CN111662212A - 一种液晶中间体及其制备方法 - Google Patents
一种液晶中间体及其制备方法 Download PDFInfo
- Publication number
- CN111662212A CN111662212A CN201910164471.9A CN201910164471A CN111662212A CN 111662212 A CN111662212 A CN 111662212A CN 201910164471 A CN201910164471 A CN 201910164471A CN 111662212 A CN111662212 A CN 111662212A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal intermediate
- ring
- alkyl
- carbon atoms
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- -1 oxyl Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 238000006138 lithiation reaction Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 4
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000000543 intermediate Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000007806 chemical reaction intermediate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- ZYJCSKAGKUQLQK-UHFFFAOYSA-N 4-pentylcyclohexane-1-carbonitrile Chemical compound CCCCCC1CCC(C#N)CC1 ZYJCSKAGKUQLQK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
- C09K2019/3036—Cy-C2H4-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3048—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon double bonds
- C09K2019/3053—Cy-CH=CH-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
- C09K2019/3075—Cy-COO-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于液晶化合物的技术领域，具体地说，涉及一种液晶中间体及其制备方法。一种液晶中间体，具有如下式(I)所示的结构：
Description
技术领域
本发明属于液晶化合物的技术领域，具体地说，涉及一种液晶中间体及其制备方法。
背景技术
近十几年来，液晶显示技术迅速发展，液晶显示产品在人们的普通生活中快速普及。新型液晶显示方式主要有光学补偿弯曲模式(OCB)、共面转变液晶显示(IPS)、垂直取向模式(VA)、轴对称微结构液晶显示(ASM)、多畴扭曲液晶显示等。各种显示方式液晶盒的设计不同、驱动方式不同，液晶分子指向矢和玻璃基板方向不同，其中，光学补偿弯曲模式(OCB)、共面转变液晶显示(IPS)液晶分子指向矢和玻璃基板方向是平行的，而垂直取向模式(VA)、轴对称微结构液晶显示(ASM)在无电场状态下液晶分子指向矢和玻璃基板方向垂直。平行排列方式的IPS，液晶的介电各向异性(Δε)既可以是正的，也可以是负的。
垂直取向模式(VA)所有液晶分子在零场时和玻璃基板方向垂直，与垂直入射光线平行。当偏振片正交时，会显示良好的暗态，所以该类器件有良好的对比度，用到液晶的介电各向异性(Δε)必须是负的。液晶的光学各向异性(Δη)、液晶盒的厚度(d)、入射光的波长(λ)几乎影响不到对比度。垂直取向模式(VA)的响应时间比扭曲型器件要短得多，约为一半左右。在外加电压影响下，VA器件主要产生的是液晶分子的弯曲形变，ECB产生的是液晶分子的展曲形变，而扭曲显示产生的是液晶分子的扭曲形变，其响应时间也分别与弯曲、展曲、扭曲弹性常数成反比，由于大部分的液晶在通常的情况下液晶的弯曲弹性常数大于展曲弹性常数，展曲弹性常数又大于扭曲弹性常数，这也是VA器件响应时间较快的原因。
