CN104496742A - Liquid crystal compound, liquid crystal composition and application of liquid crystal compound and liquid crystal composition - Google Patents

Liquid crystal compound, liquid crystal composition and application of liquid crystal compound and liquid crystal composition Download PDF

Info

Publication number
CN104496742A
CN104496742A CN 201410841681 CN201410841681A CN104496742A CN 104496742 A CN104496742 A CN 104496742A CN 201410841681 CN201410841681 CN 201410841681 CN 201410841681 A CN201410841681 A CN 201410841681A CN 104496742 A CN104496742 A CN 104496742A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
formula
compound
liquid crystal
composition
step
Prior art date
Application number
CN 201410841681
Other languages
Chinese (zh)
Other versions
CN104496742B (en )
Inventor
田肖雄
Original Assignee
京东方科技集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Abstract

The invention discloses a liquid crystal compound and a liquid crystal composition. The structural formula of the liquid crystal compound is shown in a formula I. The liquid crystal composition provided by the invention is a composition containing the liquid crystal compound. The liquid crystal compound disclosed by the invention is a novel 7-hydrobenzo[de] anthracene liquid crystal compound which has relatively good physical and chemical stabilities and a relatively high clearing point. The liquid crystal composition comprising the compound has a relatively wide nematic phase range, so that the application field is extremely expanded. The formula is shown in the description.

Description

一种液晶化合物、组合物及其应用 A liquid crystal compounds, compositions and uses thereof

技术领域 FIELD

[0001] 本发明涉及一种液晶化合物以及包括所述液晶化合物的组合物及其应用,更具体的说,本发明涉及一种7-氢苯[de]并蒽类液晶化合物及包括所述化合物的组合物及其应用。 [0001] The present invention relates to a composition comprising a liquid crystalline compound and liquid crystal composition of the compound and its application, and more particularly, the present invention relates to a hydrogen phenyl 7- [de] anthracene-based liquid crystal compound and the compound comprising the compositions and uses thereof.

背景技术 Background technique

[0002] 液晶显示器现在广泛应用在社会生活的各个方面,液晶显示技术发展至今,各种各样的液晶化合物得到实际的应用。 [0002] LCD monitors are now widely used in various aspects of social life, liquid crystal display technology development so far, a variety of liquid crystal compounds obtained practical application. 一些通用的对液晶化合物的要求,包括液晶化合物的相变温度,光学各向异性,介电各向异性,粘度,电阻率等,都对液晶材料最终的应用有着很大的影响。 Some common liquid crystal compound, comprising a liquid crystal phase transition temperature of the compound, optical anisotropy, dielectric anisotropy, viscosity, resistivity, etc., the final application of the liquid crystal material has a great impact. 新的液晶化合物的开发以及其组成的组合物,来改善液晶的各种性质,改善液晶显示的应用效果极其重要。 The development of new liquid crystal compounds and compositions of the composition to improve various properties of liquid crystals, the effect of improving the application of the liquid crystal display is extremely important.

发明内容 SUMMARY

[0003] 发明了一种新的化合物,此化合物具有液晶特性,可用于液晶组合物中,用于液晶显示器。 [0003] The invention is a novel compound, having liquid crystal properties of this compound, it can be used in liquid crystal composition, a liquid crystal display. 该化合物具有较好的物理和化学稳定性和较高的清亮点。 The compound has good physical and chemical stability and high clearing points.

[0004] 本发明提供的化合物,即7-氢苯[de]并蒽类液晶化合物,其结构式如式I所示: [0004] The present invention provides compounds, i.e., benzene, hydrogen 7- [de] anthracene-based liquid crystal compounds and having the formula as shown in Formula I:

[0005] [0005]

Figure CN104496742AD00071

[0006] 本发明还提供制备所述的液晶化合物的方法,包括以下步骤: The method of the liquid crystal compound [0006] The present invention further provides the preparation, comprising the steps of:

[0007] 步骤a.使式II所示的化合物在四氢呋喃中与N-溴代丁二酰亚胺进行溴代反应,以得到式1-2所示的化合物;反应式如下所示: . [0007] Step a compound of the formula II shown in tetrahydrofuran brominated with N- bromosuccinimide, to give a compound represented by formula 1-2; reaction scheme is shown below:

[0008] [0008]

Figure CN104496742AD00072

[0009] 步骤b.使在步骤a中获得的式1-2所示的化合物与丙基溴化镁在甲苯中在催化剂存在下进行反应得到式1-3所示的化合物;反应式如下所示: . [0009] Step b of formula obtained in step with a compound represented by 1-2 propylmagnesium bromide in the presence of a catalyst in toluene to obtain the compound of formula 1-3; reaction scheme as follows It shows:

[0010] [0010]

Figure CN104496742AD00081

[0011] 步骤c.使在步骤b中获得式1-3所示的化合物在二氯甲烷中与溴进行溴代反应, 以得到式1-4所示的化合物;反应式如下所示: . [0011] Step c so as to obtain a compound represented by formula 1-3 bromination with bromine in methylene chloride in step b, to obtain a compound represented by formula 1-4; reaction scheme is shown below:

[0012] [0012]

Figure CN104496742AD00082

[0013] 步骤d.使在步骤c中获得的式1-4所示的化合物制成格氏试剂后与 [0013] Step d. Formula obtained in step c compound shown in Figure 1-4 and the prepared Grignard reagent

Figure CN104496742AD00083

在四氢呋喃中进行加成反应,然后进行脱水、还原,以得到式1-5所示的化合物;反应式如下所示: Addition reaction in tetrahydrofuran, followed by dehydration, reduction, to give a compound represented by formula 1-5; reaction scheme is shown below:

[0014] [0014]

