具体实施方式Detailed ways

下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from open commercial channels unless otherwise specified.

下面实施例用于解释本发明，但本发明不仅限于下面实施例。所述方法如无特别说明均为常规方法。所述材料如无特别说明均能从公开商业途径而得。下面实施例中GC表示气相色谱纯度，HPLC表示液相色谱纯度，MP表示熔点，MS表示质谱，1H-NMR表示核磁氢谱，△ε表示介电各向异性，△n表示光学各向异性。The following examples are used to explain the present invention, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The materials can be obtained from public commercial sources unless otherwise specified. In the following examples, GC represents gas chromatography purity, HPLC represents liquid chromatography purity, MP represents melting point, MS represents mass spectrum, 1H-NMR represents hydrogen nuclear magnetic spectrum, Δε represents dielectric anisotropy, and Δn represents optical anisotropy.

下述实施例所得式I所示产物均利用气相色谱、液相色谱、GC-MS所得质谱图和1H-NMR鉴定证实结构正确性。GC由安捷伦公司的HP6820型气相色谱分析仪进行测定，GC-MS分析测定装置为安捷伦公司的MS5975C型，1H-NMR由Bruker.Biospin公司的DRX-500分析装置进行测定，熔点测定使用WRX-1S显微热分析仪，设定升温速率为3℃/min。The products represented by formula I obtained in the following examples were identified by gas chromatography, liquid chromatography, GC-MS mass spectrum and 1H-NMR to confirm the correctness of the structure. GC was measured by HP6820 gas chromatograph analyzer of Agilent Company, GC-MS analysis and determination device was MS5975C model of Agilent Company, 1H-NMR was determined by DRX-500 analysis device of Bruker.Biospin Company, and melting point was determined by WRX-1S Microthermal analyzer, set the heating rate to 3°C/min.

下述实施例所得式I所示产物的物性均使用两种方式进行测定：将化合物本身作为试样进行测定和将化合物与母体液晶混合作为试样进行测定。将化合物与母体液晶混合作为试样测定化合物物性的方式为：首先将15%的液晶化合物与85%的母体液晶混合来制作试样，然后根据所得试样的测定值，按照下述式中所示的外推法来计算外推值，The physical properties of the product represented by formula I obtained in the following examples are measured in two ways: the compound itself is used as a sample for measurement and the compound is mixed with a matrix liquid crystal as a sample for measurement. The method of mixing the compound and the matrix liquid crystal as a sample to measure the physical properties of the compound is as follows: first, mix 15% of the liquid crystal compound with 85% of the matrix liquid crystal to prepare a sample, and then according to the measured value of the obtained sample, according to the following formula The extrapolation method shown to calculate the extrapolated value,

外推值=[100×(试样的测定值)-(母体液晶的重量百分率)×(母体液晶的测定值)]/化合物的重量百分率，从而得出单体液晶化合物的物性。Extrapolated value=[100×(measured value of sample)-(weight percentage of matrix liquid crystal)×(measured value of matrix liquid crystal)]/weight percentage of compound, so as to obtain the physical properties of monomeric liquid crystal compound.

所用母体液晶组成如下：The composition of the matrix liquid crystal used is as follows:

液晶化合物的物理性质测定方法按照本行业的规范进行，参见《液晶器件手册》航空工业出版社出版The method for measuring the physical properties of liquid crystal compounds is carried out in accordance with the norms of this industry, see "Liquid Crystal Device Handbook" published by Aviation Industry Press

化合物的物性测定方法：The physical property determination method of the compound:

1.相结构以及传递温度（℃）的测定1. Determination of phase structure and transfer temperature (°C)

①在具备偏光显微镜熔点仪[梅特勒（Mettler）公司FP-52型]，加热板上放置化合物，一边以3℃/min速度加热，一边利用偏光显微镜来观察相态变化，从而确定相态种类。① Place the compound on a heating plate equipped with a polarizing microscope melting point instrument (Mettler FP-52 type), heat at a speed of 3°C/min, and use a polarizing microscope to observe the phase change, so as to determine the phase state type.

②利用梅特勒公司差示量热扫描仪DSC822e，以1℃/min的速度升温或降温，利用外推法求出伴随试样的相变化的吸热波峰或发热波峰的起始点，从而确定转移温度。②Use Mettler’s differential calorimetry scanner DSC822e to heat up or cool down at a rate of 1°C/min, and use the extrapolation method to find the starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample, so as to determine transfer temperature.

结晶表示为C，近晶相为S，向列相为N，液体为I。The crystalline is represented by C, the smectic phase is S, the nematic phase is N, and the liquid is I.

2.粘度：η在20℃下测定mPa.s，使用体积粘度计测定。γ₁表示旋转粘度在20℃下测定cP，用Toyo6254综合测试仪测定。2. Viscosity: η is measured in mPa.s at 20°C and measured with a bulk viscometer. γ ₁ means that the rotational viscosity is measured at 20°C in cP and measured with a Toyo6254 comprehensive tester.

3.光学各向异性（折射率各向异性在25℃下测定△n），测定在25℃下，用波长589nm的光，使用阿贝折射仪进行测定△n。在一个方向对主棱镜（Pri3m）的表面进行摩擦后，将试样滴加到主棱镜上。折射率（n₁₁）是在偏光方向与摩擦方向平行时测定所得数值，折射率（n_⊥）是在偏光方向与摩擦方向垂直时测定所得数值，光学各向异性（△n）的值由△n=n₁₁-n_⊥来计算。3. Optical anisotropy (refractive index anisotropy is measured at 25°C for △n), measured at 25°C with light with a wavelength of 589nm, using an Abbe refractometer to measure △n. After rubbing against the surface of the main prism (Pri3m) in one direction, the sample is dropped onto the main prism. The refractive index (n ₁₁ ) is the value measured when the polarization direction is parallel to the rubbing direction, the refractive index (n _⊥ ) is the value measured when the polarization direction is perpendicular to the rubbing direction, and the value of optical anisotropy (△n) is determined by △ n=n ₁₁ -n _⊥ to calculate.