为了能使显示器件的性能更加接近理想化，人们一直致力于研究新的液晶化合物，液晶化合物及显示器件的性能仍在不断的向前发展。近几年，侧位含氟，含氰等多种负性材料在液晶混合物中得到了大量应用，但是，这些液晶材料的性能还有待提升，液晶材料领域的研发仍远未完成，为了改进液晶显示器元件的性能，需要不断尝试研发能够优化显示器性能的新型液晶化合物或者前期的中间体。
有鉴于此特提出本发明。
发明内容
本发明要解决的技术问题在于克服现有技术的不足，提供一种液晶中间体及其制备方法。
为解决上述技术问题，本发明采用技术方案的基本构思是：
一种液晶中间体，具有如下式(I)所示的结构：
其中：
R选自氢原子，碳数1-7的烷基、烷氧基或氟代直链烷基，或者碳数2-7的直链烯基、烯氧基或氟代直链烯烃基、烃氧基，或者含烷基取代基或氟取代的芳烃基，或者有取代基的含氧或氮的五元或六元杂环基；环E为碳环或含杂原子的杂环；n为自然数。
上述的液晶中间体可以用于制备多种结构稳定的、高负性液晶单体，为进一步获得性能优异的液晶材料奠定基础。
作为一种实施方式，R为碳数2-7直链烷基或者烷氧基。
作为一种实施方式，环E选自苯基或含取代基的苯基，或者碳数3-6的环烷基或取代环烷基，或者含氧原子取代的碳数2-5的环烷基或取代环烷基。
作为一种实施方式，环E选自1，4-亚苯基、1，4-亚环己基、1-4个氟原子取代的1，4-亚苯基、
作为一种实施方式，上式中的n为0或1或2。
作为一种实施方式，上述的液晶中间体为下列物质中的一种：
上述列举的各液晶中间体所对应得到的液晶材料，可以得到更高的负性，表现出更优异的液晶性能。
本发明的另一目的在于提供一种液晶中间体的制备方法，所述的制备方法采用如下式(II)的化合物：
经锂化反应、水解反应得到对应的醛，再经还原反应制得如式(I)的液晶中间体。
作为一种实施方式，所述液晶中间体的制备方法采用下列路径：
在上式中，环腈(A-1)为液晶行业常用中间体，易于获得，价格低廉，将其通过低温锂化加入醛基化试剂，然后水解得到醛产物(A-2),然后再通过还原得到醇产物(A-3)，在还原反应中，采用硼氢化钾作为还原剂，反应温和，易于控制定向得到预设的目标产物。作为一种实施方式，所述的锂化试剂选自烷基锂或胺基锂，或者烷基锂/胺基锂+有机溶剂。优选地，所述的锂化试剂为丁基锂、二异丙胺基锂、2,2,6,6-四甲基哌啶+丁基锂，四甲基乙二胺+丁基锂
作为一种实施方式，上述的醛基化试剂为DMF(N,N-二甲基甲酰胺)或原甲酸三甲酯类物质。
作为一种实施方式，上述锂化或醛基化反应步骤采用如下的投料比例，反应底物：锂化试剂：醛基化试剂＝1：1.0～2.0:1.0～3.0，优选为1.0：1.0～1.5:1.0～1.5。
作为一种实施方式，上述锂化或醛基化反应步骤的温度控制为-30～-110℃，优选-60～-90℃。
作为一种实施方式，上述的还原剂为硼氢化钾、硼氢化钠、红铝溶液，氢化铝锂或者金属催化加氢，优选为硼氢化钾或硼氢化钠。
作为一种实施方式，上述还原反应步骤采用如下的投料比例，反应底物：还原剂＝1:0.3～5.0,优选为1：0.5～1.1；反应温度为-20～100℃，优选为0℃～40℃。
作为一种实施方式，上述还原反应步骤采用的溶剂为水、四氢呋喃、乙醇或甲醇。
作为一种实施方式，
上式的液晶化合物通过进一步化学反应，如卤代、还原、氧化或酯化，制备具有如下式(III)所示的结构的中间体衍生物：
其中，X选自-Cl,-Br，-I,-OTs,-OMs，-OSO2CF3，-COOH，-CHO。
作为一种实施方式，采用上式(III)的物质经醚化反应、酯化反应、wittig反应或加氢反应，制备负性醚类单体、酯类、烯类或烷类，如下列所示的物质：
其中，
表示芳烃类基团，选自下列结构：
作为一种实施方式，具体地，所述的液晶化合物为下列结构的一种，如：
当然，也可以将上述的结构与其他的功能基团连接以得到新的液晶单体化合物。
采用本发明所述的液晶中间体制备获得的液晶化合物，表现出优异的负性性能和高稳定性，如在专利申请CN201610231181中公开了下列结构的液晶化合物的相关实验数据，
展示了其作为液晶材料的优异性能。而本发明的液晶中间体为更便宜地得到此类液晶化合物提供了途径，降低制备难度，为获得丰富的液晶化合物材料奠定了基础。
附图说明
附图作为本发明的一部分，用来提供对本发明的进一步的理解，本发明的示意性实施例及其说明用于解释本发明，但不构成对本发明的不当限定。显然，下面描述中的附图仅仅是一些实施例，对于本领域普通技术人员来说，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。在附图中：
图1是本发明实施例1制备的液晶中间体(1-3)的质谱图；
图2是本发明实施例2制备的液晶中间体(2-3)的质谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面结合部分实施例对本发明的技术方案进行清楚、完整地描述，以下实施例仅用于说明本发明，不用于限制本发明的范围。
实施例1
液晶中间体(1-3)的制备反应化学如下：