Figure CN104496742AD00084

[0015] 步骤e.使在步骤d中获得的式1-5所示的化合物在甲苯中用甲酸进行水解,得到式1-6所示的化合物;反应式如下所示: . [0015] Step e of formula obtained in step d compound shown in Figure 1-5 with formic acid in toluene is hydrolyzed to obtain the compound of formula 1-6; reaction scheme is shown below:

Figure CN104496742AD00085

[0017] 步骤f.使在步骤e中获得的式1-6所示的化合物与甲氧基甲基三苯基氯化鱗、叔丁醇钾进行维蒂希反应,然后用盐酸水解,以得到式1-7所示的化合物;反应式如下所示: [0017] to step f. Of the formula obtained in step e 1-6 compound represented methoxymethyl triphenylphosphonium chloride scales, potassium t-butoxide Wittig reaction, and then hydrolyzed with hydrochloric acid, to obtain the compound of formula 1-7; reaction scheme is shown below:

[0018] [0018]

Figure CN104496742AD00086

[0019] 步骤g.式1-7所示的化合物经硼氢化钠还原得到式1-8所示的化合物;反应式如下所示: [0019] Step g reduction of the compound of Formula 1-7 to give a compound of formula 1-8 by sodium borohydride; the reaction formula as follows:

[0020] [0020]

Figure CN104496742AD00091

[0021] 步骤h.式1-8所示的化合物在二氯甲烷中和对甲苯磺酰氯反应生成式1-9所示的化合物;反应式如下所示: [0021] Step h in the compound represented by the formula 1-8 compound represented by Formula 1-9 methylene chloride and p-toluenesulfonyl chloride; reaction scheme is shown below:

Figure CN104496742AD00092

[0023] 步骤i.式1-9所示的化合物和烯丙基溴化镁进行偶联反应得到式I所示的化合物; [0023] Step i and allylmagnesium bromide compound of the formula as shown for compound 1-9 to give a coupling reaction shown in formula I;

Figure CN104496742AD00093

[0025] 本发明还提供含有所述的液晶化合物的组合物。 [0025] The present invention further provides a liquid crystal composition containing the compound of the.

[0026] 在本发明的一个实施方式中,本发明的组合物包括式I所示的化合物、式II所示的化合物、式ΠΙ所示的化合物、式IV所示的化合物、式V所示的化合物、式VI所示的化合物和式VII所示的化合物; [0026] In one embodiment of the invention, the compounds of the present invention comprises a composition of Formula I, the compounds represented by formulas II, a compound of formula ΠΙ, the compound of Formula IV, Formula V , compounds of formula VI and a compound of formula VII shown;

[0027] [0027]

Figure CN104496742AD00101

[0028] 其中,所述组合物包括的组分组成分别为: [0028] wherein the composition comprises constituents were:

[0029] 式I所示的化合物5〜20% ; Compound [0029] Formula I 5~20%;

[0030] 式II所示的化合物4〜8% ; A compound represented by [0030] Formula II 4~8%;

[0031] 式III所示的化合物8〜16% ; Compound [0031] represented by Formula III 8~16%;

[0032] 式IV所示的化合物7〜20 % Compound [0032] represented by Formula IV 7~20%

[0033] 式V所示的化合物8〜15 % A compound represented by [0033] formula V 8~15%

[0034] 式VI所示的化合物7〜20 %,和 Compound 7~20% [0034] shown in formula VI, and

[0035] 式VII所示的化合物8〜60%。 A compound represented by [0035] Formula VII 8~60%.

[0036] 其中,在本发明一个技术方案中,本发明的组合物由下述组分组成: [0036] wherein, in one aspect of the present invention, the compositions of the present invention consists of the following components:

[0037] 式I所示的化合物5〜20% ; Compound [0037] Formula I 5~20%;

[0038] 式II所示的化合物4〜8% ; A compound represented by [0038] Formula II 4~8%;

[0039] 式III所示的化合物8〜16% ; Compound [0039] represented by Formula III 8~16%;

[0040] 式IV所示的化合物7〜20 % Compound [0040] represented by Formula IV 7~20%

[0041] 式V所示的化合物8〜15 % A compound represented by [0041] formula V 8~15%

[0042] 式VI所示的化合物7〜20 %,和 Compound 7~20% [0042] shown in formula VI, and

[0043] 式VII所示的化合物30〜60%。 A compound represented by [0043] Formula VII 30~60%.

[0044] 优选的,所述组合物由下述组分组成: [0044] Preferably, the composition consists of the following components:

[0045] 式I所示的化合物8% ; Compound [0045] 8% of Formula I;

[0046] 式II所示的化合物6% ; A compound represented by [0046] Formula II 6%;

[0047] 式III所示的化合物15% ; Compound [0047] represented by Formula III 15%;

[0048] 式IV所示的化合物15% Compound [0048] represented by the formula IV 15%

[0049] 式V所示的化合物10 % A compound represented by [0049] 10% of the Formula V

[0050] 式VI所示的化合物9 %,和 Compound [0050] 9% as shown in formula VI, and

[0051] 式VII所示的化合物37%。 A compound represented by [0051] formula VII 37%.

[0052] 在本发明的另一个技术方案中,本发明的组合物所述组合物中还包括式VIII所示的化合物、式IX所示的化合物和式X所示的化合物; [0052] In another aspect of the present invention, the composition of the composition of the present invention further comprises compounds of formula, the compound of formula IX and a compound represented by formula X as shown in VIII;

[0053] [0053]

Figure CN104496742AD00111

[0054] 在本发明的又一个技术方案中,本发明的组合物由下述组分组成: [0054] In yet another aspect of the present invention, the compositions of the present invention consists of the following components:

[0055] 式I所示的化合物8〜18% ; Compound [0055] Formula I 8~18%;

[0056] 式II所示的化合物5〜6% ; A compound represented by [0056] Formula II 5~6%;

[0057] 式III所示的化合物10〜12% ; Compound [0057] represented by Formula III 10~12%;

[0058] 式IV所示的化合物10〜15% Compound [0058] represented by the formula IV 10 ~ 15%

[0059] 式V所示的化合物10〜13% A compound represented by [0059] formula V 10~13%

[0060] 式VI所示的化合物8〜15%, As shown in [0060] a compound of formula VI 8~15%,

[0061] 式VII所示的化合物8-18% A compound represented by [0061] formula VII 8-18%

[0062] 式VIII所示的化合物15〜22% ;和, [0062] The compound of Formula VIII 15~22%; and,

[0063] 式XI所示的化合物8〜15%。 A compound represented by [0063] Formula XI 8~15%.

