CN111253210A - 一种4``-烷基-2,4,3`-三氟-三联苯类液晶单体的制备方法 - Google Patents
一种4``-烷基-2,4,3`-三氟-三联苯类液晶单体的制备方法 Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- AGYWDGVTLKNTBS-UHFFFAOYSA-N 4-bromo-1-chloro-2-fluorobenzene Chemical compound FC1=CC(Br)=CC=C1Cl AGYWDGVTLKNTBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- MGHBDQZXPCTTIH-UHFFFAOYSA-N 1-bromo-2,4-difluorobenzene Chemical compound FC1=CC=C(Br)C(F)=C1 MGHBDQZXPCTTIH-UHFFFAOYSA-N 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
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- 239000003960 organic solvent Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000007818 Grignard reagent Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000004795 grignard reagents Chemical class 0.000 claims description 6
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- -1 boric acid ester Chemical class 0.000 claims description 4
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 4
- 229910052763 palladium Inorganic materials 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 5
- GSPXIXSHISJQLY-UHFFFAOYSA-N 1-chloro-4-(2,4-difluorophenyl)-2-fluorobenzene Chemical group ClC1=C(C=C(C=C1)C1=C(C=C(C=C1)F)F)F GSPXIXSHISJQLY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 238000003747 Grignard reaction Methods 0.000 abstract description 2
- NZONRWNNLXYGHB-UHFFFAOYSA-N boric acid;1-chloro-2-fluorobenzene Chemical compound OB(O)O.FC1=CC=CC=C1Cl NZONRWNNLXYGHB-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- CMJQIHGBUKZEHP-UHFFFAOYSA-N (4-chloro-3-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C(F)=C1 CMJQIHGBUKZEHP-UHFFFAOYSA-N 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- QQLRSCZSKQTFGY-UHFFFAOYSA-N (2,4-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(F)C=C1F QQLRSCZSKQTFGY-UHFFFAOYSA-N 0.000 description 2