4.介电常数各向异性（△ε，在25℃下测定）由惠普公司HP4284a精密LCR测试仪进行测定。测定液晶分子在长轴方向的介电常数ε_‖，测定液晶分子在短轴方向的介电常数（ε_⊥），介电各向异性△ε通过△ε=ε_‖-ε_⊥来计算。4. Dielectric constant anisotropy (△ε, measured at 25°C) was measured by HP4284a precision LCR tester from Hewlett-Packard Company. Measure the dielectric constant ε _‖ of liquid crystal molecules in the long axis direction, measure the dielectric constant (ε _⊥ ) of liquid crystal molecules in the short axis direction, and calculate the dielectric anisotropy △ε by △ε=ε _‖ -ε _⊥ .

测定值中，当以液晶化合物本身作为试样时，记录所得值作为实验值，当以液晶化合物与母液晶的混合物作为试样时，记录由外推法得到的值作为实验值。Among the measured values, when the liquid crystal compound itself is used as the sample, the obtained value is recorded as the experimental value, and when the mixture of the liquid crystal compound and the mother liquid crystal is used as the sample, the value obtained by extrapolation is recorded as the experimental value.

实施例1化合物

步骤1（I-14-a）合成Step 1 (I-14-a) synthesis

1L三口瓶中加入400ml四氢呋喃(溶剂)101g（0.25mol）碘甲烷膦盐（反应物），搅拌下降温至0℃，分批加入28g（0.25mol）叔丁醇钾（反应物），加完搅拌1小时，滴加42g(0.2mol)3，5-二氟苯环己酮（反应物）和100ml四氢呋喃的溶液，滴完搅拌1小时，加入300ml水，搅拌10分钟，分液，蒸净溶剂，加入300ml石油醚柱层析，蒸干溶剂得产品37.4g收率90%，气相色谱纯度97%；Add 400ml tetrahydrofuran (solvent) and 101g (0.25mol) methyl iodide phosphonium salt (reactant) into a 1L three-necked flask, stir and cool down to 0°C, add 28g (0.25mol) potassium tert-butoxide (reactant) in batches, and complete the addition Stir for 1 hour, add dropwise a solution of 42g (0.2mol) 3,5-difluorophencyclohexanone (reactant) and 100ml tetrahydrofuran, stir for 1 hour after dropping, add 300ml water, stir for 10 minutes, separate the liquids, and steam Solvent, add 300ml of petroleum ether column chromatography, evaporate to dryness to obtain product 37.4g yield 90%, gas chromatography purity 97%;

步骤2（I-14-b）的合成Synthesis of Step 2 (I-14-b)

1L三口瓶中加入300ml乙醚(溶剂)，62.4g(0.3mol)（I-14-a）（反应物），31.4g(0.483mol)锌（催化剂）和1.5g乙酸铜(II)一水合物（催化剂），随后滴加60g（0.33mol）三氯乙酰氯（反应物），反应放热至回流，在室温下反应24小时。将固体过滤出来，弃去，滤液用水洗涤，蒸干，通过柱层析纯化得52.7g油状物氯化环丁酮。Add 300ml ether (solvent), 62.4g (0.3mol) (I-14-a) (reactant), 31.4g (0.483mol) zinc (catalyst) and 1.5g copper (II) acetate monohydrate to a 1L three-necked flask (catalyst), followed by dropwise addition of 60 g (0.33 mol) of trichloroacetyl chloride (reactant), the reaction was exothermic to reflux, and reacted at room temperature for 24 hours. The solid was filtered out and discarded. The filtrate was washed with water, evaporated to dryness, and purified by column chromatography to obtain 52.7 g of cyclobutanone chloride as an oily product.

将上步的氯化环丁酮（反应物），加入200ml冰乙酸(溶剂)，在温度小于80度下分批加入36.5g锌粉（反应物），加完后在80℃搅拌2小时，冷却至室温下加入200ml水，加入200ml甲基叔丁基醚，搅拌10分钟，分液，洗涤，干燥，蒸干溶剂得产品52.5g收率70%，气相色谱纯度98%；Add 200ml of glacial acetic acid (solvent) to the cyclobutanone chloride (reactant) in the previous step, add 36.5g of zinc powder (reactant) in batches at a temperature less than 80 degrees, and stir at 80°C for 2 hours after the addition is complete. Cool to room temperature, add 200ml of water, add 200ml of methyl tert-butyl ether, stir for 10 minutes, separate liquid, wash, dry, and evaporate the solvent to obtain 52.5g of product with a yield of 70% and a purity of 98% by gas chromatography;

步骤3（I-14-c）的合成Synthesis of Step 3 (I-14-c)

在1L三口瓶中加入6.6g镁屑（反应物），200ml四氢呋喃(溶剂)，加热回流滴加30.8g溴丙烷（反应物），制备格氏试剂，降温到20℃，滴加50g(0.2mol)（I-14-b）（反应物）的四氢呋喃溶液，搅拌2小时，加入到30ml盐酸水溶液中，水解20分钟，加入乙酸乙酯萃取，旋干。Add 6.6g of magnesium chips (reactant) and 200ml of tetrahydrofuran (solvent) into a 1L three-necked flask, add 30.8g of bromopropane (reactant) dropwise under reflux to prepare the Grignard reagent, cool down to 20°C, and add dropwise 50g (0.2mol ) (I-14-b) (reactant) in tetrahydrofuran, stirred for 2 hours, added to 30ml of hydrochloric acid aqueous solution, hydrolyzed for 20 minutes, added ethyl acetate for extraction, and spin-dried.

另一1L三口瓶中加入上面所得产品，500ml干燥的二氯甲烷（溶剂），氮气保护下，降温至-25～-20℃，滴加63.3ml（0.397mol）三乙基硅氢（反应物），滴毕，向体系中滴加50ml（0.397mol）三氟化硼乙醚（反应物），滴毕保持-25～-20℃搅拌2小时，自然升至0℃，加入碳酸氢钠饱和水溶液（调节PH值）至无气泡放出，分液，水洗至中性，旋干溶剂，用2倍乙醇（溶剂）重结晶，抽滤，得近白色晶体粉末38.9g，收率70%，气相色谱纯度99%。Add the product obtained above, 500ml of dry dichloromethane (solvent) into another 1L three-necked flask, cool down to -25～-20°C under nitrogen protection, add 63.3ml (0.397mol) of triethylsilylhydrogen (reactant) dropwise ), after dropping, add 50ml (0.397mol) boron trifluoride diethyl ether (reactant) dropwise to the system, keep stirring at -25～-20°C for 2 hours after dropping, naturally rise to 0°C, add saturated aqueous solution of sodium bicarbonate (Adjust the pH value) until no bubbles are released, separate the liquid, wash with water until neutral, spin dry the solvent, recrystallize with 2 times ethanol (solvent), and filter with suction to obtain 38.9g of near-white crystal powder with a yield of 70%. Gas chromatography 99% purity.

