CN112979434B - 苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 - Google Patents
苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 Download PDFInfo
- Publication number
- CN112979434B CN112979434B CN202011382547.4A CN202011382547A CN112979434B CN 112979434 B CN112979434 B CN 112979434B CN 202011382547 A CN202011382547 A CN 202011382547A CN 112979434 B CN112979434 B CN 112979434B
- Authority
- CN
- China
- Prior art keywords
- pyrene
- triphenylene
- liquid crystal
- reaction
- drying
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 title claims abstract description 16
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- -1 triphenylene-2-yl Chemical group 0.000 claims abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 238000010898 silica gel chromatography Methods 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- OSXGWTSPWMDJLH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyren-2-yl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC2=CC=C(C=C(C=C3C=C4)B5OC(C)(C)C(C)(C)O5)C3=C2C4=C1 OSXGWTSPWMDJLH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims 2
- 230000005669 field effect Effects 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CATVHUNBFWPEKR-UHFFFAOYSA-N triphenylen-1-ol Chemical compound C1=CC=CC2=C3C(O)=CC=CC3=C(C=CC=C3)C3=C21 CATVHUNBFWPEKR-UHFFFAOYSA-N 0.000 description 2
- 125000005580 triphenylene group Chemical group 0.000 description 2
- WVQUWXDIIXVMTM-UHFFFAOYSA-N (5,8,11-triboronoperylen-2-yl)boronic acid Chemical class OB(O)c1cc2cc(cc3c4cc(cc5cc(cc(c(c1)c23)c45)B(O)O)B(O)O)B(O)O WVQUWXDIIXVMTM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VKAXMPSDLOLBFZ-UHFFFAOYSA-N CCCCCCOC1=CC=CC2=C(C(C=C(C(C)=C3)O)=C3C(C3=C4)=CC(OCCCCCC)=C4OCCCCCC)C3=CC(OCCCCCC)=C12 Chemical group CCCCCCOC1=CC=CC2=C(C(C=C(C(C)=C3)O)=C3C(C3=C4)=CC(OCCCCCC)=C4OCCCCCC)C3=CC(OCCCCCC)=C12 VKAXMPSDLOLBFZ-UHFFFAOYSA-N 0.000 description 1
- RMQQPNTWJQWETJ-UHFFFAOYSA-N CCCCCCOC1=CC=CC2=C(C(C=C(C(OCCCCCC)=C3)O)=C3C(C3=C4)=CC(OCCCCCC)=C4OCCCCCC)C3=CC(OCCCCCC)=C12 Chemical group CCCCCCOC1=CC=CC2=C(C(C=C(C(OCCCCCC)=C3)O)=C3C(C3=C4)=CC(OCCCCCC)=C4OCCCCCC)C3=CC(OCCCCCC)=C12 RMQQPNTWJQWETJ-UHFFFAOYSA-N 0.000 description 1
- SYTWTVZNCBCOHU-UHFFFAOYSA-N OBO.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O Chemical compound OBO.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SYTWTVZNCBCOHU-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006795 borylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种含多条烷氧链的基于2,7‑双(3,6,7,10,11‑五(烷氧基)苯并菲‑2‑基)芘的盘状液晶三联体化合物的合成,其特征在于具有通式(Ⅰ)所示的结构。其中R1为C6~C10的烷基链,R2为C1~C10的烷基链。上述通式(Ⅰ)化合物在较宽的温度范围内能自组装成六方柱状液晶中间相和向列相。本发明还提供了一种含多条烷氧链的基于2,7‑双(3,6,7,10,11‑五(烷氧基)苯并菲‑2‑基)芘的盘状液晶三联体化合物的制备方法,其合成路线简单快捷且条件温和,产率较高。