[0064] 优选的,所述组合物由下述组分组成: [0064] Preferably, the composition consists of the following components:

[0065] 式I所示的化合物10% ; Compound [0065] 10% of Formula I;

[0066] 式II所示的化合物5% ; A compound represented by [0066] Formula II 5%;

[0067] 式III所示的化合物12% ; Compound [0067] represented by Formula III 12%;

[0068] 式IV所示的化合物12% Compound [0068] represented by the formula IV 12%

[0069] 式V所示的化合物11 % A compound represented by [0069] formula V 11%

[0070] 式VI所示的化合物8 %, As shown in [0070] 8% of a compound of formula VI,

[0071] 式VII所示的化合物12% A compound represented by [0071] Formula VII, 12%

[0072] 式VIII所示的化合物20% ;和, [0072] The compound of Formula VIII 20%; and,

[0073] 式XI所示的化合物10%。 A compound represented by [0073] Formula XI 10%.

[0074] 上述液晶化合物或所述的组合物在制备液晶显示装置中的应用也属于本发明的保护范围。 [0074] The liquid crystal compound or composition in the manufacture of liquid crystal display device applications are also within the scope of the present invention.

[0075] 基于上述技术方案,本发明的液晶化合物是一种新的7-氢苯[de]并蒽类液晶化合物,该化合物具有较好的物理和化学稳定性和较高的清亮点。 [0075] Based on the above technical solution, the liquid crystal compounds of the present invention is a novel 7- hydrobenzo [de] anthracene-based liquid crystal compound which has good physical and chemical stability and high clearing points. 本发明提供的包含本发明化合物的液晶组合物具有较宽的向列相范围,极大的拓宽了应用领域。 The present invention provides a liquid crystal composition comprising a compound of the present invention has a wide nematic phase range, greatly broadening the application field.

附图说明 BRIEF DESCRIPTION

[0076] 图1为本发明液晶化合物的IH-NMR谱图。 [0076] FIG. 1 IH-NMR spectrum of the liquid crystal compounds of the invention.

具体实施方式 detailed description

[0077] 基于本发明,提供一种液晶化合物,其结构式如式I所示: [0077] Based on the present invention, there is provided a liquid crystal compound having the structural formula shown in Formula I:

[0078] [0078]

Figure CN104496742AD00121

[0079] 式I所示的化合物的合成流程如下所示: Synthetic Scheme I as compounds of the [0079] formula is as follows:

[0080] [0080]

Figure CN104496742AD00131

[0081] 本发明还提供含有所述的液晶化合物的组合物。 [0081] The present invention further provides a liquid crystal composition containing the compound of the.

[0082] 在本发明的一个实施方式中,本发明的组合物包括式I所示的化合物、式II所示的化合物、式ΠΙ所示的化合物、式IV所示的化合物、式V所示的化合物、式VI所示的化合物和VII所示的化合物; [0082] In one embodiment of the invention, the compounds of the present invention comprises a composition of Formula I, the compounds represented by formulas II, a compound of formula ΠΙ, the compound of Formula IV, Formula V , compounds VII and a compound represented by formula VI;

[0083] [0083]

Figure CN104496742AD00141

[0084] 在本发明的另一个实施方式中,本发明的组合物所述组合物中还包括式VIII所示的化合物和式IX所示的化合物; [0084] In another embodiment of the present invention, the composition of the composition of the present invention further comprises a compound of formula IX and formula VIII as shown in FIG;

Figure CN104496742AD00142

[0085] [0085]

[0086] [0086]

[0087] 实施例 [0087] Example

Figure CN104496742AD00151

[0088] 在下述实施例中涉及的液晶组合物中,除式I所示的液晶化合物以外,其它原料或组分均由市售购得。 [0088] In the following embodiment relates to a liquid crystal composition in the embodiment, other than the liquid crystal compound represented by Formula I, or other materials by commercially available components.

[0089] 实施例1、式I所示的液晶化合物的制备 Preparation of the liquid crystal compound [0089] Embodiment 1, in the illustrated embodiment of Formula I

[0090] [0090]

Figure CN104496742AD00152

[0091] 步骤a.在250ml三口瓶中,将2. 5克具有下式II的化合物7, 7-二甲基-7H-苯并[de]蒽(根据专利W02011/115378制备)溶解在50ml四氢呋喃中,在搅拌下加入1.8 克N-溴代丁二酰亚胺,升温至35°C反应1小时,然后,加入80毫升水,析出黄色固体,过滤, 干燥,产品质谱(m/e) :324,得到式1-2的化合物。 [0091] Step a. In 250ml three-neck flask, 2.5 g the compound has the formula II, 7, 7-dimethyl--7H- benzo [de] anthracene (Patent W02011 / 115378 was prepared according to) was dissolved in 50ml tetrahydrofuran, with stirring 1.8 g of N- bromosuccinimide, warmed to 35 ° C for 1 hour, then 80 ml of water, the precipitated yellow solid was filtered and dried, the product mass spectrum (m / e) : 324, to give compounds of formula 1-2. 反应式如下: The following reaction formula:

[0092] [0092]