步骤4（I-14-d）的合成Synthesis of Step 4 (I-14-d)

在反应瓶中加入27.8g（0.1mol）（Ⅰ-14-c）（反应物），200ml四氢呋喃（溶剂），通氮气保护，降温至-60℃，滴加0.11mol正丁基锂（反应物），滴加过程控温-55℃～-60℃，滴毕，继续控温搅拌反应1小时。降温至-70℃，滴加28g（0.13mol）二氟二溴甲烷和100ml四氢呋喃的溶液（反应物），滴加过程控温-65℃～-70℃，滴毕，继续控温搅拌反应30分钟，升温至室温，加入20ml浓盐酸（调节PH值）+50ml水（溶剂）水解，分液，100ml二氯甲烷（溶剂）提取水相，水洗有机相至中性，蒸干溶剂得淡黄色液体40g（Ⅰ-14-d），收率90%，液相色谱纯度65%。Add 27.8g (0.1mol) (I-14-c) (reactant) and 200ml tetrahydrofuran (solvent) to the reaction flask, protect it with nitrogen, cool down to -60°C, add dropwise 0.11mol n-butyllithium (reactant ), the dropwise addition process was controlled at -55°C to -60°C, and after the dropwise addition was completed, the reaction was continued for 1 hour under temperature control and stirring. Cool down to -70°C, add dropwise a solution (reactant) of 28g (0.13mol) difluorodibromomethane and 100ml tetrahydrofuran, and control the temperature during the dropwise addition -65°C to -70°C, after the drop is complete, continue to control the temperature and stir for 30 minutes , warmed to room temperature, added 20ml of concentrated hydrochloric acid (to adjust the PH value) + 50ml of water (solvent) for hydrolysis, liquid separation, 100ml of dichloromethane (solvent) to extract the water phase, washed the organic phase with water until neutral, evaporated to dryness to obtain a light yellow liquid 40g (I-14-d), yield 90%, liquid chromatography purity 65%.

步骤5step 5

在反应瓶中加入0.1mol（Ⅰ-14-d）（反应物）,100mlDMSO（溶剂），0.2mol无水碳酸钾（反应物），0.12mol3，4，5-三氟苯酚（反应物），搅拌加热至65～70℃反应2小时。降温至室温，过滤固体，并用300ml二氯甲烷（溶剂）冲洗滤饼，滤液加入100ml水，搅拌，分液，用200ml二氯甲烷（溶剂）提取水层，水洗有机相至中性，蒸干溶剂。浓缩物溶于500ml甲苯（溶剂），过硅胶柱脱色，用甲苯（溶剂）洗脱，收集洗脱液并蒸除溶剂，所得物用无水乙醇（溶剂）重结晶3次，得到白色针状晶体（Ⅰ-14），收率40%，气相色谱纯度99.9%。Add 0.1mol (Ⅰ-14-d) (reactant), 100mlDMSO (solvent), 0.2mol anhydrous potassium carbonate (reactant), 0.12mol3,4,5-trifluorophenol (reactant) to the reaction flask, Stir and heat to 65-70°C for 2 hours. Cool down to room temperature, filter the solid, and wash the filter cake with 300ml of dichloromethane (solvent), add 100ml of water to the filtrate, stir, separate the layers, extract the aqueous layer with 200ml of dichloromethane (solvent), wash the organic phase with water until neutral, evaporate to dryness solvent. The concentrate was dissolved in 500ml of toluene (solvent), passed through a silica gel column for decolorization, eluted with toluene (solvent), collected the eluate and evaporated to remove the solvent, and the resulting product was recrystallized 3 times with absolute ethanol (solvent) to obtain white needles Crystal (I-14), yield 40%, gas chromatography purity 99.9%.

该产物的结构确认数据如下：The structural confirmation data of this product are as follows:

MP：60℃；MP: 60°C;

MS：m/s%474(3.2),327(100),176(2.8),189(3.7),MS: m/s%474(3.2),327(100),176(2.8),189(3.7),

1H-NMR：δ（ppm）0.90(t,3H),1.28(m,4H),1.44(m,4H)1.65(m,4H),1.90(m,5H),2.72(，m，1H),6.54(d,2H),6.89(m,2H)；1H-NMR: δ (ppm) 0.90(t, 3H), 1.28(m, 4H), 1.44(m, 4H), 1.65(m, 4H), 1.90(m, 5H), 2.72(, m, 1H), 6.54(d,2H),6.89(m,2H);

由上可知，该产物结构正确，为式I-14所示化合物。As can be seen from the above, the product has a correct structure and is a compound shown in formula I-14.

该化合物的液晶性能如下所示：The liquid crystal properties of this compound are as follows:

△ε：15.3（20℃，589nm）△ε: 15.3 (20°C, 589nm)

△n：0.119（20℃，1000Hz）Δn: 0.119 (20°C, 1000Hz)

由上可知，该化合物具有光热稳定性，具有宽的液晶态温度范围，较好的低温互溶性，较大的介电各向异性△ε，光学器件使用时可实现较低的阈值电压和低旋转粘度γ₁，可以改善液晶组合物材料和显示器性能，对实现显示器的快速响应具有重要意义。It can be seen from the above that the compound has photothermal stability, wide liquid crystal temperature range, good low-temperature mutual solubility, large dielectric anisotropy △ε, and can achieve lower threshold voltage and The low rotational viscosity γ ₁ can improve the properties of the liquid crystal composition material and the display, and is of great significance for realizing the fast response of the display.

