134] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula VI-2 is selected from the group consisting of compounds represented by the following formulae VI-2-1 to VI-2-4,

[0135]

[0136] The liquid crystal composition of the present invention, preferably, the compound represented by formula VI-2 in the aforementioned liquid crystal composition is selected from the group consisting of compounds represented by the following formulae VI-3-1 to VI-3-8,

[0137]

[0138] The liquid crystal composition of the present invention, preferably, further comprises one or more compounds represented by formula VII,

[0139]

[0140] in,

[0141] R 12 represents a chain alkyl group having 1 to 10 carbon atoms, and R 12 Any of -CH 2 -optionally substituted by cyclopropylene or cyclopentylene.

[0142] In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula VII is selected from the group consisting of compounds represented by the following formulae VII-1 to VII-19,

[0143]

[0144] In the liquid crystal composition of the present invention, preferably, the mass content of the compound represented by the above formula VII is 0.1-1%.

[0145] The liquid crystal composition of the present invention, preferably, further comprises one or more polymerizable compounds.

[0146] In the liquid crystal composition of the present invention, preferably, dopants with various functions may be added to the aforementioned liquid crystal compound.

[0147] In the liquid crystal composition of the present invention, preferably, the aforementioned dopant is mainly an antioxidant, an ultraviolet absorber, a chiral agent, and the like.

[0148] Antioxidants include,

[0149]

[0150] Here, t represents an integer from 1 to 10.

[0151] Examples of the ultraviolet absorber include:

[0152]

[0153] Preferred chiral agents (levorotatory or dextrorotatory) include, for example:

[0154]

[0155]

[0156] In the liquid crystal composition of the present invention, preferably, the mass percentage content of the aforementioned dopant is preferably between 0.01-1%.

[0157] [Liquid crystal display element or liquid crystal display]

[0158] The present invention also relates to a liquid crystal display element or a liquid crystal display comprising any one of the above liquid crystal compositions; the display element or the display is an active matrix display element or the display.

[0159] Furthermore, the liquid crystal display element or liquid crystal display is a TV with Mini LED backlight.

[0160] The aforementioned active matrix display element or display may specifically include, for example, IPS-TFT or FFS-TFT liquid crystal display elements or other TFT displays, and is particularly suitable for IPS-TFT mode liquid crystal display elements or liquid crystal displays.

[0161] The liquid crystal display element or liquid crystal display of the present invention comprises the liquid crystal composition disclosed in the present invention, and is very suitable for use in television displays. It has the characteristics of high brightness, high contrast, fast response speed, no afterimage, low energy consumption, and long service life. It is very suitable for preparing 65-inch to 100-inch television displays with a resolution of 4K or 8K and a Mini LED backlight.

[0162] Example

[0163] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0164] In the present invention, the preparation methods are conventional methods unless otherwise specified, the raw materials used are all available from public commercial channels unless otherwise specified, the percentages are all mass percentages, the temperatures are in degrees Celsius (°C), and the specific meanings of other symbols and test conditions are as follows:

[0165] Tni represents the clearing point of liquid crystal (℃), measured by DSC quantitative method;

[0166] Δn represents optical anisotropy, Δn = n e -n o , where n o is the refractive index of ordinary light, n e It is the refractive index of extraordinary light, tested under two conditions: 25±2℃ and 60±2℃, 589nm, and Abbe refractometer.

[0167] Δε represents dielectric anisotropy, Δε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥is the dielectric constant perpendicular to the molecular axis, the test conditions are 25±0.5℃, 20 μm antiparallel box, INSTEC:ALCT-IR1 test;

[0168] γ 1 It represents the rotational viscosity (mPa·s), the test conditions are 25±0.5℃, 20 micron vertical box, INSTEC: ALCT-IR1 test;

[0169] K 11 is the splay elastic constant, K 33 is the bending elastic constant, the test conditions are: 25 °C, INSTEC:ALCT-IR1, 20 μm antiparallel box;

[0170] VHR stands for voltage holding ratio (%), and the test conditions are 60±2℃, voltage ±5V, pulse width 10ms, and voltage holding time 16.7ms. The test equipment is TOYO Model 6254 LCD performance comprehensive tester;

[0171] Afterimage: The afterimage of a liquid crystal display device is evaluated by visually observing the residual level of the inherent pattern when the entire screen is uniformly displayed after displaying a specified fixed pattern in the display area for 1000 hours, and the following 4 levels are used:

[0172] ◎No residue

[0173] ○There is a very small amount of residue, which is an acceptable level

[0174] △ There is residue, which is an unacceptable level

[0175] ×There is residue, which is quite bad.

[0176] The preparation method of the liquid crystal composition is as follows: each liquid crystal monomer is weighed according to a certain ratio and put into a stainless steel beaker, and the stainless steel beaker containing each liquid crystal monomer is placed on a magnetic stirring instrument to heat and melt. After most of the liquid crystal monomers in the stainless steel beaker are melted, a magnetic rotor is added to the stainless steel beaker, and the mixture is stirred evenly. After cooling to room temperature, the liquid crystal composition is obtained.

[0177] The liquid crystal monomer structure of the embodiment of the present invention is represented by a code, and the code representation method of the liquid crystal ring structure, end group, and connecting group is shown in Table 1 and Table 2 below.

[0178] Table 1 Corresponding codes of ring structure

[0179]

[0180]

[0181] Table 2 Corresponding codes of terminal groups and linking groups

[0182]

[0183] Example:

[0184] Its code is L-Phe-3-OT; Its code is D-Phe-3-OT;

[0185] Its code is CC-3-V;

[0186] Its code is PUQU-3-F;

[0187] Its code is PGUQK-3-F; Its code is APUQU-Cp-F; Its code is DPUQU-3-F; Its code is DGUQK-2-F; Its code is CY-3-O4;

[0188] Its code is CCY-3-O2;

[0189] Its code is CPY-4-O2;

[0190] Its code is CCP-V-1;

[0191] Its code is CPP-1V-2;

[0192] Its code is PPGU-Cp-F;

[0193] Its code is CDEPU-3-F.