Figure CN104496742AD00153

[0093] 步骤b.在250ml三口瓶中,将2. 9克在步骤a中获得的具有式1-2的化合物溶解在50ml甲苯中,然后加入催化量(大约0· Ig)的四(三苯基磷)钯催化剂,搅拌下于30°C 滴加27克15 %的丙基溴化镁的四氢呋喃溶液,然后保温反应3小时,加水,分液,有机层水洗后硫酸镁干燥,硅胶柱层析,石油醚:二氯甲烷=10 :1洗脱,得到产品,产品质谱(m/ e) :286,得到式1-3的化合物。 [0093] Step b. In 250ml three-neck flask, 2.9 g compound having the formula 1-2 is dissolved in 50ml of toluene, followed by addition of a catalytic amount (about 0 · Ig) of tetrakis (obtained in step a. triphenylphosphine) palladium catalyst, stirring at 30 ° C was added dropwise 27 g of 15% tetrahydrofuran solution of propyl magnesium bromide, and then incubated for 3 hours, water was added, after liquid separation, the organic layer was washed with water dried over magnesium sulfate, silica gel column chromatography, petroleum ether: dichloromethane = 10: 1 to give the product, the product mass spectrum (m / e): 286, to give compounds of formula 1-3. 其中反应式如下: Wherein the reaction is as follows:

[0094] [0094]

Figure CN104496742AD00154

7 7

[0095] 步骤c. 250ml三口瓶中,将2. 55克在步骤b获得的具有式1-3的化合物溶解在50ml二氯甲烷中,控制反应温度保持在25°C,滴加I. 6g溴的5毫升二氯甲烷溶液。 [0095] Step c. 250ml three-neck flask, and 2.55 g of a compound having the formula 1-3 is dissolved in 50ml of methylene chloride, controlling the reaction temperature was maintained at 25 ° C, was added dropwise I. 6g obtained in step b 5 ml of methylene chloride solution of bromine. 加毕维持25°C反应2小时,加水,分液,有机层亚硫酸氢钠水溶液洗涤,水洗,硫酸镁干燥,硅胶柱层析,石油醚:二氯甲烷=10 :1洗脱,得到产品,产品质谱(m/e) :366,得到式1-4的化合物。 After complete addition maintain 25 ° C for 2 hours, water was added, liquid separation, washed with aqueous sodium bisulfite organic layer was washed with water, dried over magnesium sulfate, and column chromatography on silica gel, petroleum ether: dichloromethane = 10: 1 to give the product product mass spectrum (m / e): 366, to give compounds of formula 1-4. 其反应式如下: Reaction is as follows:

[0096] [0096]

Figure CN104496742AD00161

[0097] 步骤d. 250ml三口瓶中加入0· 28克金属镁,5毫升四氢呋喃,少量1,2_二溴乙烷, 反应引发后,在搅拌下,滴加3. 5克在步骤c中获得的具有式1-4的化合物溶于20ml四氢呋喃中的溶液,加毕,回流反应30分钟后制得格氏试剂,然后降温至25°C。 [0097] Step d. 250ml three-neck flask was added 0.28 g of metallic magnesium, 5 ml of tetrahydrofuran, a small amount 1,2_ dibromoethane, after the reaction initiation, with stirring, a solution of 3.5 g in step c a compound having the formula 1-4 was dissolved in 20ml of tetrahydrofuran was added, the addition was complete, the reaction was refluxed for 30 minutes to prepare a Grignard reagent, and then cooled to 25 ° C. 向其中加入2. 7 克 Thereto was added 2.7 g

Figure CN104496742AD00162

和10毫升四氢呋喃配成的溶液,加毕,回流30分钟,然后降至室温,加入氯化铵溶液水解。 And 10 ml of tetrahydrofuran was dubbed, the addition was completed, refluxed for 30 minutes, then lowered to room temperature, hydrolyzed ammonium chloride solution was added. 然后分液,水洗,接着向有机层中加入300毫升甲苯,2克乙二醇, 2克单水合对甲苯磺酸回流分水15小时,降温,水洗,有机层浓缩至干,加入20毫升甲苯,20 毫升乙酸乙酯,0. 3克5 %的钯/碳,在高压釜内,于氢气压力0. IMPa下进行氢化反应2小时,将反应液除去催化剂后,浓缩至干,硅胶柱层析,石油醚:二氯甲烷=10 :1洗脱,得到产品,产品质谱(m/e) :508,即得到式1-5的化合物。 Then liquid separation, washed with water, followed by addition of 300 ml of toluene to the organic layer, 2 g of ethylene glycol, 2 g p-toluenesulfonic acid monohydrate refluxing 15 hours, cooled, washed with water, the organic layer was concentrated to dryness, 20 ml of toluene 20 ml of ethyl acetate, 0.3 g of 5% palladium / carbon, in an autoclave, carried out at a hydrogen pressure of 0. IMPa hydrogenation reaction for 2 hours, the reaction solution after removing the catalyst, concentrated to dryness and silica gel column analysis, petroleum ether: dichloromethane = 10: 1 to give the product, the product mass spectrum (m / e): 508, i.e., to give a compound of formula 1-5. 其反应式如下: Reaction is as follows:

[0098] [0098]

Figure CN104496742AD00163

[0099] 步骤e、250ml三口瓶中,将4. 2克在步骤d获得的具有式1-5的化合物溶解在50ml 甲苯中,在搅拌同时,加入3克80%甲酸溶液,回流反应2小时,降温,水洗,有机层浓缩至干,石油醚重结晶,产品质谱(m/e) :464,即得到式1-6所示的化合物。 [0099] Step e, 250ml three-neck flask, 4.2 g will be obtained in step d compound having the formula 1-5 is dissolved in 50ml of toluene, while stirring, adding 3 g of 80% formic acid and refluxed for 2 hours , cooling, washing with water, the organic layer was concentrated to dryness, petroleum ether, the product mass Spectrum (m / e): 464, i.e., to obtain the compound of formula 1-6. 其反应式如下: Reaction is as follows:

Figure CN104496742AD00164

[0101] 步骤f、在500ml三口瓶中,加入2.3克甲氧基甲基三苯基氯化鱗和20毫升四氢呋喃,降温至-KTC,分批加入0. 78克叔丁醇钾,然后,将3. 3克在步骤e获得式1-6所示的化合物溶于IOml四氢呋喃中,滴加入上述500毫升三口瓶,然后将反应温度缓慢升至25°C, 反应40分钟。 [0101] Step F, in a 500ml three-neck flask, was added 2.3 g methoxymethyl triphenylphosphonium chloride and 20 ml of tetrahydrofuran scales, cooled to -KTC, was added portionwise 0.78 g of potassium t-butoxide, and then, 3.3 g the compound obtained in step e IOml of formula 1-6 is dissolved in tetrahydrofuran, was added dropwise the above-described three 500 ml flask, and the reaction temperature was slowly raised to 25 ° C, for 40 minutes. 加水,分液,有机层浓缩至干后,加入30晕升石油醚,充分搅拌,析出固体,抽滤,得到母液,将母液浓缩至干,加入50毫升二氯甲烷,10毫升35 %浓度的盐酸,回流反应30分钟,降温,分液,水洗至中性。 Water was added, liquid separation, the organic layer was concentrated to dryness, petroleum ether was added 30 liters of halo, sufficiently stirred, and the precipitated solid was suction filtered, mother liquor, the mother liquor was concentrated to dryness, 50 ml of methylene chloride, 10 ml of 35% concentration hydrochloric acid, refluxed for 30 minutes, cooled, separated, washed with water until neutral. 有机层浓缩至干,乙醇和石油醚混合溶剂重结晶,得到产品,产品质谱(m/e) :478,即得到式1-7所示的化合物。 The organic layer was concentrated to dryness, petroleum ether mixed solvent of ethanol and recrystallized to give the product, the product mass spectrum (m / e): 478, i.e., the compounds shown in Formula 1-7. 其反应式如下; The reaction equation is as follows;

Figure CN104496742AD00171

[0103] 步骤g、250ml三口瓶中,加入2. 4克式1-7所示的化合物,50毫升四氢呋喃,于25°C分批加入0. 5克硼氢化钠,加毕保持25°C反应4小时,加水搅拌,析出固体,抽滤,将得到的固体用乙醇重结晶,产品质谱(m/e) :480,即得到式1-8所示的化合物。 [0103] Step g, 250ml three-neck flask, added the compound of formula 1-7 2.4 g, 50 ml of tetrahydrofuran, 25 ° C Case added portionwise 0.5 g of sodium borohydride was added dropwise, maintaining 25 ° C for 4 hours, water was added with stirring, the precipitated solid was suction filtered and the resulting solid was recrystallized from ethanol, the product mass spectrum (m / e): 480, i.e., to obtain the compound of formula 1-8. 其反应式如下; The reaction equation is as follows;

Figure CN104496742AD00172

[0105] 步骤h、250ml三口瓶中加入50毫升二氯甲烷,0. 5克吡啶,及2. Og式1-8所示的化合物,然后控制30°C,分批加入1. 2克对甲苯磺酰氯,加毕,于30°C反应6小时,过滤,母液浓缩至干,用甲苯重结晶,得到式1-9所示的化合物。 [0105] Step h, 250ml three-neck flask were added 50 ml of methylene chloride, 0.5 g of pyridine, and the compound represented by Formula 2. Og 1-8, then control 30 ° C, was added portionwise 1.2 g of toluenesulfonyl chloride addition was completed, the reaction at 30 ° C 6 hours, filtered and mother liquor was concentrated to dryness, and recrystallized from toluene to give the compound of formula 1-9. 反应式如下所示: The reaction formula is shown below:

Figure CN104496742AD00173

[0107] 步骤i.在250ml三口瓶中,加入50毫升四氢呋喃,10毫升0.1mol/L的四氯铜酸二锂溶液,及3. 2克在步骤h中获得的具有式1-9的化合物。 [0107] Step i. In 250ml three-neck flask, 50 ml of tetrahydrofuran, 10 ml 0.1mol / L solution of lithium dimethyl copper tetrachloride, and 3.2 g of a compound having the formula 1-9 obtained in step h . 于30°C滴加6毫升Imol/ L的烯丙基溴化镁的乙醚溶液,然后保温反应3小时,加水,分液,有机层水洗后硫酸镁干燥,硅胶柱层析,石油醚:二氯甲烷=10:1洗脱,洗脱液浓缩至干,用石油醚和乙醇混合溶剂重结晶除去顺式异构体,得到式I所示的化合物9-((ls,Γ s,4S,4'R)-4'-(3-丁烯-1-基)-[1,Γ-双(环己基)]-4_基)-7,7_二甲基-3-丙基-7H-苯并[de]蒽;化合物的IH-NMR谱图见图1.反应式如下所示: At 30 ° C was added dropwise 6 ml Imol / L diethyl ether solution of allyl magnesium bromide, then incubated for 3 hours, water was added, after liquid separation, the organic layer was washed with water dried over magnesium sulfate, and column chromatography on silica gel, petroleum ether: two chloride = 10: 1 eluate was concentrated to dryness, a mixed solvent of petroleum ether and recrystallized from ethanol to cis isomer was removed, to give a compound of formula I as 9 - ((ls, Γ s, 4S, 4'R) -4 '- (3- buten-1-yl) - [1, Γ- bis (cyclohexyl)] - 4_ yl) -7H -7,7_ dimethyl-3-propyl - benzo [de] anthracene; IH-NMR spectrum shown in Figure 1. the compound shown in the following reaction formula:

Figure CN104496742AD00174

[0109] 经检测,式I所示的化合物的清亮点为281°C,并且具有较好的物理和化学稳定性。 [0109] After testing, the clearing point of the compound of Formula I is 281 ° C, and has good physical and chemical stability.