实施例2、

步骤1（I-15-a）合成Step 1 (I-15-a) synthesis

1L三口瓶中加入400ml四氢呋喃(溶剂)101g（0.25mol）碘甲烷膦盐（反应物），搅拌下降温至0℃，分批加入28g（0.25mol）叔丁醇钾（反应物），加完搅拌1小时，滴加34.8g(0.2mol)苯基环己酮（反应物）和100ml四氢呋喃的溶液，滴完搅拌1小时，加入300ml水，搅拌10分钟，分液，蒸净溶剂，加入500ml石油醚柱层析，蒸干溶剂得产品31g，收率90%，气相色谱纯度97%Add 400ml tetrahydrofuran (solvent) and 101g (0.25mol) methyl iodide phosphonium salt (reactant) into a 1L three-necked flask, stir and cool down to 0°C, add 28g (0.25mol) potassium tert-butoxide (reactant) in batches, and complete the addition Stir for 1 hour, add dropwise a solution of 34.8g (0.2mol) phenylcyclohexanone (reactant) and 100ml tetrahydrofuran, stir for 1 hour after dropping, add 300ml of water, stir for 10 minutes, separate liquids, evaporate the solvent, add 500ml Petroleum ether column chromatography, evaporated to dryness to obtain product 31g, yield 90%, gas chromatography purity 97%

步骤2（I-15-b）的合成Synthesis of Step 2 (I-15-b)

1L三口瓶中加入400ml乙醚(溶剂)，51.6g(0.3mol)（I-15-a）（反应物），31.4g(0.483mol)锌（催化剂）和1.5g乙酸铜（II）一水合物（催化剂），随后滴加60g（0.33mol）三氯乙酰氯（反应物），反应放热至回流，在室温下反应24小时。将固体过滤出来，弃去，滤液用水洗涤，蒸干，通过柱层析纯化得80g油状物。Add 400ml ether (solvent), 51.6g (0.3mol) (I-15-a) (reactant), 31.4g (0.483mol) zinc (catalyst) and 1.5g copper (II) acetate monohydrate to a 1L three-necked flask (catalyst), followed by dropwise addition of 60 g (0.33 mol) of trichloroacetyl chloride (reactant), the reaction was exothermic to reflux, and reacted at room temperature for 24 hours. The solid was filtered out and discarded. The filtrate was washed with water, evaporated to dryness, and purified by column chromatography to obtain 80 g of an oil.

将上步的氯化环丁酮（反应物），加入200ml冰乙酸(溶剂)，在温度小于80度下分批加入36.5g锌粉（反应物），加完后在80℃搅拌2小时，冷却至室温下加入200ml水，加入200ml甲基叔丁基醚，搅拌10分钟，分液，洗涤，干燥，蒸干溶剂得产品45g，收率70%，气相色谱纯度98%。Add 200ml of glacial acetic acid (solvent) to the cyclobutanone chloride (reactant) in the previous step, add 36.5g of zinc powder (reactant) in batches at a temperature less than 80 degrees, and stir at 80°C for 2 hours after the addition is complete. Cool to room temperature, add 200ml of water, add 200ml of methyl tert-butyl ether, stir for 10 minutes, separate, wash, dry, and evaporate the solvent to obtain 45g of the product, with a yield of 70% and a purity of 98% by gas chromatography.

步骤3（I-15-c）的合成Synthesis of Step 3 (I-15-c)

在1L三口瓶中加入6.6g镁屑（反应物），200ml四氢呋喃(溶剂)，加热回流滴加30.8g溴丙烷（反应物），制备格氏试剂，降温到20℃，滴加42.8g(0.2mol)（I-15-b）（反应物）的四氢呋喃溶液，搅拌2小时，加入到30ml盐酸水溶液中，水解20分钟，加入乙酸乙酯萃取，旋干。Add 6.6g magnesium chips (reactant) and 200ml tetrahydrofuran (solvent) into a 1L three-necked flask, add 30.8g bromopropane (reactant) dropwise under reflux to prepare Grignard reagent, cool down to 20°C, add dropwise 42.8g (0.2 mol) (I-15-b) (reactant) in tetrahydrofuran, stirred for 2 hours, added to 30ml of hydrochloric acid aqueous solution, hydrolyzed for 20 minutes, added ethyl acetate for extraction, and spin-dried.

另一1L三口瓶中加入上面所得产品，500ml干燥的二氯甲烷（溶剂），氮气保护下，降温至-25～-20℃，滴加63.3ml（0.397mol）三乙基硅氢（反应物），滴毕，向体系中滴加50ml（0.397mol）三氟化硼乙醚（反应物），滴毕保持-25～-20℃搅拌2小时，自然升至0℃，加入碳酸氢钠饱和水溶液（调节PH值）至无气泡放出，分液，水洗至中性，旋干溶剂，产品减压蒸馏得33.9g，收率70%，气相色谱纯度98%。Add the product obtained above, 500ml of dry dichloromethane (solvent) into another 1L three-necked flask, cool down to -25～-20°C under nitrogen protection, add 63.3ml (0.397mol) of triethylsilylhydrogen (reactant) dropwise ), after dropping, add 50ml (0.397mol) boron trifluoride diethyl ether (reactant) dropwise to the system, keep stirring at -25～-20°C for 2 hours after dropping, naturally rise to 0°C, add saturated aqueous solution of sodium bicarbonate (Adjust the pH value) until no bubbles are released, separate the liquids, wash with water until neutral, spin to dry the solvent, and distill the product under reduced pressure to obtain 33.9g, with a yield of 70% and a purity of 98% by gas chromatography.

步骤4（I-15-d）的合成Synthesis of Step 4 (I-15-d)

1L三口瓶中加入48.4g（0.2mol）（I-15-c）（反应物），200ml二氯甲烷（溶剂），10g无水三氯化铁（催化剂），控温10℃下滴加32g（0.2mol）液溴（反应物），滴完搅拌反应10小时，加入300ml水，分液，水洗。常规处理，产品用二倍乙醇重结晶一次，得45g，收率70%，气相色谱纯度98%Add 48.4g (0.2mol) (I-15-c) (reactant), 200ml dichloromethane (solvent), 10g anhydrous ferric chloride (catalyst) to a 1L three-necked flask, and add 32g dropwise at a temperature of 10°C (0.2mol) liquid bromine (reactant), after dripping, stir and react for 10 hours, add 300ml of water, separate liquid, and wash with water. Conventional treatment, the product is recrystallized once with two times of ethanol, and 45g is obtained, the yield is 70%, and the purity of gas chromatography is 98%.