[0194] The present invention is described below using the following specific embodiments:

[0195] Synthesis Examples of Compounds

[0196] 1. Z 1 represents a single bond, express The synthetic route of the compound is as follows:

[0197]

[0198] Z 1 Indicates -CH 2 CH 2 -, express The synthetic route of the compound is as follows:

[0199]

[0200] 2. Z 1 Indicates -CH 2 O-, express The synthetic route of the compound is as follows:

[0201]

[0202] 3. Z 1 represents a single bond, express The synthetic route of the compound is as follows:

[0203]

[0204] 4. Z 1 Indicates -CH 2 CH 2 -, express The synthetic route of the compound is as follows:

[0205]

[0206] The present invention is further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. The raw materials described can be obtained from public commercial channels unless otherwise specified.

[0207] The progress of the reaction is generally monitored by TLC. The post-treatment after the reaction is generally washing with water, extraction, drying after combining the organic phases, removing the solvent under reduced pressure, and recrystallization and column chromatography. Those skilled in the art can implement the present invention according to the following description.

[0208] Example 1

[0209] This embodiment provides a liquid crystal compound I-1-2, whose structural formula is as follows:

[0210]

[0211] The synthetic route of the compound is as follows:

[0212]

[0213] Step (1)

[0214] Dissolve 2-fluoro-4-chlorobromobenzene (20 g, 0.095 mol) in 60 mL tetrahydrofuran to obtain 2-fluoro-4-chlorobromobenzene tetrahydrofuran solution; dissolve propylcyclohexanone (12 g, 0.86 mol) in 25 mL tetrahydrofuran to obtain propylcyclohexanone tetrahydrofuran solution; put magnesium chips (2.52 g, 0.11 mol) into a 250 mL three-necked flask, add 2-fluoro-4-chlorobromobenzene tetrahydrofuran solution dropwise to initiate Grignard reaction, continue to add dropwise until 2-fluoro-4-chlorobromobenzene tetrahydrofuran solution is added dropwise, reflux for 1 hour, then add propylcyclohexanone tetrahydrofuran solution dropwise, reflux for 1 hour after addition is completed, cool naturally, and pour the reaction solution into 50 mL The mixture was extracted three times with 25 mL of ethyl acetate in 1 mol / L hydrochloric acid, and the organic phases were combined, washed with 50 mL of saturated brine, dried over anhydrous sodium sulfate for 2 h, and concentrated to obtain intermediate 1 (20 g, 0.074 mol) as a yellow oil with a yield of 86.1%.

[0215] Step (2)

[0216] In a 250 mL three-necked flask, intermediate 1 (20 g, 0.074 mol), 200 mL toluene and p-toluenesulfonic acid (2 g) were added, water was separated by a water separator, refluxed for 2 h, cooled, 200 mL of water was added to the reaction solution, washed with water, separated, the organic phase was passed through a column, concentrated to obtain a crude intermediate 2, and recrystallized from ethanol to obtain a white solid intermediate 2 (18 g, 0.069 mol), with a yield of 93.7%;

[0217] Step (3)

[0218] Add intermediate 2 (18 g, 0.069 mol), 3-fluoro-4-trifluoromethoxyphenylboronic acid (15.5 g, 0.069 mol), anhydrous potassium carbonate (12 g, 0.083 mol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.35 mmol) and 200 mL toluene to a 250 mL three-necked flask, reflux for 4 h, cool to room temperature, add 200 mL of water, wash with water, flush the organic phase into the column, concentrate to obtain the crude intermediate 3, slurry with ethanol, and filter to obtain the white solid intermediate 3 (24 g, 0.061 mol), with a yield of 87.4%;.

[0219] Step (4)

[0220] To a 500mL three-necked flask, add intermediate 3 (24g, 0.061mol) and 150mL tetrahydrofuran, cool the solution to -78°C, slowly add n-butyllithium (53mL, 0.13mol), control the temperature and react for 1h, add DMF (11g, 0.15mol), control the temperature and react for 1h, raise the temperature to -20°C, add 100mL water, extract three times with 150mL ethyl acetate, wash with 250mL saturated brine, dry with anhydrous sodium sulfate for 2h, concentrate to obtain a yellow oil, slurry with petroleum ether, and filter to obtain a yellow solid intermediate 4 (17g, 0.038mol) with a yield of 62.1%.

[0221] Step (5)

[0222] Dissolve 80% hydrazine hydrate (5.9 g, 0.094 mol) in 25 mL of glacial acetic acid to obtain a glacial acetic acid solution of hydrazine hydrate; add intermediate 4 (17 g, 0.038 mol) and 200 mL of glacial acetic acid into a 250 mL three-necked flask, heat to reflux, slowly add dropwise the glacial acetic acid solution of hydrazine hydrate, after the dropwise addition, reflux for 5 h, cool, filter to obtain a yellow solid, and use toluene and ethanol to recrystallize to obtain a white solid compound I-1-2 (11 g, 0.026 mol), with a yield of 69.9%, MS (m / z) (M+): 420.15.