500ml反应瓶内加入4-戊基环己腈(1-1)18g,四氢呋喃200ml，二异丙胺15g。氮气保护下，降温到-78℃，滴加丁基锂(2.5mol/L)45ml,加完-80～-85℃保温2小时，然后滴加10.9gDMF(N,N-二甲基甲酰胺)，滴加完毕后逐渐升至室温，搅拌2小时。加入100ml水，用盐酸调至酸性，水解1小时，得到反应中间体(1-2)的混合溶液。
控温反应器内的温度为0～10℃，向反应中间体(1-2)的混合溶液中加入氢氧化钠调至中性，分批缓慢加入6g硼氢化钾固体粉末，加完升温到室温搅拌5小时。冰浴下，加入100ml水，滴加稀盐酸调至酸性，水解1小时。随后经过提取、中和、水洗等后处理步骤，蒸干溶剂得到22g黄色液体(液晶中间体1-3)，纯度81％，并通过质谱检测对其进行了确认，其质谱图如图1所示。
上述的液晶中间体1-3可以进一步进行蒸馏或者结晶提纯，进一步反应用于制备液晶单体。
例如，按照下列反应式进行进一步优化：
向反应器内加入22g黄色液体(中间体1-3)，二氯甲烷100ml，加入对甲基苯磺酰氯(TsCl)30.4g,搅拌均匀，控温10～20℃，滴加12g吡啶，加完后缓慢升温，回流5小时。降至室温，经过水洗提取干燥等后处理过程，蒸干溶剂得到黄色固体，经过乙醇结晶得到白色固体(1-4)19g,该化合物的熔点：80.1℃。
白色固体(1-4)为活性磺酸酯，有良好的晶型有利于提纯，同时也可以与酚类物质较好地进行醚化反应，制备其他的液晶化合物。
实施例2
液晶中间体(2-3)的制备反应化学如下：
500ml反应瓶内加入反应底物(2-1)18g,四氢呋喃200ml，二异丙胺15g。氮气保护下，降温到-78℃，滴加丁基锂(2.5mol/L)45ml,加完-80～-85℃保温2小时，然后滴加10.9gDMF(N,N-二甲基甲酰胺)，滴加完毕后逐渐升至室温，搅拌2小时。加入100ml水，用盐酸调至酸性，水解1小时，得到反应中间体(2-2)的混合溶液。
控温反应器内的温度为0～10℃，向反应中间体(2-2)的混合溶液中加入氢氧化钠调至中性，分批缓慢加入6g硼氢化钾固体粉末，加完升温到室温搅拌5小时。冰浴下，加入100ml水，滴加稀盐酸调至酸性，水解1小时。随后经过提取、中和、水洗等后处理步骤，蒸干溶剂得到22g黄色液体(液晶中间体2-3)，纯度89％，并通过质谱检测对其进行了确认，其质谱图如图2所示。
上述的液晶中间体2-3可以进一步进行蒸馏或者结晶提纯，进一步反应用于制备液晶单体。
以上所述仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专利的技术人员在不脱离本发明技术方案范围内，当可利用上述提示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明方案的范围内。
Claims (7)
1.一种液晶中间体，其特征在于，具有如下式(I)所示的结构：
其中：
R选自氢原子，碳数1-7的烷基、烷氧基或氟代直链烷基，或者碳数2-7的直链烯基、烯氧基或氟代直链烯烃基、烃氧基，或者含烷基取代基或氟取代的芳烃基，或者有取代基的含氧或氮的五元或六元杂环基；环E为碳环或含杂原子的杂环；n为自然数。
2.根据权利要求1所述的液晶中间体，其特征在于，R为碳数2-7直链烷基或者烷氧基。
3.根据权利要求1或2所述的液晶中间体，其特征在于，环E选自苯基或含取代基的苯基，或者碳数3-6的环烷基或取代环烷基，或者含氧原子取代的碳数2-5的环烷基或取代环烷基。
4.根据权利要求1-3任一项所述的液晶中间体，其特征在于，环E选自1，4-亚苯基、1，4-亚环己基、1-4个氟原子取代的1，4-亚苯基、
5.根据权利要求1-4任一项所述的液晶中间体，其特征在于，n为0或1或2。
6.一种液晶中间体的制备方法，其特征在于，采用如下式(II)的化合物：
经锂化反应、水解反应得到对应的醛，再经还原反应制得如式(I)的液晶中间体。
7.根据权利要求6所述的液晶中间体的制备方法，其特征在于，采用下列路径：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910164471.9A CN111662212A (zh) | 2019-03-05 | 2019-03-05 | 一种液晶中间体及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910164471.9A CN111662212A (zh) | 2019-03-05 | 2019-03-05 | 一种液晶中间体及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111662212A true CN111662212A (zh) | 2020-09-15 |
Family