步骤5（I-15-e）的合成Synthesis of Step 5 (I-15-e)

1L三口瓶中加入32.1g（0.1mol）（I-15-d）（反应物），15.8g（0.1mol）3,5-二氟苯硼酸（反应物），0.3g四三苯基膦钯（催化剂），0.2mol碳酸钾，甲苯100ml（溶剂），水100ml乙醇100ml（溶剂），加热回流4小时，降至室温，分液，按常规处理，产品用二倍乙醇重结晶一次，得28.3g，纯度98%Add 32.1g (0.1mol) (I-15-d) (reactant), 15.8g (0.1mol) 3,5-difluorophenylboronic acid (reactant), 0.3g tetrakistriphenylphosphine palladium to a 1L three-necked flask (catalyst), 0.2mol potassium carbonate, toluene 100ml (solvent), water 100ml ethanol 100ml (solvent), heated to reflux for 4 hours, lowered to room temperature, separated liquids, processed as usual, and the product was recrystallized once with double ethanol to obtain 28.3 g, purity 98%

步骤6（I-15-f）的合成Synthesis of Step 6 (I-15-f)

在反应瓶中加入35.4g（0.1mol）（Ⅰ-15-e）（反应物），200ml四氢呋喃（溶剂），通氮气保护，降温至-60℃，滴加0.11mol正丁基锂（反应物），滴加过程控温-55℃～-60℃，滴毕，继续控温搅拌反应1小时。降温至-70℃，滴加28g（0.13mol）二氟二溴甲烷和100ml四氢呋喃的溶液，2小时滴完（反应物），滴加过程控温-65℃～-70℃，滴毕，继续控温搅拌反应30分钟，升温至室温，加入20ml浓盐酸（调节PH值）+50ml水（溶剂）水解，分液，100ml二氯甲烷（溶剂）提取水相，水洗有机相至中性，蒸干溶剂得淡黄色固体46g（Ⅰ-15-f），折纯收率61.7%，液相色谱纯度65%。Add 35.4g (0.1mol) (I-15-e) (reactant) and 200ml tetrahydrofuran (solvent) to the reaction flask, protect with nitrogen, cool to -60°C, add dropwise 0.11mol n-butyllithium (reactant ), the dropwise addition process was controlled at -55°C to -60°C, and after the dropwise addition was completed, the reaction was continued for 1 hour under temperature control and stirring. Cool down to -70°C, add dropwise a solution of 28g (0.13mol) difluorodibromomethane and 100ml tetrahydrofuran, and finish dropping (reactant) in 2 hours. Stir for 30 minutes, warm up to room temperature, add 20ml of concentrated hydrochloric acid (to adjust the pH value) + 50ml of water (solvent) for hydrolysis, separate the liquids, extract the water phase with 100ml of dichloromethane (solvent), wash the organic phase with water until neutral, and evaporate to dryness Solvent was used to obtain 46 g of light yellow solid (I-15-f), with a pure yield of 61.7% and a liquid chromatography purity of 65%.

步骤7step 7

在反应瓶中加入0.1mol（折纯）（Ⅰ-15-f）（反应物）,100mlDMSO（溶剂），0.2mol无水碳酸钾（反应物），0.12mol3，4，5-三氟苯酚（反应物），搅拌加热至65～70℃反应2小时。降温至室温，过滤固体，并用300ml二氯甲烷（溶剂）冲洗滤饼，滤液加入100ml水，搅拌，分液，用200ml二氯甲烷（溶剂）提取水层，水洗有机相至中性，蒸干溶剂。浓缩物溶于500ml甲苯（溶剂），过硅胶柱脱色，用甲苯（溶剂）洗脱，收集洗脱液并蒸除溶剂，所得物用无水乙醇（溶剂）重结晶3次，得到白色针状晶体（Ⅰ-15），收率40%，气相色谱纯度99.9%。Add 0.1mol (reduced pure) (Ⅰ-15-f) (reactant), 100mlDMSO (solvent), 0.2mol anhydrous potassium carbonate (reactant), 0.12mol3,4,5-trifluorophenol ( reactant), stirred and heated to 65-70°C for 2 hours. Cool down to room temperature, filter the solid, and wash the filter cake with 300ml of dichloromethane (solvent), add 100ml of water to the filtrate, stir, separate the layers, extract the aqueous layer with 200ml of dichloromethane (solvent), wash the organic phase with water until neutral, evaporate to dryness solvent. The concentrate was dissolved in 500ml of toluene (solvent), passed through a silica gel column for decolorization, eluted with toluene (solvent), collected the eluate and evaporated to remove the solvent, and the resulting product was recrystallized 3 times with absolute ethanol (solvent) to obtain white needles Crystal (I-15), yield 40%, gas chromatography purity 99.9%.

该产物的结构确认数据如下：The structural confirmation data of this product are as follows:

MP：85℃；MP: 85°C;

MS：m/s%：550（2.3），403(100),252(3.6),278(5.4)；MS: m/s%: 550 (2.3), 403 (100), 252 (3.6), 278 (5.4);

1H-NMR：δ（ppm）0.90(t,3H),1.2,9(m,4H),1.44(m,4H)1.67(m,4H),1.96(m,5H),2.72(，m，1H),6.89(m,2H),7.22(d,2H),7.36（s，4H）；1H-NMR: δ (ppm) 0.90(t, 3H), 1.2, 9(m, 4H), 1.44(m, 4H), 1.67(m, 4H), 1.96(m, 5H), 2.72(, m, 1H ),6.89(m,2H),7.22(d,2H),7.36(s,4H);

由上可知，该产物结构正确，为式I-15所示化合物。As can be seen from the above, the product has a correct structure and is a compound shown in formula I-15.