[0223] Example 2

[0224] This embodiment provides a liquid crystal compound I-1-5, whose structural formula is as follows:

[0225]

[0226] The synthetic route of the compound is as follows:

[0227]

[0228] The synthesis method of step (1) to step (5) is the same as that of compound Example 1, except that 3-fluoro-4-trifluoromethoxyphenylboronic acid is replaced by 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid to obtain intermediate 5 (8.6 g, 0.02 mol) with a yield of 61.5%;

[0229] Step (6)

[0230] The intermediate 5 (8.6 g, 0.02 mol) was dissolved in 100 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate 5; diisopropylamine (6 g, 0.06 mol) was added to a 500 mL three-necked flask, the temperature was lowered to -20°C, n-butyl lithium (24 mL, 0.06 mol) was added dropwise, the reaction was kept warm for 1 h, the temperature was lowered to -78°C, the tetrahydrofuran solution of the intermediate 5 was added dropwise to the three-necked flask, the reaction was kept warm for 2 h, the temperature was raised to -20°C, 100 mL of water was added, and 150 mL of ethyl acetate was extracted 3 times. The organic phases were combined, washed with 200 mL of saturated brine, dried with anhydrous sodium sulfate for 2 h, and dried to obtain a gray-black solid. The white solid compound I-1-5 (5.3 g, 0.013 mol) was obtained by recrystallization using toluene and ethanol. The yield was 64.6%, MS (m / z) (M+): 414.16.

[0231] Example 3

[0232] This embodiment provides a liquid crystal compound I-1-7, whose structural formula is as follows:

[0233]

[0234] The synthetic route of the compound is as follows:

[0235]

[0236] The specific synthesis method is the same as that of Compound Example 2, except that 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid is replaced by 3-fluoro-4-(3,3,3-trifluoropropyl)phenylboronic acid, and the final product I-1-7 (3.8 g, 0.0089 mol) is obtained with a yield of 58.2%, MS (m / z) (M+): 428.18.

[0237] The formula of the liquid crystal composition and the corresponding properties are shown in Table 7 below.

[0238] Table 7 Formulation of the liquid crystal composition of Example 3 and corresponding properties

[0239] Example 4

[0240] This embodiment provides a liquid crystal compound I-2-2, whose structural formula is as follows:

[0241]

[0242] The synthetic route of the compound is as follows:

[0243]

[0244] Step (1)

[0245] 1,2-dibromoethane (40 g, 0.22 mol) was dissolved in 50 mL of tetrahydrofuran to obtain a 1,2-dibromoethane tetrahydrofuran solution; 2-fluoro-4-chlorobromobenzene (30 g, 0.14 mol) was dissolved in 150 mL of tetrahydrofuran to obtain a 2-fluoro-4-chlorobromobenzene tetrahydrofuran solution, the temperature was lowered to -78°C, n-butyl lithium (69 mL, 0.17 mol) was added dropwise, after the addition was completed, the temperature was kept for reaction for 1 h, 1,2-dibromoethane tetrahydrofuran solution was added dropwise, the temperature was naturally raised, the reaction was carried out at room temperature for 12 h, the temperature was lowered to -40°C, 200 mL of water was added, and 150 mL of ethyl acetate was extracted three times. The organic phases were combined, washed with 200 mL of saturated brine, dried over anhydrous sodium sulfate for 2 h, and concentrated to obtain a yellow oil intermediate 1 (29 g, 0.12 mol) with a yield of 86.1%.

[0246] Step (2)

[0247] Into a 250mL three-necked flask, intermediate 1 (29g, 0.12mol) and triphenylphosphine (48g, 0.19mol) were added, and 60mL of DMF was added. The temperature was raised and kept at 130°C for 4h. The temperature was lowered, DMF was removed by vortexing, and 250mL of ethyl acetate was used for slurrying. The white solid intermediate 2 (50g, 0.1mol) was obtained by suction filtration with a yield of 81%.

[0248] Step (3)

[0249] Propylcyclohexanone (13 g, 0.095 mol) was dissolved in 50 mL of tetrahydrofuran to obtain a propylcyclohexanone tetrahydrofuran solution; intermediate 2 (50 g, 0.1 mol) and 250 mL of tetrahydrofuran were added into a 500 mL three-necked flask, stirred evenly, cooled to -20°C, potassium tert-butoxide (13 g, 0.12 mol) was added, the temperature was controlled to react for 1 h, the propylcyclohexanone tetrahydrofuran solution was added dropwise, the temperature was controlled to -20°C to react for 2 h, the reaction solution was poured into 250 mL of water, extracted 3 times with 150 mL of ethyl acetate, the organic phases were combined, washed with 200 mL of saturated brine, dried over anhydrous sodium sulfate, concentrated to obtain a reddish-brown solid, slurried with ethanol, and filtered to obtain a white solid intermediate 3 (21 g, 0.076 mol) with a yield of 80.1%.

[0250] Step (4)

[0251] Into a 250mL three-necked flask, intermediate 3 (21g, 0.076mol), p-toluenesulfonic acid (43g, 0.23mol) and 150mL toluene were added, refluxed for 2h, poured into 200mL water, the organic phase was washed, separated, the organic phase was flushed into a column, and concentrated to obtain white solid intermediate 4 (21g, 0.075mol) with a yield of 99.1%.

[0252] Step (5)

[0253] Add intermediate 4 (21.1 g, 0.075 mol), 3-fluoro-4-trifluoromethoxyphenylboronic acid (17 g, 0.075 mol), anhydrous potassium carbonate (12 g, 0.09 mol), tetrakis(triphenylphosphine)palladium (0.43 g, 0.00038 mol) and 250 mL toluene to a 250 mL three-necked flask, reflux for 4 h, cool to room temperature, add 200 mL of water, wash with water, flush the column with the organic phase, concentrate to obtain the crude intermediate 3, slurry with ethanol, and filter to obtain the white solid intermediate 5 (28 g, 0.066 mol), with a yield of 88.2%;.

[0254] Step (6)

[0255] To a 500mL three-necked flask, add intermediate 5 (28g, 0.066mol) and 150mL tetrahydrofuran, cool the solution to -78°C, slowly add n-butyllithium (67mL, 0.17mol), control the temperature and react for 1h, add DMF (7.2g, 0.1mol), control the temperature and react for 1h, raise the temperature to -20°C, add 100mL water, extract three times with 150mL ethyl acetate, wash with 250mL saturated brine, dry with anhydrous sodium sulfate for 2h, concentrate to obtain a yellow oil, slurry with petroleum ether, and filter to obtain a yellow solid intermediate 6 (26g, 0.053mol) with a yield of 80.5%.