ID=72381532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910164471.9A Pending CN111662212A (zh) | 2019-03-05 | 2019-03-05 | 一种液晶中间体及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111662212A (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088538A2 (en) * | 2006-12-20 | 2008-07-24 | Donald Wesley Stoutamire | Esters of 2-phenylalkanenitriles and antifungal compositions containing them |
| CN107298980A (zh) * | 2016-04-14 | 2017-10-27 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
| CN107345141A (zh) * | 2016-05-06 | 2017-11-14 | 北京八亿时空液晶科技股份有限公司 | 一种异戊基类负介电各向异性的液晶化合物及其应用 |
| CN108251128A (zh) * | 2018-02-01 | 2018-07-06 | 烟台显华化工科技有限公司 | 一种具有负介电各向异性的液晶化合物及其制备方法和应用 |
| CN109181711A (zh) * | 2018-08-20 | 2019-01-11 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
-
2019
- 2019-03-05 CN CN201910164471.9A patent/CN111662212A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088538A2 (en) * | 2006-12-20 | 2008-07-24 | Donald Wesley Stoutamire | Esters of 2-phenylalkanenitriles and antifungal compositions containing them |
| CN107298980A (zh) * | 2016-04-14 | 2017-10-27 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
| CN107345141A (zh) * | 2016-05-06 | 2017-11-14 | 北京八亿时空液晶科技股份有限公司 | 一种异戊基类负介电各向异性的液晶化合物及其应用 |
| CN108251128A (zh) * | 2018-02-01 | 2018-07-06 | 烟台显华化工科技有限公司 | 一种具有负介电各向异性的液晶化合物及其制备方法和应用 |
| CN109181711A (zh) * | 2018-08-20 | 2019-01-11 | 河北迈尔斯通电子材料有限公司 | 一种负性液晶化合物及其制备方法 |
Non-Patent Citations (9)
| Title |
|---|
| ACS REGISTRY: "RN号1503353-81-8等", 《STN》 * |
| ACS REGISTRY: "RN号1503353-81-8等", 《STN》, 28 January 2014 (2014-01-28), pages 1 - 4 * |
| CHENG-RI PIAO ET AL.: "AlCl3-Mediated Direct Carbon-Carbon Bond-Forming Reaction of α -Hydroxyketene-S,S-acetals with Arenes and Synthesis of 3,4-Disubstituted Dihydrocoumarin Derivatives", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| CHENG-RI PIAO ET AL.: "AlCl3-Mediated Direct Carbon-Carbon Bond-Forming Reaction of α -Hydroxyketene-S,S-acetals with Arenes and Synthesis of 3,4-Disubstituted Dihydrocoumarin Derivatives", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 73, no. 6, 22 February 2008 (2008-02-22), pages 2264 - 2269 * |