[0110] 实施例2、液晶组合物的制备极其效果验证 [0110] 2. A liquid crystal composition is extremely verification results in Example

[0111] 本实施例的液晶组合物含有式I所示的化合物,具体组分及配比如表1所示,将这些组分混合均匀配制得到具有表1所示配方的液晶组合物。 [0111] The liquid crystal composition of the present embodiment comprises a compound of Formula I, and with specific components such as shown in Table 1, these components were mixed uniformly to prepare a liquid crystal composition having the formulations shown in Table 1. 将该液晶组合物的性能测试如下: The performance test of the liquid crystal composition is as follows:

[0112] 经检测,该组合物的清亮点182°C。 [0112] After testing, the clearing point of the composition is 182 ° C. 液晶组合物具有较宽的向列相范围。 A liquid crystal composition having a wide nematic phase range.

[0113] 表L [0113] Table L

Figure CN104496742AD00181

[0115] 实施例3、液晶组合物的制备及其效果验证 [0115] Example 3 Preparation and verification of the effect of the liquid crystal composition

[0116] 本实施例的液晶组合物含有式I所示的化合物,具体组分及配比如表2所示,将这些组分混合均匀配置得到具有表2所示配方的液晶组合物。 [0116] The liquid crystal composition of the present embodiment comprises a compound of Formula I, and with specific components such as shown in Table 2, the arranged components were mixed uniformly to obtain a liquid crystal composition having the formulations shown in Table 2. 将该液晶组合物的性能测试如下: The performance test of the liquid crystal composition is as follows:

[0117] 经检测,该组合物的清亮点168°C。 [0117] After testing, the clearing point of the composition is 168 ° C. 液晶组合物具有较宽的向列相范围。 A liquid crystal composition having a wide nematic phase range.

[0118] 表2. [0118] Table 2.

Figure CN104496742AD00191

Figure CN104496742AD00201

Claims (12)