该化合物的液晶性能如下所示：The liquid crystal properties of this compound are as follows:

CP：120℃；CP: 120°C;

△ε：19.3（20℃，589nm）Δε: 19.3 (20°C, 589nm)

△n：0.135（20℃，1000Hz）Δn: 0.135 (20°C, 1000Hz)

由上可知，该化合物具有光热稳定性，具有宽的液晶态温度范围，较好的低温互溶性，较大的介电各向异性△ε，光学器件使用时可实现较低的阈值电压和低旋转粘度γ₁，可以改善液晶组合物材料和显示器性能，对实现显示器的快速响应具有重要意义。It can be seen from the above that the compound has photothermal stability, wide liquid crystal temperature range, good low-temperature mutual solubility, large dielectric anisotropy △ε, and can achieve lower threshold voltage and The low rotational viscosity γ ₁ can improve the properties of the liquid crystal composition material and the display, and is of great significance for realizing the fast response of the display.

实施例3、

步骤1（Ⅰ-16-a）的合成Synthesis of Step 1 (I-16-a)

反应瓶中加入步骤得到的0.1mol(Ⅰ-15-d)（反应物）,120ml四氢呋喃（溶剂），安装密封搅拌，通氮气置换空气，降温至-70℃，滴加0.1mol浓度为2.5M的丁基锂（反应物），加完后20分钟，通入干燥的二氧化碳气体（反应物），至饱和，在此温度下反应2小时，将此反应液倒入有20ml浓盐酸（调节PH值）和100ml水的烧杯中水解，分液，50ml乙酸乙酯（溶剂）提取水相一次，合并有机相，饱和食盐水洗至中性，无水硫酸钠（干燥剂）干燥，浓缩除尽溶剂，得到浅黄色固体，用2倍甲苯和1倍乙酸乙酯（溶剂）重结晶一次，得到白色晶体（Ⅰ-16-a）。收率90%，液相色谱纯度98.0%。Add 0.1mol (Ⅰ-15-d) (reactant) obtained in the step to the reaction bottle, 120ml tetrahydrofuran (solvent), install and seal the stirring, replace the air with nitrogen, cool down to -70°C, add dropwise 0.1mol concentration of 2.5M butyllithium (reactant), 20 minutes after the addition, dry carbon dioxide gas (reactant), to saturation, reacted at this temperature for 2 hours, pour this reaction solution into 20ml concentrated hydrochloric acid (adjust pH Value) and 100ml water in a beaker for hydrolysis, liquid separation, 50ml ethyl acetate (solvent) to extract the water phase once, combine the organic phase, wash with saturated saline until neutral, dry with anhydrous sodium sulfate (desiccant), concentrate to remove the solvent , to obtain a light yellow solid, which was recrystallized once with 2 times of toluene and 1 times of ethyl acetate (solvent) to obtain white crystals (I-16-a). The yield is 90%, and the liquid chromatography purity is 98.0%.

步骤2step 2

反应瓶中加入0.1mol(Ⅰ-16-a)，30ml甲苯（溶剂）和30ml异辛烷（溶剂），加入14g1,3-丙二硫醇（反应物），搅拌下将上述悬浮液加热至50℃，在30分钟内加入三氟甲磺酸（反应物）19.2g，加完后升温至回流，分出生成的水，待分净水后，冷却降温至50℃，加入甲基叔丁基醚（溶剂）100ml，继续降温，析出晶体，在氮气保护下过滤，得到的晶体用甲基叔丁基醚（溶剂）（25ml×4）洗涤，真空干燥得到橙色晶体（二噻烷三氟甲磺酸盐）。Add 0.1mol (I-16-a), 30ml toluene (solvent) and 30ml isooctane (solvent) to the reaction flask, add 14g 1,3-propanedithiol (reactant), and heat the above suspension to 50°C, add 19.2g of trifluoromethanesulfonic acid (reactant) within 30 minutes, raise the temperature to reflux after the addition, separate the generated water, cool down to 50°C after separating the purified water, add methyl tert-butyl Base ether (solvent) 100ml, continue to cool down, crystals are precipitated, filtered under nitrogen protection, the obtained crystals are washed with methyl tert-butyl ether (solvent) (25ml×4), and dried in vacuum to obtain orange crystals (dithianetrifluoro mesylate).

步骤3step 3

在反应瓶中加入0.1mol3，4，5-三氟苯酚（反应物），0.1mol三乙胺（反应物）和130ml二氯甲烷（溶剂）的混合溶液并冷却至-70℃，滴加上述0.1mol（二噻烷三氟甲磺酸盐）晶体（反应物）的120ml二氯甲烷（溶剂）的溶液，45分钟加完，在此温度搅拌一小时后，5分钟内加入0.4mol NEt₃·3HF（反应物）。然后在-70℃下，一小时内加入0.4mol液溴（反应物）的30ml二氯甲烷（溶剂）溶液，然后在-70℃下继续反应一小时，升温至0℃，将反应液倒入32%的160ml氢氧化钠水溶液（调节PH值）和300g冰中，通过滴加大约45g32%氢氧化钠水溶液来调节反应液的PH值至5～8。分液后水相用80ml二氯甲烷（溶剂）提取，合并有机相用4g硅藻土（脱色剂）过滤，水洗，减压下蒸干溶剂。得到的粗产物柱层析后石油醚（溶剂）重结晶，得到白色晶体产品（Ⅰ-16），收率45%，GC：99.8%。Add a mixed solution of 0.1mol 3,4,5-trifluorophenol (reactant), 0.1mol triethylamine (reactant) and 130ml dichloromethane (solvent) into the reaction flask and cool to -70°C, add the above A solution of 0.1 mol (dithiane trifluoromethanesulfonate) crystals (reactant) in 120 ml of dichloromethane (solvent) was added in 45 minutes. After stirring at this temperature for one hour, 0.4 mol NEt ₃ was added within 5 minutes • 3HF (reactant). Then at -70°C, add 0.4mol liquid bromine (reactant) in 30ml dichloromethane (solvent) solution within one hour, then continue the reaction at -70°C for one hour, raise the temperature to 0°C, and pour the reaction solution into 160ml of 32% sodium hydroxide aqueous solution (to adjust the pH value) and 300g of ice, by adding about 45g of 32% sodium hydroxide aqueous solution dropwise to adjust the pH value of the reaction solution to 5-8. After liquid separation, the aqueous phase was extracted with 80ml of dichloromethane (solvent), and the combined organic phases were filtered with 4g of diatomaceous earth (decolorizer), washed with water, and the solvent was evaporated to dryness under reduced pressure. The obtained crude product was recrystallized from petroleum ether (solvent) after column chromatography to obtain a white crystal product (I-16), with a yield of 45%, GC: 99.8%.