Description
技术领域
本发明涉及一种2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘的盘状液晶三联体化合物及其制备方法。
背景技术
盘状液晶是一类独特的具有显著的电导和光电导性能的、能够通过自组装形成纳米微结构的材料。盘状液晶分子通常包括两个基本组成部分:刚性的具有平面或近平面的芳香族内核和外面围绕着的柔性脂肪侧链。这样的盘状分子在液晶相可以发生自发的自组装,通过苯环之间的π-π键的作用形成取向有序的向列相或位置有序的柱状相和层状相。这为一维电荷载体体系提供独特的可能性,电子的相互作用以及电子迁移速率的影响,使得其沿着列的叠加周期比柱间距离短得多。因此,盘状液晶被广泛应用于分子电子学、光电学、光电导性、光伏和电致发光装置等领域,被认为是有前途的有机半导体。
在1954年,Forster和Kasper首次在芘的溶液中观察到了分子间准分子,受激准分子的形成,加上长寿命的激发态,高荧光量子产率,单体和受激准分子的荧光带的出色区别以及其激发光谱对微环境变化的敏感性,使芘成为了微环境分子探针的金标准。由于这种吸引人的特性组合,就其光物理特性而言,使芘成为基础和应用光化学研究的首选生色团。然而芘通过与苯并菲全氟丁基磺酸酯的偶联来扩展p共轭共平面形成既具有液晶性又具有发光性的有机功能材料的报道仍在少数。
发明内容
基于此提供了一种含芘的盘状液晶化合物的制备方法。研究表明,该类化合物在合成上主要是通过Suzuki偶联反应得到的。以单羟基苯并菲为基础原料,与全氟丁基磺酰氟反应生成苯并菲全氟丁基磺酸酯,然后再与2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)芘发生Suzuki偶联反应。因此通过简单的取代和偶联反应就能合成我们期待的苯并菲-芘-苯并菲盘状液晶三联体化合物。这种方法不仅合成路线简短,且苯并菲为良好的液晶基元,同时芘又是良好的发光基元,因此该系列的化合物结合了良好的液晶基元和发光基元,合成了既具有液晶性又具有发光性能的苯并菲-芘-苯并菲三联体结构的化合物。该系列的化合物可以在很宽的温度范围内形成稳定的六方柱状相和向列相,是一种良好的介晶体,同时该系列的化合物还具有良好的发光性能。
此外,有必要提供含芘的盘状液晶三联体化合物的制备方法。
一种含芘的苯并菲-芘-苯并菲盘状液晶三联体化合物,其特征在于具有通式(Ⅰ)所示的结构:
其中R1为CnH2n+1,n表示碳原子数为6-10的整数;R2为CnH2n+1,n表示碳原子数为1-10的整数。
一种2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘的制备方法,其特征在于包括以下步骤。
步骤一:中间体化合物(b)的制备:
以(a)所示的化合物为原料,将其与三乙胺以1:10的摩尔比称取于50ml反应管中,加入20 ml二氯甲烷,于-50 ℃的温度条件下脱气和充氮气保护,然后按化合物(a)与全氟丁基磺酰氟的摩尔比为1:3的比例缓慢加入全氟丁基磺酰氟,然后将反应恢复至室温反应20 h。反应结束后用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:3)分离提纯得到白色泡沫状固体 (b),其中R1为-CnH2n+1,n表示碳原子数为6-10的整数;R2仍为-CnH2n+1,但n表示碳原子数为1-10的整数。
步骤二:中间体化合物(c)的制备:
按摩尔比芘:双联频哪醇硼酸酯: [Ir(OMe)COD]2: dtbpy= 1 : 2.2 : 0.05 :0.1的比例称量于100 ml反应管中并加入30 ml环己烷,在氮气保护下,在80℃下反应16 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:1),用乙酸乙酯和乙醇进行重结晶,得到白色晶体(c)。
步骤三:通式(Ⅰ)中2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘的制备:
其中所述R1为-CnH2n+1,n表示碳原子数为6-10的整数;R2为-CnH2n+1,n表示碳原子数为1-10的整数;
在50 ml反应管中以摩尔比b : c: K2CO3 : Pd(PPh3)4 = 3 : 1 : 30 : 0.2称取并加入混合溶剂水(3 ml)/THF(10 ml),在氮气保护下,在70 ℃下反应48 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=2:3),用乙酸乙酯和乙醇进行重结晶,得到白色固体(Ⅰ)。
上述2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘化合物及其制备方法,其合成路线简单快捷且条件温和,该类化合物主要是以苯并菲全氟丁基磺酸酯与2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)芘发生Suzuki偶联反应后得到,通过偶联的方式将良好的液晶基元苯并菲和发光基元芘连接在一起,形成了一个较大的p共轭体系,有效地加强了分子的刚性核以及分子之间的p-p作用,在具有强的刚性核以及外围的多条烷氧基柔性链的调节作用下,其可以在非常宽的温度范围内自组装成高度有序且稳定的六方柱状液晶中间相和向列相,在液晶材料方面有很高的应用价值。此外由于发光基元芘的介入使得该类化合物具有良好的发光性能。
附图说明
图1实施例1中所获2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)芘中间体(c)的核磁氢谱。
图2实施例2中所获R1和R2均为-C6H13的中间体(b)的核磁氢谱。
图3实施例3中所获R1和R2均为-C6H13时通式(Ⅰ)的核磁氢谱。
图4实施例4中所获R1为-C6H13, R2为-CH3中间体(b)的核磁氢谱。