  1. 1. 一种液晶化合物,其结构式如式I所示: 1. A liquid crystal compound having the formula as shown in formula I:
    Figure CN104496742AC00021
  2. 2. 制备根据权利要求1所述的液晶化合物的方法,包括以下步骤: 步骤a.使式II所示的化合物在四氢呋喃中与N-溴代丁二酰亚胺进行溴代反应,以得到式1-2所示的化合物;反应式如下所示: 2. The method of producing a liquid crystal compound according to claim 1, comprising the following steps: making a compound of Formula II is reacted with bromo-N- bromosuccinimide in tetrahydrofuran, to give formula. compounds represented 1-2; reaction scheme is shown below:
    Figure CN104496742AC00022
    步骤b.使在步骤a中获得的式1-2所示的化合物与丙基溴化镁在甲苯中在催化剂存在下进行反应得到式1-3所示的化合物;反应式如下所示: Step b of formula obtained in step with a compound represented by propyl bromide for 1-2 to give a compound of formula 1-3 in the presence of a catalyst in toluene; reaction scheme is shown below:
    Figure CN104496742AC00023
    步骤c.使在步骤b中获得式1-3所示的化合物在二氯甲烷中与溴进行溴代反应,以得到式1-4所示的化合物;反应式如下所示: Step c so as to obtain a compound represented by formula 1-3 bromination with bromine in methylene chloride in step b, to obtain a compound represented by formula 1-4; reaction scheme is shown below:
    Figure CN104496742AC00024
    步骤d.使在步骤c中获得的式1-4所示的化合物制成格氏试剂后与 Step d. Formula obtained in step c in FIGS. 1-4 is made of the compound with a Grignard reagent
    Figure CN104496742AC00025
    在四氢呋喃中进行加成反应,然后进行脱水、还原,以得到式1-5所示的化合物;反应式如下所示: Addition reaction in tetrahydrofuran, followed by dehydration, reduction, to give a compound represented by formula 1-5; reaction scheme is shown below:
    Figure CN104496742AC00026
    步骤e.使在步骤d中获得的式1-5所示的化合物在甲苯中用甲酸进行水解,得到式1-6所示的化合物;反应式如下所示: Step e of formula obtained in step d compound shown in Figure 1-5 with formic acid in toluene is hydrolyzed to obtain the compound of formula 1-6; reaction scheme is shown below:
    Figure CN104496742AC00031
    步骤f.使在步骤e中获得的式1-6所示的化合物与甲氧基甲基三苯基氯化鱗、叔丁醇钾进行维蒂希反应,然后用盐酸水解,以得到式1-7所示的化合物;反应式如下所示: To step f. Of the formula obtained in step e 1-6 compound represented methoxymethyl triphenylphosphonium chloride scales, potassium tert-butoxide Wittig reaction and then hydrolyzed with hydrochloric acid, to give a formula 1 -7 compound represented; reaction scheme is shown below:
    Figure CN104496742AC00032
    步骤g.式1-7所示的化合物经硼氢化钠还原得到式1-8所示的化合物;反应式如下所示: Step g compound of formula 1-7 by reduction with sodium borohydride to give compounds of formula 1-8; reaction scheme is shown below:
    Figure CN104496742AC00033
    步骤h.式1-8所示的化合物在二氯甲烷中和对甲苯磺酰氯反应生成式1-9所示的化合物;反应式如下所示: Step h in the compound represented by the formula 1-8 compound represented by Formula 1-9 methylene chloride and p-toluenesulfonyl chloride; reaction scheme is shown below:
    Figure CN104496742AC00034
    步骤i.式1-9所示的化合物和烯丙基溴化镁进行偶联反应得到式I所示的化合物;反应式如下所示: Step i and allylmagnesium bromide compound of the formula 1-9 shown in a coupling reaction to give a compound of Formula I; reaction scheme is shown below:
    Figure CN104496742AC00035
  3. 3. 含有权利要求1所述的液晶化合物的组合物。 3. A liquid crystal composition containing a compound according to claim 1.
  4. 4. 根据权利要求3所述的组合物,其特征在于:包括权利要求1所述式I所示的化合物、式II所示的化合物、式III所示的化合物、式IV所示的化合物、式V所示的化合物、式VI所示的化合物和VII所示的化合物; 4. The composition of claim 3, wherein: said compound of formula I as claimed in claim 1 comprising a compound of compound of Formula II, formula III, formula IV shown, compounds of formula V, VII and a compound of a compound represented by formula VI;
    Figure CN104496742AC00041
  5. 5. 根据权利要求4所述的组合物,其特征在于:所述组合物包括下述组分: 式I所示的化合物5〜20% ; 式II所示的化合物4〜8% ; 式III所示的化合物8〜16% ; 式IV所示的化合物7〜20% 式V所示的化合物8〜15% 式VI所示的化合物7〜20 %,和式VII所示的化合物8〜60%。 5. The composition as claimed in claim 4, wherein: said composition comprises the following components: a compound of Formula I 5~20%; Compound of Formula II 4 to 8%; Formula III a compound represented by 8~16%; compound of formula IV 7~20% compound represented by formula V as shown in FIG 7~20% 8~15% formula VI, formula VII and a compound represented 8~60 %.
  6. 6. 根据权利要求5所述的组合物,其特征在于:所述组合物由下述组分组成: 式I所示的化合物5〜20% ; 式II所示的化合物4〜8% ; 式III所示的化合物8〜16% ; 式IV所示的化合物7〜20% 式V所示的化合物8〜15% 式VI所示的化合物7〜20 %,和式VII所示的化合物30〜60%。 6. The composition according to claim 5, characterized in that: said composition is comprised of the following: a compound of Formula I 5~20%; the compound of formula II is 4 to 8%; formula compound III in 8~16%; compound of formula IV 7~20% compound represented by formula V as shown in FIG 7~20% 8~15% formula VI, formula VII and a compound represented by the 30~ 60%.
  7. 7. 根据权利要求6所述的组合物,其特征在于:所述组合物由下述组分组成: 式I所示的化合物8% ; 式II所示的化合物6% ; 式III所示的化合物15% ; 式IV所示的化合物15% 式V所示的化合物10% 式VI所示的化合物9%,和式VII所示的化合物37%。 7. A composition according to claim 6, characterized in that: said composition is comprised of the following: a compound of formula I as 8%; compound of Formula II 6%; formula III compound 15%; 10% of the compound represented by formula VI compound represented by the formula IV 15% of the formula V 9%, and a compound represented by the formula VII 37%.
  8. 8. 根据权利要求4所述的组合物,其特征在于:所述组合物中还包括式VIII所示的化合物和式IX所示的化合物; 8. A composition as claimed in claim 4, wherein: said composition further comprises a compound of formula VIII and formula IX shown;
    Figure CN104496742AC00051
  9. 9. 根据权利要求8所述的组合物,其特征在于:所述组合物由下述组分组成: 式I所示的化合物8〜18% ; 式II所示的化合物5〜6% ; 式III所示的化合物10〜12% ; 式IV所示的化合物10〜15% 式V所示的化合物10〜13% 式VI所示的化合物8〜15%, 式VII所示的化合物8-18% 式VIII所示的化合物15〜22% ;和, 式XI所示的化合物8〜15%。 9. The composition of claim 8, wherein: the composition consists of the following components: a compound of Formula I 8~18%; the compound of formula II is 5 to 6%; the formula compound III in 10~12%; compound of formula IV the compound represented by formula V as shown in FIG 10 ~ 15% 10~13% 8~15% formula VI, the compound of formula VII 8-18 % of compounds of formula VIII 15~22%; 8~15% and compound of formula XI in FIG.
  10. 10. 根据权利要求9所述的组合物,其特征在于:所述组合物由下述组分组成: 式I所示的化合物10% ; 式II所示的化合物5% ; 式III所示的化合物12% ; 式IV所示的化合物12% 式V所示的化合物11 % 式VI所示的化合物8%, 式VII所示的化合物12% 式VIII所示的化合物20% ;和, 式XI所示的化合物10%。 10. The composition according to claim 9, wherein: the composition consists of the following components: a compound of Formula I 10%; compound of Formula II 5%; formula III 12% compound; a compound of formula IV compound represented by the formula V 12% 11% formula VI shown in FIG 8%, 20% compound of formula VII compound represented by the formula VIII 12%; and, of formula XI 10% of the compound shown.
  11. 11. 权利要求1所述的液晶化合物或权利要求3-10中任意一项所述的组合物在制备液晶显示装置中的应用。 The liquid crystal compound according to claim 1 or a composition of claim any one of claims 3-10 in the application device 11. The liquid crystal display as claimed in claim in the manufacture.
  12. 12. 含有权利要求1所述的液晶化合物或权利要求3-10中任意一项所述的组合物的液晶显示装置。 12. The liquid crystal containing liquid crystal compound as claimed in claim 1 or claim of the claims 3-10 in a composition according to any one of the display device.
CN 201410841681 2014-12-30 2014-12-30 A liquid crystal compounds, compositions and uses thereof CN104496742B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201410841681 CN104496742B (en) 2014-12-30 2014-12-30 A liquid crystal compounds, compositions and uses thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201410841681 CN104496742B (en) 2014-12-30 2014-12-30 A liquid crystal compounds, compositions and uses thereof

Publications (2)

Publication Number Publication Date
CN104496742A true true CN104496742A (en) 2015-04-08
CN104496742B CN104496742B (en) 2016-03-30