- QPIBHIXKUQKNFP-UHFFFAOYSA-N 4-chloro-3-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(F)=C1 QPIBHIXKUQKNFP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WLCGYIWOKVWFLB-UHFFFAOYSA-N (4-propylphenyl)boronic acid Chemical compound CCCC1=CC=C(B(O)O)C=C1 WLCGYIWOKVWFLB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XRMZKCQCINEBEI-UHFFFAOYSA-N 4-bromo-2-fluoro-1-iodobenzene Chemical compound FC1=CC(Br)=CC=C1I XRMZKCQCINEBEI-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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Abstract
本发明涉及液晶显示领域,特别涉及一种用于液晶显示的4''‑烷基‑2,4,3'‑三氟‑三联苯类液晶单体的制备方法,所述制备方法是以3‑氟‑4‑氯溴苯为原料,经过格氏反应制备3‑氟‑4‑氯苯硼酸、然后与2,4‑二氟溴苯进行Suzuki偶联反应制得关键中间体4’‑氯‑2,4,3’‑三氟‑联苯,该中间体与4‑烷基苯硼酸进行Suzuki偶联反应得到该类液晶单体,该合成路线采用比较廉价原料,经过常规反应制备得最终产品,生产成本低,有利于规模化生产,具有很高的应用前景。
Description
技术领域
本发明涉及液晶显示领域,特别涉及一种用于液晶显示的4''-烷基-2,4,3'-三氟-三联苯类液晶单体的制备方法。
背景技术
含氟的三联苯液晶单体是含氟液晶单体中重要的一类,具有低熔点、高清亮点、高电阻率等优点,同时该类液晶单体具有高的折射率各向异性、很高的电荷保持率、低旋转粘度、低功耗等性质,具有非常快的相应速度,特别适用于制造大折射率的各向异性,快速相应的TN-TFT,IPS-TFT,FFS-TFT显示器。
现有合成方法存在原料贵、收率等情况,如专利CN104560053公开的制备方法,利用4’-烷基-2-氟-4-溴联苯与2,4-二氟苯硼酸发生Suzuki偶联反应进行制备,但4’-烷基-2-氟-4-溴联苯需要使用2-氟-4-溴碘苯制备,该原料价格昂贵,且碘分子量高,污染环境,利用率低;另一中间体2,4-二氟苯硼酸受2位氟的影响,制备收率很低,仅有30%左右。受以上两个因素制约,该方法原料昂贵,总收率低,生产成本高,不符合工业化生产经济要求。
发明内容
本发明要解决的技术问题是克服了现有方法收率低、生产成本高的缺点,提供了一种具有原料便宜易得,收率高,成本低的4''-烷基-2,4,3'-三氟-三联苯类液晶单体的制备方法。
本发明解决上述技术问题的技术方案如下:一种用于液晶显示的4''-烷基-2,4,3'-三氟-三联苯类液晶单体的制备方法,包括以下步骤:
1)向3-氟-4-氯溴苯中添加与所述3-氟-4-氯溴苯质量比为1:(2~5)的有机溶剂,混合均匀,然后在20℃~30℃的温度下,滴加到与所述3-氟-4-氯溴苯摩尔比为1:(1.5~3.0)的金属镁中制备3-氟-4-氯溴苯的格氏试剂。
式中,R表示具有1到7个碳原子的烷基
本发明的有益效果是:以3-氟-4-氯溴苯为原料,经过格氏反应制备3-氟-4-氯苯硼酸、然后与2,4-二氟溴苯进行Suzuki偶联反应制得关键中间体4’-氯-2,4,3’-三氟-联苯,该中间体与4-烷基苯硼酸进行Suzuki偶联反应得到该类液晶单体,该合成路线采用比较廉价原料,经过常规反应制备得最终产品,生产成本低,有利于规模化生产,具有很高的应用前景。
在上述技术方案的基础上,本发明还可以做如下改进:
进一步,步骤1)或步骤2)或步骤3)中所述的有机溶剂为四氢呋喃或甲苯中的一种或两种。
进一步,步骤1)所述的硼酸酯为硼酸三甲酯或硼酸三丁酯或硼酸三异丙酯中的一种。
进一步,步骤2)或步骤3)中所述的催化剂为醋酸钯或二氯二三苯基磷合钯或四三苯基磷合钯中的一种或两种。
进一步,步骤2)或步骤3)中所述的碱为氢氧化钾或氢氧化钠或碳酸钾或碳酸钠或磷酸钾中的一种或两种。
具体实施方式
以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例
当R为正丙基时,产品为4''-丙基-2,4,3'-三氟-[1,1';4',1'']三联苯
1)3-氟-4-氯苯硼酸的制备
向2000ml三颈瓶内加入36.5g(1.5mol)的镁屑,20℃~30℃的温度下向瓶中加入配制好的3-氟-4-氯溴苯的四氢呋喃溶液(207.9g(1.0mol) 3-氟-4-氯溴苯, 415.8g四氢呋喃),滴加完毕保温1小时备用。有机溶剂为质量比,此处没有问题。