[0256] Step (7)

[0257] 80% hydrazine hydrate (8.3 g, 0.13 mol) was dissolved in 25 mL of glacial acetic acid to obtain a hydrazine hydrate glacial acetic acid solution; intermediate 6 (26 g, 0.053 mol) and 250 mL of glacial acetic acid were added to a 250 mL three-necked flask, heated to reflux, and the hydrazine hydrate glacial acetic acid solution was slowly added dropwise. After the addition was completed, the reaction was refluxed for 5 hours, the temperature was lowered, and a yellow solid was obtained by suction filtration. The white solid compound I-2-2 (16 g, 0.035 mol) was obtained by recrystallization using toluene and ethanol. The yield was 65.2%, and the MS (m / z) (M+): 488.12.

[0258] Example 5

[0259] This embodiment provides a liquid crystal compound I-2-4, whose structural formula is as follows:

[0260]

[0261] The synthetic route of the compound is as follows:

[0262]

[0263] The specific synthesis method of step (1) to step (7) is the same as that of compound Example 4, except that 3-fluoro-4-trifluoromethoxyphenylboronic acid is replaced by 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid, and finally a white solid intermediate 7 (8.3 g, 0.018 mol) is obtained with a yield of 67.2%.

[0264] Step (8)

[0265] The intermediate 7 (8.3 g, 0.018 mol) was dissolved in 150 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate 7; diisopropylamine (5.4 g, 0.054 mol) was added to a 500 mL three-necked flask, the temperature was lowered to -20°C, n-butyl lithium (22 mL, 0.054 mol) was added dropwise, the reaction was kept warm for 1 h, the temperature was lowered to -78°C, the tetrahydrofuran solution of the intermediate 7 was added dropwise to the three-necked flask, the reaction was kept warm for 2 h, the temperature was raised to -20°C, 100 mL of water was added, and 150 mL of ethyl acetate was extracted 3 times. The organic phases were combined, washed with 200 mL of saturated brine, dried with anhydrous sodium sulfate for 2 h, and dried to obtain a yellow-brown solid. The white solid compound I-2-4 (4.2 g, 0.0095 mol) was obtained by recrystallization using toluene and ethanol. The yield was 53%, MS (m / z) (M+): 442.19.

[0266] Example 6

[0267] This embodiment provides a liquid crystal compound I-2-6, whose structural formula is as follows:

[0268]

[0269] The synthetic route of the compound is as follows:

[0270]

[0271] The specific synthesis method is the same as that of Compound Example 5, except that 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid is replaced by 3-fluoro-4-(3,3,3-trifluoropropyl)phenylboronic acid, and finally a white solid I-2-6 (7.7 g, 0.017 mol) is obtained with a yield of 77.5%, MS (m / z) (M+): 456.21.

[0272] Example 7

[0273] This embodiment provides a liquid crystal compound I-3-2, whose structural formula is as follows:

[0274]

[0275] The synthetic route of the compound is as follows:

[0276]

[0277] Step (1)

[0278] Propylcyclohexanone (20 g, 0.14 mol) was dissolved in 100 mL of tetrahydrofuran to obtain a propylcyclohexanone tetrahydrofuran solution; methyl bromide triphenylphosphine salt (56 g, 0.16 mol) and 150 mL of tetrahydrofuran were put into a 500 mL three-necked flask, cooled to -20 ° C, added with potassium tert-butoxide (19 g, 0.17 mol), kept warm for 1 h, and the propylcyclohexanone tetrahydrofuran solution was added dropwise. After the addition was completed, the reaction was kept warm for 1 h, 200 mL of water was added, and 150 mL of ethyl acetate was extracted three times. The organic phases were combined, washed with 250 mL of saturated brine, dried over anhydrous sodium sulfate for 2 h, and concentrated to obtain a yellow oily intermediate 1 (18 g, 0.13 mol) with a yield of 91.6%.

[0279] Step (2)

[0280] Intermediate 1 (18 g, 0.13 mol), m-chloroperbenzoic acid (27 g, 0.16 mol) and 200 mL of dichloromethane were placed in a 500 mL three-necked flask and stirred at room temperature for 24 h. The reaction solution was washed with 200 mL of water, dried over anhydrous sodium sulfate for 2 h, and concentrated to obtain a light yellow oily intermediate 2 (17 g, 0.11 mol) with a yield of 83.1%.

[0281] Step (3)

[0282] The intermediate 2 (17 g, 0.11 mol) was dissolved in 100 mL of DMF to obtain an intermediate 2DMF solution; 2-Fluoro-4-bromo-phenol (21 g, 0.11 mol), sodium hydride (2.9 g, 0.12 mol) and 100 mL of DMF were put into a 500 mL three-necked flask, stirred evenly and then cooled to 0°C, and the intermediate 2DMF solution was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and reacted for 4 h, poured into 500 mL of ice water, extracted twice with 250 mL of ethyl acetate, the organic phases were combined, washed with 500 mL of saturated brine, dried over anhydrous sodium sulfate for 2 h, and concentrated to obtain a red oily intermediate 3 (32 g, 0.091 mol) with a yield of 83.9%.

[0283] Step (4)

[0284] Intermediate 3 (32 g, 0.091 mol), p-toluenesulfonic acid (1.7 g, 9.1 mmol) and 250 mL of toluene were placed in a 500 mL three-necked flask, and the water was separated using a water separator. The mixture was refluxed for 3 h, and the reaction solution was washed with 250 mL of water. The organic phase was flushed through a column and concentrated to obtain a crude product. The crude product was recrystallized from ethanol to obtain a white solid intermediate 4 (23 g, 0.071 mol) with a yield of 78.3%.