该产物的结构确认数据如下：The structural confirmation data of this product are as follows:

MP：50℃MP: 50°C

MS：m/s%438（5.6），291(100),148(13.7),140(8.7),MS: m/s%438 (5.6), 291 (100), 148 (13.7), 140 (8.7),

1H-NMR：δ（ppm）0.90(t,3H),1.28(m,4H),1.44(m,4H)1.72(m,6H),1.97(m,3H),2.72(，m，1H),6.89(m,2H),7.25(m,4H)1H-NMR: δ (ppm) 0.90 (t, 3H), 1.28 (m, 4H), 1.44 (m, 4H), 1.72 (m, 6H), 1.97 (m, 3H), 2.72 (, m, 1H), 6.89(m,2H),7.25(m,4H)

由上可知，该产物结构正确，为式I-16所示化合物。As can be seen from the above, the product has a correct structure and is a compound shown in formula I-16.

该化合物的液晶性能如下所示：The liquid crystal properties of this compound are as follows:

△ε：12.3（20℃，589nm）△ε: 12.3 (20°C, 589nm)

△n：0.115（20℃，1000Hz）Δn: 0.115 (20°C, 1000Hz)

由上可知，该化合物具有光热稳定性，具有宽的液晶态温度范围，较好的低温互溶性，较大的介电各向异性△ε，光学器件使用时可实现较低的阈值电压和低旋转粘度γ₁，可以改善液晶组合物材料和显示器性能，对实现显示器的快速响应具有重要意义。It can be seen from the above that the compound has photothermal stability, wide liquid crystal temperature range, good low-temperature mutual solubility, large dielectric anisotropy △ε, and can achieve lower threshold voltage and The low rotational viscosity γ ₁ can improve the properties of the liquid crystal composition material and the display, and is of great significance for realizing the fast response of the display.

实施例4、

步骤1step 1

反应瓶中加入0.1mol(Ⅰ-16-a),冰乙酸100ml，5%Pt/C10g,搅拌下常压加氢6小时，过滤除去催化剂，蒸干溶剂，加入50ml甲苯重结晶，收率50%得（Ⅰ-17-a）Add 0.1mol (I-16-a), 100ml of glacial acetic acid, 10g of 5% Pt/C to the reaction flask, hydrogenate under normal pressure for 6 hours under stirring, remove the catalyst by filtration, evaporate the solvent to dryness, add 50ml of toluene for recrystallization, the yield is 50 % get (Ⅰ-17-a)

步骤2step 2

反应瓶中加入0.1mol(Ⅰ-17-a)，30ml甲苯（溶剂）和30ml异辛烷（溶剂），加入14g1,3-丙二硫醇（反应物），搅拌下将上述悬浮液加热至50℃，在30分钟内加入三氟甲磺酸（反应物）19.2g，加完后升温至回流，分出生成的水，待分净水后，冷却降温至90℃，在70-90℃之间45分钟内加入甲基叔丁基醚（溶剂）100ml，继续降温，析出晶体，在氮气保护下过滤，得到的晶体用甲基叔丁基醚（溶剂）（25ml×4）洗涤，真空干燥得到橙色晶体（二噻烷三氟甲磺酸盐）。Add 0.1mol (I-17-a), 30ml toluene (solvent) and 30ml isooctane (solvent) to the reaction flask, add 14g 1,3-propanedithiol (reactant), and heat the above suspension to 50°C, add 19.2g of trifluoromethanesulfonic acid (reactant) within 30 minutes, raise the temperature to reflux after the addition, separate the generated water, and cool down to 90°C after separating the purified water. Add 100ml of methyl tert-butyl ether (solvent) within 45 minutes, continue to cool down, precipitate crystals, filter under nitrogen protection, and wash the obtained crystals with methyl tert-butyl ether (solvent) (25ml×4), vacuum Drying gave orange crystals (dithiane triflate).

步骤3step 3

在反应瓶中加入0.1mol3,4,5-三氟苯酚（反应物），0.1mol三乙胺（反应物）和130ml二氯甲烷（溶剂）的混合溶液并冷却至-70℃，滴加上述0.1mol（二噻烷三氟甲磺酸盐）晶体（反应物）的120ml二氯甲烷（溶剂）的溶液，45分钟加完，在此温度搅拌一小时后，5分钟内加入0.4mol NEt₃·3HF（反应物）。然后在-70℃下，一小时内加入0.4mol液溴（反应物）的30ml二氯甲烷（溶剂）溶液，然后在-70℃下继续反应一小时，升温至0℃，将反应液倒入32%的160ml氢氧化钠水溶液（调节PH值）和300g冰中，通过滴加大约45g32%氢氧化钠水溶液来调节反应液的PH值至5～8。分液后水相用80ml二氯甲烷（溶剂）提取，合并有机相用4g硅藻土（脱色剂）过滤，水洗，减压下蒸干溶剂。得到的粗产物柱层析后石油醚（溶剂）重结晶，得到白色晶体产品（Ⅰ-17），收率45%，GC：99.5%。Add a mixed solution of 0.1mol 3,4,5-trifluorophenol (reactant), 0.1mol triethylamine (reactant) and 130ml dichloromethane (solvent) into the reaction flask and cool to -70°C, add the above A solution of 0.1 mol (dithiane trifluoromethanesulfonate) crystals (reactant) in 120 ml of dichloromethane (solvent) was added in 45 minutes. After stirring at this temperature for one hour, 0.4 mol NEt ₃ was added within 5 minutes • 3HF (reactant). Then at -70°C, add 0.4mol liquid bromine (reactant) in 30ml dichloromethane (solvent) solution within one hour, then continue the reaction at -70°C for one hour, raise the temperature to 0°C, and pour the reaction solution into 160ml of 32% sodium hydroxide aqueous solution (to adjust the pH value) and 300g of ice, by adding about 45g of 32% sodium hydroxide aqueous solution dropwise to adjust the pH value of the reaction solution to 5-8. After liquid separation, the aqueous phase was extracted with 80ml of dichloromethane (solvent), and the combined organic phases were filtered with 4g of diatomaceous earth (decolorizer), washed with water, and the solvent was evaporated to dryness under reduced pressure. The obtained crude product was recrystallized from petroleum ether (solvent) after column chromatography, and the product (I-17) was obtained as white crystals in a yield of 45%, GC: 99.5%.