向另一个2000ml三颈瓶内加入156g(1.5mol)硼酸三甲酯和312g四氢呋喃,控温0℃~10℃将上述制备好的格氏试剂滴入,滴加毕保温2小时,保温毕,倒入208.5g浓盐酸和417g水的混合溶液中水解,水解毕减压脱除四氢呋喃,过滤,所得白色滤饼用甲苯打浆一次,烘干后得产品149.6g,HPLC:98.89%,收率86.0%。
2)4'-氯-2,4,3'-三氟-联苯的制备
向2000ml三颈瓶中加入96.0g(0.5mol)2,4-二氟溴苯、138.0g(1.0mol)碳酸钾、56.0mg(0.025mmol)醋酸钯、205.0mg(0.05mmol) 2-二环己基膦-2',6'-二甲氧基联苯、288.0g四氢呋喃,435.0g水,氮气保护下,控温60℃~70℃加入3-氟-4-氯苯硼酸的四氢呋喃溶液(87.0g(0.5mol)3-氟-4-氯苯硼酸,261.0g四氢呋喃),滴加毕保温2小时,保温毕,降温,分层,水相用484.0g甲苯萃取一次,合并有机相,每次用300.0g水洗,水洗两次,有机相用20.0g无水硫酸钠进行干燥,然后过装有30.0g硅胶的层析柱,过柱液减压脱除溶剂,然后减压蒸馏得白色固体111.3g,GC:99.56%,收率92.3%。
3) 4''-丙基-2,4,3'-三氟-[1,1';4',1'']三联苯
向2000ml三颈瓶中加入121.0g(0.5mol) 4'-氯-2,4,3'-三氟-联苯、86.1g(0.525mol)4-正丙基苯硼酸、138.0g(1.0mol)碳酸钾、56.0mg(0.025mmol)醋酸钯、205.0mg(0.05mmol)2-二环己基膦-2',6'-二甲氧基联苯、544.0g四氢呋喃,544.0g水,氮气保护下,控温60℃~70℃反应2小时,保温毕,降温,分层,水相用652.0g甲苯萃取一次,合并有机相,每次用400.0g水洗,水洗两次,有机相用30.0g无水硫酸钠进行干燥,然后过装有40.0g硅胶的层析柱,过柱液减压脱除溶剂,然后用甲苯/无水乙醇体系重结晶2次,烘干得白色固体138.9g,GC:99.92%,收率85.2%。
1H NMR(400MHz,CDCl3);δ:7.48-7.52(m, 3H);7.40-7.46(m,1H); 7.29 - 7.35(t,2H);7.26-7.28(d,2H);6.90-6.98(m,2H);2.62-2.66(t,2H);1.64-1.74(m,2H);0.96-1.00(t,3H); 13C NMR(400MHz,CDCl3);δ:163.84,163.72, 161.35,161.24,160.87,158.59,158.48,158.41,142.52,135.54,135.46,132.61,131.29,131.25,131.20,130.67,130.63,128.82,128.79,128.41,128.27,124.76,124.73,124.70,123.91,123.78,116.66,116.63,116.42,116.39,111.90,111.86,111.69,111.65,104.84,104.58,104.32,37.80,25.71,13.92; MS;m/z 326(M+)。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种4''-烷基-2,4,3'-三氟-三联苯类液晶单体的制备方法,其特征在于,包括以下步骤:
1)向3-氟-4-氯溴苯中添加与所述3-氟-4-氯溴苯质量比为1:(2~5)的有机溶剂,混合均匀,然后在20℃~30℃的温度下,滴加到与所述3-氟-4-氯溴苯摩尔比为1:(1.5~3.0)的金属镁中制备3-氟-4-氯溴苯的格氏试剂。
2)向上述化合物(I)中加入2,4-二氟溴苯、碱、有机溶剂、催化剂,于60℃~80℃的温度下反应得到化合物(II),其结构式为:
式中,R表示具有1到7个碳原子的烷基
根据权利要求1所述的制备方法,其特征在于,步骤1)或步骤2)或步骤3)中所述的有机溶剂为四氢呋喃或甲苯中的一种或两种。
3.根据权利要求1所述的制备方法,其特征在于,步骤1)所述的硼酸酯为硼酸三甲酯或硼酸三丁酯或硼酸三异丙酯中的一种。
4.根据权利要求1所述的制备方法,其特征在于,步骤2)或步骤3)中所述的催化剂为醋酸钯或二氯二三苯基磷合钯或四三苯基磷合钯中的一种或两种。
5.根据权利要求1所述的制备方法,其特征在于,步骤2)或步骤3)中所述的碱为氢氧化钾、氢氧化钠、碳酸钾、碳酸钠、磷酸钾中的一种或两种。
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CN116283515B (zh) * | 2023-03-17 | 2024-05-28 | 南京工业大学 | 一种芳基氟与芳基溴的直接交叉偶联方法 |
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