[0285] Step (5)

[0286] In a 250 mL three-necked flask, intermediate 4 (23 g, 0.071 mol), 3-fluoro-4-trifluoromethoxyphenylboronic acid (16 g, 0.071 mol), anhydrous potassium carbonate (12 g, 0.085 mol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.36 mmol) and 150 mL toluene were added, refluxed for 4 h, cooled to room temperature, 150 mL of water was added, washed with water, the organic phase was flushed into the column, concentrated to obtain a crude product, ethanol was used for slurrying, and suction filtration was performed to obtain a white solid intermediate 5 (26 g, 0.061 mol), with a yield of 85.2%;.

[0287] Step (6)

[0288] To a 500mL three-necked flask, add intermediate 5 (26g, 0.061mol) and 100mL tetrahydrofuran, cool the solution to -78°C, slowly add n-butyllithium (54mL, 0.13mol), control the temperature and react for 1h, add DMF (11g, 0.15mol), control the temperature and react for 1h, raise the temperature to -20°C, add 100mL water, extract three times with 150mL ethyl acetate, wash with 250mL saturated brine, dry with anhydrous sodium sulfate for 2h, concentrate to obtain a yellow oil, slurry with petroleum ether, and filter to obtain a yellow solid intermediate 6 (18g, 0.038mol) with a yield of 62.2%.

[0289] Step (7)

[0290] 80% hydrazine hydrate (7.1 g, 0.11 mol) was dissolved in 25 mL of glacial acetic acid to obtain a glacial acetic acid solution of hydrazine hydrate; intermediate 6 (18 g, 0.038 mol) and 200 mL of glacial acetic acid were added to a 250 mL three-necked flask, heated to reflux, and the glacial acetic acid solution of hydrazine hydrate was slowly added dropwise. After the addition was completed, the reaction was refluxed for 5 h, the temperature was lowered, and a yellow solid was obtained by suction filtration. The white solid compound I-3-2 (8.1 g, 0.018 mol) was obtained by recrystallization using toluene and n-heptane. The yield was 47.3%, and the MS (m / z) (M+): 450.16.

[0291] Example 8

[0292] This embodiment provides a liquid crystal compound I-3-4, whose structural formula is as follows:

[0293]

[0294] The synthetic route of the compound is as follows:

[0295]

[0296] The specific synthesis method of step (1) to step (7) is the same as that of compound Example 7, except that 3-fluoro-4-trifluoromethoxyphenylboronic acid is replaced by 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid, and finally a white solid intermediate 7 (11.6 g, 0.025 mol) is obtained with a yield of 67.1%.

[0297] Step (8)

[0298] The intermediate 7 (11.6 g, 0.025 mol) was dissolved in 150 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate 7; diisopropylamine (7.6 g, 0.075 mol) was added to a 500 mL three-necked flask, the temperature was lowered to -20°C, n-butyl lithium (30 mL, 0.075 mol) was added dropwise, the reaction was kept warm for 1 h, the temperature was lowered to -78°C, the tetrahydrofuran solution of the intermediate 7 was added dropwise to the three-necked flask, the reaction was kept warm for 2 h, the temperature was raised to -20°C, 150 mL of water was added, and 150 mL of ethyl acetate was extracted 3 times. The organic phases were combined, washed with 200 mL of saturated brine, dried with anhydrous sodium sulfate for 2 h, and dried to obtain a gray-black solid. The white solid compound I-3-4 (8.1 g, 0.018 mol) was obtained by recrystallization using toluene and ethanol. The yield was 72.9%, MS (m / z) (M+): 444.17.

[0299] Example 9

[0300] This embodiment provides a liquid crystal compound I-3-6, whose structural formula is as follows:

[0301]

[0302] The synthetic route of the compound is as follows:

[0303]

[0304] The specific synthesis method is the same as that of Compound Example 8, except that 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid is replaced by 3-fluoro-4-(3,3,3-trifluoropropyl)phenylboronic acid, and finally a white solid I-3-6 (5.1 g, 0.011 mol) is obtained with a yield of 45.8%, MS (m / z) (M+): 458.19.

[0305] Example 10

[0306] This embodiment provides a liquid crystal compound I-4-2, whose structural formula is as follows:

[0307]

[0308] The synthetic route of the compound is as follows:

[0309]

[0310] Step (1)

[0311] 2-Fluoro-4-bromobenzaldehyde (15 g, 0.074 mol), propyl propanediol (13 g, 0.11 mol), p-toluenesulfonic acid (1.4 g, 7.4 mmol) and 250 mL of toluene were placed in a 500 mL three-necked flask, separated by a water separator, and refluxed for 4 h. 200 mL of water was added to wash the reaction solution, separated, and the organic phase was flushed into a column and concentrated to obtain a colorless oily intermediate 1 (21 g, 0.069 mol) with a yield of 93.7%.

[0312] Step (2)

[0313] Add intermediate 1 (21 g, 0.069 mol), 3-fluoro-4-trifluoromethoxyphenylboronic acid (15.5 g, 0.069 mol), anhydrous potassium carbonate (11.5 g, 0.083 mol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.35 mmol) and 200 mL toluene to a 250 mL three-necked flask, reflux for 4 h, cool to room temperature, add 200 mL of water, wash with water, flush the organic phase into the column, concentrate to obtain the crude intermediate 2, slurry with ethanol, filter to obtain a white solid, and recrystallize with toluene and n-heptane to obtain a white solid intermediate 2 (21 g, 0.052 mol), with a yield of 75.7%;.