该产物的结构确认数据如下：The structural confirmation data of this product are as follows:

MP：35℃；MP: 35°C;

MS：m/s%444（45.3），296(56.8),148(37.4),69(100),MS: m/s%444 (45.3), 296 (56.8), 148 (37.4), 69 (100),

1H-NMR：δ（ppm）0.90(t,3H),1.27(m,10H),1.45(m,12H)1.72(m,2H),1.96(m,3H),2.48(，m，1H),6.89(m,2H)1H-NMR: δ (ppm) 0.90(t, 3H), 1.27(m, 10H), 1.45(m, 12H), 1.72(m, 2H), 1.96(m, 3H), 2.48(, m, 1H), 6.89(m,2H)

由上可知，该产物结构正确，为式I-17所示化合物。As can be seen from the above, the product has a correct structure and is a compound shown in formula I-17.

该化合物的液晶性能如下所示：The liquid crystal properties of this compound are as follows:

△ε：9.5（20℃，589nm）△ε: 9.5 (20°C, 589nm)

△n：0.065（20℃，1000Hz）Δn: 0.065 (20°C, 1000Hz)

由上可知，该化合物具有光热稳定性，具有宽的液晶态温度范围，较好的低温互溶性，较大的介电各向异性△ε，光学器件使用时可实现较低的阈值电压和低旋转粘度γ₁，可以改善液晶组合物材料和显示器性能，对实现显示器的快速响应具有重要意义。It can be seen from the above that the compound has photothermal stability, wide liquid crystal temperature range, good low-temperature mutual solubility, large dielectric anisotropy △ε, and can achieve lower threshold voltage and The low rotational viscosity γ ₁ can improve the properties of the liquid crystal composition material and the display, and is of great significance for realizing the fast response of the display.

参照实施例1-4，仅按照产物的结构式相应替换反应物结构式中的基团，得到如下式I所示化合物：With reference to Examples 1-4, only correspondingly replace the group in the reactant structural formula according to the structural formula of the product, obtain the compound shown in the following formula I:

实施例3、液晶混合物aEmbodiment 3, liquid crystal mixture a

按照如下重量份将各组分混匀，得到本发明提供的液晶混合物a：Mix the components according to the following parts by weight to obtain the liquid crystal mixture a provided by the invention:

该混合物的性能如下所示：The properties of this mixture are as follows:

△n：0.105；Δn: 0.105;

cp[℃]：95℃；cp[°C]: 95°C;

△ε：7.2；△ε: 7.2;

γ₁：65。Gamma _1:65 .

由上可知，该混合物具有适当高的清亮点，适当的光学各向异性，较低的旋转粘度和较快的响应速度，可适用于液晶显示器中，尤其适用与TN-TFT，IPS-TFT显示模式。It can be seen from the above that the mixture has a suitable high clearing point, suitable optical anisotropy, low rotational viscosity and fast response speed, and can be used in liquid crystal displays, especially suitable for TN-TFT and IPS-TFT displays model.

实施例4、液晶混合物bEmbodiment 4, liquid crystal mixture b

按照如下重量份将各组分混匀，得到本发明提供的液晶混合物b：Mix the components according to the following parts by weight to obtain the liquid crystal mixture b provided by the invention:

该混合物的性能如下所示：The properties of this mixture are as follows:

△n：0.110；Δn: 0.110;

cp[℃]：94℃；cp[°C]: 94°C;

△ε：7.0；△ε: 7.0;

γ₁：60。Gamma _1:60 .

由上可知，该混合物具有高的清亮点，适当的光学各向异性，低的旋转粘度和较快的响应速度，可适用于液晶显示器中。It can be seen from the above that the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be suitable for liquid crystal displays.

实施例5、液晶混合物cEmbodiment 5, liquid crystal mixture c

按照如下重量份将各组分混匀，得到本发明提供的液晶混合物c：Mix the components according to the following parts by weight to obtain the liquid crystal mixture c provided by the present invention:

该混合物的性能如下所示：The properties of this mixture are as follows:

△n：0.095；Δn: 0.095;

cp[℃]：100℃；cp[°C]: 100°C;

△ε：8.0；△ε: 8.0;

γ₁：78。Gamma _1:78 .

由上可知，该混合物具有高的清亮点，适当的光学各向异性，低的旋转粘度和较快的响应速度，可适用于液晶显示器中。It can be seen from the above that the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be suitable for liquid crystal displays.

实施例6、液晶混合物dEmbodiment 6, liquid crystal mixture d

按照如下重量份将各组分混匀，得到本发明提供的液晶混合物d：Mix the components uniformly according to the following parts by weight to obtain the liquid crystal mixture d provided by the present invention:

单体                                            重量百分比Monomer Weight %

                                                            （%）(%)

该混合物的性能如下所示：The properties of this mixture are as follows:

△n：0.090；Δn: 0.090;

cp[℃]：85℃；cp[°C]: 85°C;

△ε：8.5；△ε: 8.5;

γ₁：55。Gamma _1:55 .

由上可知，该混合物具有高的清亮点，适当的光学各向异性，低的旋转粘度和较快的响应速度，可适用于液晶显示器中。It can be seen from the above that the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be suitable for liquid crystal displays.

实施例7、液晶混合物eEmbodiment 7, liquid crystal mixture e

按照如下重量份将各组分混匀，得到本发明提供的液晶混合物e：Mix the components uniformly according to the following parts by weight to obtain the liquid crystal mixture e provided by the present invention:

该混合物的性能如下所示：The properties of this mixture are as follows:

△n：0.100；Δn: 0.100;

cp[℃]：105℃；cp[°C]: 105°C;

△ε：6.5；△ε: 6.5;

γ₁：70。Gamma _1:70 .

由上可知，该混合物具有高的清亮点，适当的光学各向异性，低的旋转粘度和较快的响应速度，可适用于液晶显示器中。It can be seen from the above that the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be suitable for liquid crystal displays.