| GEN-QIANG CHEN ET AL.: "Catalyst-Dependent Divergent Synthesis of Pyrroles from 3-Alkynyl Imine Derivatives: A Noncarbonylative and Carbonylative Approach", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| GEN-QIANG CHEN ET AL.: "Catalyst-Dependent Divergent Synthesis of Pyrroles from 3-Alkynyl Imine Derivatives: A Noncarbonylative and Carbonylative Approach", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》, vol. 53, no. 32, 31 December 2014 (2014-12-31), pages 8492 - 8497 * |
| 原著JIE JACK LI，荣国斌译, vol. 2003, 华东理工大学出版社, pages: 47 - 16 * |
| 原著JIE JACK LI，荣国斌译, 华东理工大学出版社 * |
| 张晓军等: "4-［2′-（反式-4"-戊基环己基）乙基］环己酮的合成", 《精细化工》, vol. 19, no. 7, 31 July 2002 (2002-07-31), pages 400 - 402 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107298980B (zh) | 一种负性液晶化合物及其制备方法 | |
| KR20150086177A (ko) | 2,3-디플루오로페닐 기를 함유하는 음성 액정 화합물, 및 그의 제조 방법 및 용도 | |
| CN102795974B (zh) | 液晶介质及液晶组合物 | |
| CN113234045B (zh) | 具有负介电各向异性的液晶化合物、液晶组合物、液晶显示器件 | |
| CN110577833B (zh) | 一种负性液晶化合物及其制备方法 | |
| US20170349831A1 (en) | Liquid crystal compound containing difluormethoxy bridge, composition and application thereof | |
| US20150252261A1 (en) | Cycloheptane derivative and preparation method and use thereof | |
| CN114517097B (zh) | 一种含环己烯结构的液晶化合物及其制备方法与应用 | |
| CN110117277B (zh) | 一种负性液晶单体及制备方法 | |
| CN105505406A (zh) | 一种含支链结构弯曲分子的蓝相液晶复合材料的制备方法 | |
| CN109628107A (zh) | 一种具有高光学各向异性的液晶化合物及其应用 | |
| CN107779202B (zh) | 一种负性液晶化合物的制备方法 | |
| CN109181711B (zh) | 一种负性液晶化合物及其制备方法 | |
| CN117070229B (zh) | 一种液晶混合物及其应用 | |
| CN102994100B (zh) | 液晶组合物和含有该液晶组合物的液晶显示器件 | |
| CN102659533A (zh) | 作为液晶介质的组分的茚衍生物及其制备方法和应用 | |
| TWI792117B (zh) | 一種負介電的液晶化合物及其製備和應用 | |
| CN111662212A (zh) | 一种液晶中间体及其制备方法 | |
| CN114105919A (zh) | 一种液晶化合物及其制备方法和应用 | |
| CN114105966A (zh) | 一种液晶化合物及其制备方法和应用 | |
| CN112646589B (zh) | 一种液晶化合物及其应用 | |
| CN103087724B (zh) | 液晶组合物和含有该液晶组合物的液晶显示器件 | |
| CN106398716B (zh) | 一种4，5－二氟-7-甲基茚满类液晶化合物及其制备方法与应用 | |
| WO2014125924A1 (ja) | 誘電率異方性が負の環構造を有する新規な化合物およびその製造方法、液晶組成物および液晶電気光学素子 | |
| CN111592889B (zh) | 一种液晶化合物及其制备方法与应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200915 |