[0314] Step (3)

[0315] To a 500mL three-necked flask, add intermediate 2 (21g, 0.052mol) and 100mL tetrahydrofuran, cool the solution to -78°C, slowly add n-butyllithium (51mL, 0.11mol), control the temperature and react for 1h, add DMF (9.5g, 0.13mol), control the temperature and react for 1h, raise the temperature to -20°C, add 100mL water, extract three times with 150mL ethyl acetate, wash with 200mL saturated brine, dry with anhydrous sodium sulfate for 2h, concentrate to obtain a yellow oil, slurry with petroleum ether, and filter to obtain a brown solid intermediate 3 (17g, 0.037mol) with a yield of 71.3%.

[0316] Step (4)

[0317] Dissolve 80% hydrazine hydrate (5.8 g, 0.093 mol) in 25 mL of glacial acetic acid to obtain a glacial acetic acid solution of hydrazine hydrate; add intermediate 3 (17 g, 0.037 mol) and 200 mL of glacial acetic acid into a 250 mL three-necked flask, heat to reflux, slowly add dropwise the glacial acetic acid solution of hydrazine hydrate, after the dropwise addition, reflux for 5 h, cool, filter to obtain a yellow solid, and use toluene and ethanol to recrystallize to obtain a white solid compound I-4-2 (4.5 g, 0.011 mol), with a yield of 28.5%, MS (m / z) (M+): 426.13.

[0318] Embodiment 11

[0319] This embodiment provides a liquid crystal compound I-4-4, whose structural formula is as follows:

[0320]

[0321] The synthetic route of the compound is as follows:

[0322]

[0323] The specific synthesis method of step (1) to step (4) is the same as that of compound Example 10, except that 3-fluoro-4-trifluoromethoxyphenylboronic acid is replaced by 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid, and finally a white solid intermediate 4 (11.3 g, 0.026 mol) is obtained with a yield of 71.2%.

[0324] Step (5)

[0325] The intermediate 4 (11.3 g, 0.026 mol) was dissolved in 100 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate 4; diisopropylamine (7.9 g, 0.078 mol) was added to a 250 mL three-necked flask, the temperature was lowered to -20 ° C, n-butyl lithium (31 mL, 0.078 mol) was added dropwise, the reaction was kept warm for 1 h, the temperature was lowered to -78 ° C, the tetrahydrofuran solution of the intermediate 4 was added dropwise to the three-necked flask, the reaction was kept warm for 2 h, the temperature was raised to -20 ° C, 150 mL of water was added, and 150 mL of ethyl acetate was extracted 3 times. The organic phases were combined, washed with 200 mL of saturated brine, dried with anhydrous sodium sulfate for 2 h, and dried to obtain an orange-red solid. The white solid compound I-4-4 (7.9 g, 0.019 mol) was recrystallized using toluene and ethanol. The yield was 72.3%, MS (m / z) (M+): 420.13.

[0326] Example 12

[0327] This embodiment provides a liquid crystal compound I-4-6, whose structural formula is as follows:

[0328]

[0329] The synthetic route of the compound is as follows:

[0330]

[0331] The specific synthesis method is the same as that of compound Example 11, except that 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid is replaced by 3-fluoro-4-(3,3,3-trifluoropropyl)phenylboronic acid, and finally a white solid I-4-6 (8.8 g, 0.02 mol) is obtained with a yield of 77.4%, MS (m / z) (M+): 434.15.

[0332] Embodiment 13

[0333] This embodiment provides a liquid crystal compound I-5-2, whose structural formula is as follows:

[0334]

[0335] The synthetic route of the compound is as follows:

[0336]

[0337] Step (1)

[0338] In a 250mL three-necked flask, p-bromocinnamaldehyde (20g, 0.087mol), propyl propanediol (15g, 0.13mol), p-toluenesulfonic acid (1.7g, 8.7mmol) and 150mL toluene were added. The water was separated by using a water separator. The reaction mixture was refluxed for 4h. The reaction solution was washed with 200mL of water, separated, and the organic phase was flushed into a column. The reaction mixture was concentrated to obtain a light yellow solid intermediate 1 (25g, 0.076mol) with a yield of 87.4%.

[0339] Step (2)

[0340] Add intermediate 1 (25 g, 0.076 mol), 3-fluoro-4-trifluoromethoxyphenylboronic acid (17 g, 0.076 mol), anhydrous potassium carbonate (13 g, 0.091 mol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.38 mmol) and 200 mL toluene to a 250 mL three-necked flask, reflux for 4 h, cool to room temperature, add 200 mL of water, wash with water, flush the column with the organic phase, concentrate to obtain the crude intermediate 2, slurry with ethanol, filter to obtain a white solid, and recrystallize with toluene and ethanol to obtain a white solid intermediate 2 (29 g, 0.068 mol), with a yield of 89.1%. .

[0341] Step (3)

[0342] Intermediate 2 (29 g, 0.068 mol), hydrogenated palladium carbon (2.9 g, 10 wt%), and 250 mL of tetrahydrofuran were placed in a 500 mL flask, and hydrogen was charged under stirring for 12 h. The palladium carbon was removed by suction, and the filtrate was concentrated to obtain an off-white solid intermediate 3 (27 g, 0.063 mol) with a yield of 92.2%.

[0343] Step (4)

[0344] To a 500mL three-necked flask, add intermediate 3 (27g, 0.063mol) and 200mL tetrahydrofuran, cool the solution to -78°C, slowly add n-butyllithium (55mL, 0.14mol), control the temperature and react for 1h, add DMF (12g, 0.16mol), control the temperature and react for 1h, raise the temperature to -20°C, add 150mL water, extract three times with 150mL ethyl acetate, wash with 200mL saturated brine, dry with anhydrous sodium sulfate for 2h, concentrate to obtain a yellow oil, slurry with petroleum ether, and filter to obtain a light yellow solid intermediate 4 (22g, 0.045mol) with a yield of 71.8%.