Family

ID=52938219

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201410841681 CN104496742B (en) 2014-12-30 2014-12-30 A liquid crystal compounds, compositions and uses thereof

Country Status (1)

Country Link
CN (1) CN104496742B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018107A (en) * 2015-07-23 2015-11-04 广西科技大学 Liquid crystal compound containing 4- (3-ethyl tetrahydropyrane) phenyl, composition and preparation method and application thereof
CN105062501A (en) * 2015-07-23 2015-11-18 广西科技大学 Difluorobiphenyl group-containing liquid crystal compound, composition as well as preparation method therefor and application thereof
CN105131973A (en) * 2015-07-23 2015-12-09 广西科技大学 Liquid crystal compound containing p-trifluoromethoxyphenyl, composition, and preparation method and application thereof
CN106146242A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound and preparation method thereof, liquid crystal composition and liquid crystal display panel
CN106147783A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparation method thereof, liquid crystal composition and liquid crystal display panel
CN106147784A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparing method thereof, liquid crystal composition and liquid crystal display panel
CN106146243A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparation method thereof, liquid crystal composition and liquid crystal display panel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992801A (en) * 2014-05-23 2014-08-20 京东方科技集团股份有限公司 7-hydrobenzo (de) anthracene liquid crystal compound and liquid crystal composition thereof
CN104017585A (en) * 2014-05-29 2014-09-03 京东方科技集团股份有限公司 Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel
CN104163748A (en) * 2014-05-30 2014-11-26 京东方科技集团股份有限公司 Compound and preparation method thereof, liquid crystal composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992801A (en) * 2014-05-23 2014-08-20 京东方科技集团股份有限公司 7-hydrobenzo (de) anthracene liquid crystal compound and liquid crystal composition thereof
CN104017585A (en) * 2014-05-29 2014-09-03 京东方科技集团股份有限公司 Liquid crystal compound, liquid crystal composition, preparation methods thereof and liquid crystal display panel
CN104163748A (en) * 2014-05-30 2014-11-26 京东方科技集团股份有限公司 Compound and preparation method thereof, liquid crystal composition and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146243A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparation method thereof, liquid crystal composition and liquid crystal display panel
CN106146242A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound and preparation method thereof, liquid crystal composition and liquid crystal display panel
CN106147783A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparation method thereof, liquid crystal composition and liquid crystal display panel
CN106147784A (en) * 2015-04-14 2016-11-23 北京欣奕华科技有限公司 Liquid crystal compound, preparing method thereof, liquid crystal composition and liquid crystal display panel
CN105062501A (en) * 2015-07-23 2015-11-18 广西科技大学 Difluorobiphenyl group-containing liquid crystal compound, composition as well as preparation method therefor and application thereof
CN105131973A (en) * 2015-07-23 2015-12-09 广西科技大学 Liquid crystal compound containing p-trifluoromethoxyphenyl, composition, and preparation method and application thereof
CN105018107A (en) * 2015-07-23 2015-11-04 广西科技大学 Liquid crystal compound containing 4- (3-ethyl tetrahydropyrane) phenyl, composition and preparation method and application thereof
CN105018107B (en) * 2015-07-23 2017-10-31 广西科技大学 The liquid crystal compound containing 4- (3-tetrahydropyranyl) phenyl, composition and preparation method and application

Also Published As

Publication number Publication date Type
CN104496742B (en) 2016-03-30 grant

Similar Documents

Publication Publication Date Title
CN102924243A (en) Liquid crystal compound containing cyclopentyl and difluorometheneoxy linking group, preparation method and applications thereof
CN101139319A (en) Substituted quinoline trimer indene derivative and method for making same
CN102964226A (en) Liquid crystal compound containing cyclobutyl and difluoromethylenedioxy connecting radical as well as preparation method and application thereof
CN102477305A (en) Liquid crystal compound and liquid crystal mixture
CN103204832A (en) Compound containing tetrahydrofuran, preparation method and application
CN1847210A (en) Process of producing pentafluorophenol
CN102675062A (en) Method for preparing difluoromethoxy bridge type liquid crystal
CN101560396A (en) Method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal
CN103074073A (en) Negative dielectric anisotropic liquid crystal mixture
CN103058968A (en) Liquid crystal compound containing benzoxazole and difluoromethylenedioxy bridged linkage and preparation method and application thereof
CN103030534A (en) Negative liquid crystal compound containing 2,3-difluorophenyl group, and preparation method and application thereof
CN103320144A (en) Liquid crystal compound containing dihydrobenzofuran and preparation method and application thereof
CN102153442A (en) Alkyl dicyclohexyl 2,3-difluorophenylbutenoid liquid crystal compound and application thereof
CN102690167A (en) Liquid crystal compound containing saturated indene rings and composition thereof
JPH07316082A (en) Liquid crystal compound and liquid crystal composition
CN104449761A (en) Liquid crystal compound containing difluoromethoxy bridged bonds and application thereof
CN1962580A (en) Method for preparing bis cyclohexane monomer liquid crystal using grignard reaction
CN102634347A (en) Liquid crystal composition with high optical anisotropy and liquid crystal display element
CN103194242A (en) Liquid crystal compound containing deuterium and preparation method as well as application thereof
CN104926765A (en) 4,6-difluorodibenzofuran derivatives
CN102559201A (en) Allyloxy lateral multi-fluoric liquid crystal compound and preparation method thereof
CN102826966A (en) Preparation method for liquid crystal monomer of o-difluoroalkoxybenzene derivative
CN103773386A (en) Liquid crystal compound containing 1,4-dioxane and pentafluoro-allyloxy structure and liquid crystal composition thereof
CN103102887A (en) Benzofuran derivative liquid crystal compound as well as composition and application thereof
CN102146015A (en) 1,3 conjugated diyne compound and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model