[0345] Step (5)

[0346] Dissolve 80% hydrazine hydrate (6.2 g, 0.099 mol) in 100 mL of glacial acetic acid to obtain a glacial acetic acid solution of hydrazine hydrate; add intermediate 4 (22 g, 0.045 mol) and 250 mL of glacial acetic acid into a 500 mL three-necked flask, heat to reflux, slowly add dropwise the glacial acetic acid solution of hydrazine hydrate, after the dropwise addition, reflux for 5 hours, cool, filter to obtain a yellow solid, and use toluene and ethanol to recrystallize to obtain a white solid compound I-5-2 (7.1 g, 0.016 mol), with a yield of 34.8%, MS (m / z) (M+): 454.16.

[0347] Embodiment 14

[0348] This embodiment provides a liquid crystal compound I-5-4, whose structural formula is as follows:

[0349]

[0350] The synthetic route of the compound is as follows:

[0351]

[0352] The specific synthesis method of step (1) to step (5) is the same as that of compound Example 13, except that 3-fluoro-4-trifluoromethoxyphenylboronic acid is replaced by 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid, and finally a white solid intermediate 5 (8.9 g, 0.019 mol) is obtained with a yield of 41.2%.

[0353] Step (5)

[0354] The intermediate 5 (8.9 g, 0.019 mol) was dissolved in 100 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the intermediate 5; diisopropylamine (5.8 g, 0.057 mol) was added to a 250 mL three-necked flask, the temperature was lowered to -20 ° C, n-butyl lithium (23 mL, 0.057 mol) was added dropwise, the reaction was kept warm for 1 h, the temperature was lowered to -78 ° C, the tetrahydrofuran solution of the intermediate 5 was added dropwise to the three-necked flask, the reaction was kept warm for 2 h, the temperature was raised to -20 ° C, 100 mL of water was added, and 100 mL of ethyl acetate was extracted 3 times. The organic phases were combined, washed with 200 mL of saturated brine, dried with anhydrous sodium sulfate for 2 h, and dried to obtain a gray-black solid. The white solid compound I-5-4 (4.6 g, 0.01 mol) was recrystallized using toluene and ethanol. The yield was 54%, MS (m / z) (M+): 448.17.

[0355] Embodiment 15

[0356] This embodiment provides a liquid crystal compound I-5-6, whose structural formula is as follows:

[0357]

[0358] The synthetic route of the compound is as follows:

[0359]

[0360] The specific synthesis method is the same as that of Compound Example 14, except that 3-fluoro-4-(2,2,2-trifluoroethyl)phenylboronic acid is replaced by 3-fluoro-4-(3,3,3-trifluoropropyl)phenylboronic acid, and finally a white solid I-5-6 (6.7 g, 0.014 mol) is obtained with a yield of 71.1%, MS (m / z) (M+): 462.18.

[0361] As shown in Table 3 below, compared with dibenzothiophene and benzochromene compounds with similar structures, the compounds containing phenanthrene structures provided by the present invention have higher vertical dielectric constants, which is beneficial to improving the transmittance of the liquid crystal composition, and have lower rotational viscosity and larger elastic coefficient, which is beneficial to improving the response speed of the liquid crystal composition, and also have higher clearing points and optical anisotropy.

[0362] Table 3

[0363]

[0364] Composition Examples

[0365] Liquid crystal composition examples M1 to M7 were prepared according to the following table.

[0366] Table 4 Liquid crystal composition examples M1 to M7

[0367]

[0368]

[0369] Table 5 Performance parameters of liquid crystal composition examples M1 to M7

[0370] M1 M2 M3 M4 M5 M6 M7 Δε[1KHz,25℃]: 3.98 2.56 3.99 3.44 3.07 3.06 3.43 <![CDATA[ε ⊥ [1KHz,25℃]:]]> 6.79 4.51 6.92 5.99 5.35 5.37 5.92 Δn[589nm,25℃]: 0.123 0.106 0.118 0.105 0.116 0.119 0.109 Cp[℃]: 98.2 91.9 94.4 91.2 96.5 97.3 90.3 <![CDATA[γ 1 [mPa.S]:]]> 77.8 67.8 74.3 74.5 76.0 79.3 69.1 <![CDATA[K 11 :]]> 18.1 16.2 17.2 16.4 17.4 18.1 17.0 <![CDATA[γ 1 / K 11 :]]> 4.29 4.18 4.31 4.53 4.38 4.37 4.06 <![CDATA[ε ⊥ / No:]]> 1.71 1.76 1.73 1.74 1.74 1.75 1.73

[0371] Composition Comparative Example

[0372] The compounds L-Phe-3-OT and D-Phe-3-OT represented by Formula I in Example M1 are replaced in equal amounts by Formula A and Formula B shown below as composition comparative example 1, and are replaced in equal amounts by Formula C and Formula D shown below as composition comparative example 2.

[0373]

[0374] The performance comparison between Example M1 and Comparative Examples 1 and 2 is shown in Table 6 below.

[0375] Table 6 Corresponding properties of Example M1, Comparative Examples 1 and 2

[0376] Example M1 Comparative Example 1 Comparative Example 2 Δε[1KHz,25℃]: 3.98 3.79 3.65 <![CDATA[ε ⊥ [1KHz,25℃]:]]> 6.79 6.49 6.27 Δn[589nm,25℃]: 0.123 0.118 0.117 Cp[℃]: 98.2 95.4 94.1 <![CDATA[γ 1 [mPa.S]:]]> 77.8 85.3 96.6 <![CDATA[K 11 :]]> 18.1 16.8 16.2 <![CDATA[γ 1 / K 11 :]]> 4.29 5.08 5.96 <![CDATA[ε ⊥ / No:]]> 1.71 1.71 1.72

[0377] It can be seen from Table 6 above that compared with Comparative Examples 1 and 2, Example M1 has a higher clearing point, a higher dielectric anisotropy Δε, a higher optical anisotropy Δn, and a lower γ 1 / K 11 . Lower γ 1 / K 11 A higher Δn is beneficial to improving the response speed of the liquid crystal composition, and a higher Δε is beneficial to reducing the driving voltage of the liquid crystal composition and reducing power consumption. ⊥ / Δε is comparable thereto, and the transmittance of the liquid crystal composition can be kept at a higher level.

[0378] UV aging test and backlight aging test were performed on Example M1, Comparative Examples 1 and 2. In the production process of liquid crystal panels, there is a UV curing process, and ultraviolet light has a destructive effect on liquid crystal materials. Compared with the traditional side backlight, the light intensity of Mini LED directly irradiated on the liquid crystal material is higher, and the damage to the liquid crystal material is also stronger than the side backlight. Therefore, the liquid crystal material should have a certain ability to resist ultraviolet light and long-term light exposure.

[0379] Before conducting the UV and backlight aging experiments, the VHR data of the liquid crystal composition is measured as initial VHR data. Then, the liquid crystal composition is subjected to UV and backlight aging tests, and the VHR data of the liquid crystal composition is measured again after the experiments.

[0380] Ultraviolet aging experiment: The liquid crystal composition was poured into a test box and irradiated with 5000 mJ energy under an ultraviolet lamp with a wavelength of 365 nm.

[0381] Backlight aging experiment: The liquid crystal composition is poured into a test box and placed on a Mini LED backlight panel for 500 hours. The backlight intensity is 15,000 nit. The Mini LED backlight used in the experiment is blue LED + QD film (quantum dot film).

[0382] Afterimage experiment: Expose the Mini LED backlight panel for 1000 hours.

[0383] Table 7 below shows the UV, high temperature, backlight aging and image retention experimental data of Example M1 and Comparative Examples 1 and 2.

[0384] Table 16 UV aging, backlight aging and image retention test data

[0385]

[0386]

[0387] It can be seen from Table 7 above that compared with Comparative Examples 1 and 2, Example M1 still has a higher VHR after UV and backlight aging experiments. And there is no residual image defect after long-term backlight irradiation. Comparative Examples 1 and 2 both showed a significant decrease in VHR after long-term backlight irradiation, and a certain amount of residue appeared in the residual image test experiment, resulting in the problem of residual image defect.

[0388] In summary, the compound provided by the present invention has a higher vertical dielectric constant, which is beneficial to improve the transmittance of the liquid crystal composition, and has a lower rotational viscosity and a larger elastic coefficient, which is beneficial to improve the response speed of the liquid crystal composition, and also has a higher clearing point and optical anisotropy. The present invention also provides a positive dielectric anisotropic liquid crystal composition containing the phenanthrene structure compound, which has the characteristics of high transmittance, low rotational viscosity, and fast response speed, and has good resistance to high temperature and ultraviolet light, and has strong stability under long-term high-brightness light. The liquid crystal composition is particularly suitable for use in the field of television. A liquid crystal display containing the compound or liquid crystal composition has the characteristics of high brightness, high contrast, fast response speed, no residual image, low energy consumption, and long service life.

[0389] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A compound containing a phenanthrene structure, It is characterized in that The compound is as shown in formula I, in, R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene; R 2 represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms; Z 1 Represents a single bond, -CH 2 -、-CH 2 CH 2 -、-CH 2 O-; express 2. The liquid crystal compound according to claim 1, It is characterized in that The liquid crystal compound is selected from the group consisting of compounds represented by the following formulas Ⅰ-1 to Ⅰ-5, in, R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene; R 2 It represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms.

3. The liquid crystal compound according to claim 2, It is characterized in that The compounds represented by formulas I-1 to I-5 are selected from the group consisting of compounds represented by formulas I-1-1 to I-5-8 below, 4. A liquid crystal composition with positive dielectric anisotropy containing a phenanthrene structure compound, It is characterized in that The liquid crystal composition comprises one or more compounds represented by formula I and one or more compounds represented by formula II. in, R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 1 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene; R 2 represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms or a fluorine-substituted alkenyl group having 2 to 10 carbon atoms; Z 1 Represents a single bond, -CH 2 -、-CH 2 CH 2 -、-CH 2 O-; express R 3 represents a chain alkyl group having 1 to 10 carbon atoms, and R 3 Any of -CH 2 -optionally substituted with cyclopropylene or cyclopentylene; R 4 Indicates H or CH3; express express 5. The liquid crystal composition according to claim 4, It is characterized in that The liquid crystal composition further comprises one or more compounds represented by formula III, in, R 5 , R 6 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

6. The liquid crystal composition according to claim 4, It is characterized in that The liquid crystal composition further comprises one or more compounds represented by formula IV, in, R 7 , R 8 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; express Z 2 Represents a single bond or -CH 2 CH 2 -; p represents 1 or 2; when p represents 2, Can be the same or different.

7. The liquid crystal composition according to claim 4, It is characterized in that The liquid crystal composition further comprises one or more compounds represented by formula V, in, R 9 , R 10 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; express 8. The liquid crystal composition according to claim 4, It is characterized in that The liquid crystal composition further comprises one or more compounds represented by formula VI, in, R 11 represents a chain alkyl group having 1 to 10 carbon atoms, and R 11 Any -CH2- in is optionally substituted by cyclopropylene or cyclopentylene; Z 3 Represents a single bond or -CH 2 CH 2 -; q represents 0 or 1.

9. The liquid crystal composition according to claim 4, It is characterized in that The liquid crystal composition further comprises one or more compounds represented by formula VII, in, R 12 represents a chain alkyl group having 1 to 10 carbon atoms, and R 12 Any of -CH 2 -optionally substituted by cyclopropylene or cyclopentylene.

10. A liquid crystal display element or a liquid crystal display, It is characterized in that A liquid crystal display device comprising the compound according to any one of claims 1 to 3 or comprising the liquid crystal composition according to any one of claims 4 to 9, wherein the liquid crystal display device is an active matrix display device or a passive matrix display device.

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