图5实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的核磁氢谱。
图6实施例3中所获R1和R2均为-C6H13时通式(Ⅰ)的DSC曲线图。
图7实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的DSC曲线图。
图8实施例3中所获R1和R2均为-C6H13时通式(Ⅰ)的偏光织构图。
图9实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的偏光织构图。
图10中曲线TPT6为实施例3中所获R1和R2均为-C6H13时通式(Ⅰ)的紫外-可见吸收图。
图10中曲线TPT61为实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的紫外-可见吸收图。
图11中曲线TPT6为实施例3中所获R1和R2均为-C6H13时通式(Ⅰ)的液体荧光发射光谱图。
图11中曲线TPT61为实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的液体荧光发射光谱图。
图12中曲线TPT6为实施例3中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的固体薄膜荧光发射光谱图。
图12中曲线TPT61为实施例5中所获R1为-C6H13, R2为-CH3时通式(Ⅰ)的固体薄膜荧光发射光谱图。
具体实施方式
下面给出的实例是对本发明的具体描述,必须强调的是下面给出的实施例子只是对本发明的进一步阐述,而不是对本发明的保护范围的一种限制。本领域熟练技术人员根据上述发明内容在实际实施过程中,涉及到的改进或者调整若不是本质意义上的改变,仍然属于本发明的保护范围。
值得说明的是,以下各个实施案例中所用到的原料单羟基苯并菲和2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)芘, 合成均为现有技术(Zhao, K.-Q.; Jing,M.; An, L.-L.; Du, J.-Q.; Wang, Y.-H.; Hu, P.;Wang, B.-Q.; Monobe, H.;Heinrich, B.; Donnio, B. Faciletransformation of 1-aryltriphenylenes intodibenzo[fg,op]tetracenesby intramolecular Scholl cyclodehydrogenation:synthesis, selfassembly, and charge carrier mobility of large p-extendeddiscogens.J. Mater. Chem. C 2017, 5, 669-682.;
Coventry, D. N.; Batsanov, A. S.; Goeta, A. E.; Howard,J. A. K.;Marder, T. B.;Perutz, R. N.Selective Ir-catalysed borylation of polycyclicaromatic hydrocarbons:structuresofnaphthalene-2,6-bis(boronate),pyrene-2,7-bis(boronate)and perylene-2,5,8,11-tetra(boronate) esters . Chem.Commun.2005, 2172–2174.)。
实施例1
本实施例提供的化合物是通式(Ⅰ)中化合物的中间体(c),其制备反应如下:
以芘(1.0 g,4.944 mmol)为原料,将其与双联频哪醇硼酸酯(2.763 g,10.88mmol)、[Ir(OMe)COD]2(0.1707 g,0.2472 mmol)和dtbpy(0.1354 g,0.4944 mmol)按摩尔比芘:双联频哪醇硼酸酯: [Ir(OMe)COD]2: dtbpy= 1 : 2.2 : 0.05 : 0.1的比例称量于100 ml反应管中并加入30 ml环己烷,在氮气保护下,在80℃下反应16 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:1),用乙酸乙酯和乙醇进行重结晶,得到白色晶体(c) (1.4 g,产率62%) 。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:8.62(s, 2H, ArH), 8.08(s, 4H,ArH), 1.46(s, 24H, CH3)。
实施例2
本实施例提供的化合物是R1和R2均为-C6H13的中间体(b),其制备反应如下:
以3,6,7,10,11-五(己氧基)-2-羟基苯并菲(a)(3.0 g,4.03 mmol)为原料,将其与三乙胺(4.07 g,40.3 mmol)以1:10的摩尔比称取于50ml反应管中,加入20 ml用烧结过的无水氯化钙干燥后的二氯甲烷,于-50 ℃的温度条件下脱气和充氮气保护,然后再按化合物(a)与全氟丁基磺酰氟的摩尔比为1:3的比例缓慢加入全氟丁基磺酰氟(3.65 g,12.1mmol),然后将反应恢复至室温反应20 h。反应结束后用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:3)分离提纯得到白色泡沫状固体(b) (2.98 g,产率72%)。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:8.16(s, 1H, ArH), 7.83(s, 1H,ArH), 7.78 (s, 3H, ArH), 7.68 (s, 1H, ArH), 4.20-4.28 (m, 10 H, OCH2), 1.94-2.00(m, 10H, CH2), 1.57-1.60 (m, 10H, CH2), 1.40-1.42 (m, 20H, CH2), 0.96 (t,J=8.0 Hz, 15H, CH3)。
实施例3
本实施例提供的是通式(Ⅰ)的化合物的制备,其中R1和R2均为-C6H13,制备反应如下:
以化合物的摩尔比为1 :2.8: 30 : 0.2的比例依次称取(c)(100 mg, 0.2202mmol)、(b)(633.3 mg, 0.6165 mmol)、 K2CO3(912.8 mg, 6.605 mmol)和Pd(PPh3)4(50.89mg, 0.044 mmol)于50 ml反应管中并加入混合溶剂水(3 ml)/THF(10 ml),在氮气保护下,在70 ℃下反应48 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:2,用乙酸乙酯和乙醇进行重结晶,得到白色固体(Ⅰ)(249.6 mg, 产率68%)。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:8.62(s, 2H, ArH), 8.54(s, 4H,ArH), 8.18(s, 4H, ArH), 8.03(s, 2H, ArH), 7.97(s, 4H, ArH), 7.89(s, 4H, ArH),4.22-4.29(m, 20H, OCH2), 1.92-2.00(m, 20H, CH2), 1.54-1.62 (m, 22H, CH2),1.31-1.44(m, 38H, CH2), 0.84-0.98 (m, 30H, CH3)。
实施例4
本实施例提供的化合物是R1为-C6H13, R2为-CH3中间体(b),其制备反应如下:
以6,7,10,11-四(己氧基)-3-甲基-2-羟基苯并菲(a)(1.0 g,1.48 mmol)为原料,将其与三乙胺(1.5 g,14.8mmol)以1:10的摩尔比称取于50ml反应管中,加入20 ml用烧结过的无水氯化钙干燥后的二氯甲烷,于-50 ℃的温度条件下脱气和充氮气保护,然后再按化合物(a)与全氟丁基磺酰氟的摩尔比为1:3的比例缓慢加入全氟丁基磺酰氟(1.34 g,4.44 mmol),然后将反应恢复至室温反应20 h。反应结束后用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:3)分离提纯得到白色泡沫状固体(b) (1.065g, 产率75%)。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:8.20(s, 1H, ArH), 7.88(s, 1H,ArH), 7.82 (s, 1H, ArH), 7.80 (s, 2H, ArH), 7.70(s, 1H, ArH), 4.22-4.26 (m,8H, OCH2), 4.13(s, 3H, OCH3)1.91-1.98 (m, 8H, CH2), 1.54-1.58 (m, 8H, CH2),1.40-1.43 (m,16H, CH2), 0.92-0.96 (m, 12H, CH3)。
实施例5
本实施例提供的是通式(Ⅰ)的化合物的制备,其中R1为-C6H13, R2为-CH3,其制备反应如下:
以化合物的摩尔比为1 :2.8: 30 : 0.2的比例依次称取(c)(100 mg, 0.2202mmol)、(b)(590 mg, 0.6165 mmol)、 K2CO3(912.8 mg, 6.605 mmol)和Pd(PPh3)4(50.89mg, 0.044 mmol)于50 ml反应管中并加入混合溶剂水(3 ml)/THF(10 ml),在氮气保护下,在70 ℃下反应48 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=2:3),用乙酸乙酯和乙醇进行重结晶,得到白色固体(Ⅰ)(232 mg, 产率69%)。
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:8.60(s, 2H, ArH), 8.52(s, 4H,ArH), 8.22(s, 4H, ArH), 8.01(d,J=8.0 Hz, 6H, ArH), 7.89(s, 4H, ArH), 4.22-4.29(m, 16H, OCH2), 4.12(s, 6H, OCH3), 1.89-2.01(m, 16H, CH2), 1.54-1.64(m,18H, CH2), 1.34-1.44(m, 30H, CH2), 0.86-0.98(m, 24H, CH3)。
Claims (5)
2.一种权利要求1所述的通式(Ⅰ)2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘的制备方法,其特征在于包括以下步骤:
步骤一:中间体b(3,6,7,10,11-五(烷氧基)苯并菲-2-基)全氟丁基磺酸酯的制备:
以3,6,7,10,11-五(烷氧基)-2-羟基苯并菲(a)所示的化合物为原料,将其与三乙胺以1:10的摩尔比称取于50ml反应管中,加入20 ml二氯甲烷,于-50 ℃的温度条件下脱气和充氮气保护,然后按3,6,7,10,11-五(烷氧基)-2-羟基苯并菲与全氟丁基磺酰氟的摩尔比为1:3的比例缓慢加入全氟丁基磺酰氟,然后将反应恢复至室温反应20 h,反应结束后用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析分离提纯,洗脱剂为V二氯甲烷:V石油醚=1:3,得到白色泡沫状固体 (b),其中R1为-CnH2n+1,n表示碳原子数为6-10的整数,R2仍为-CnH2n+1,但n表示碳原子数为1-10的整数;
步骤二:中间体2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)芘(c)的合成:
按摩尔比芘:双联频哪醇硼酸酯: [Ir(OMe)COD]2: dtbpy= 1 : 2.2 : 0.05 : 0.1的比例称量于100 ml反应管中并加入30 ml环己烷,在氮气保护下,在80℃下反应16 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析分离提纯,洗脱剂为V二氯甲烷:V石油醚=1:1,用乙酸乙酯和乙醇进行重结晶,得到白色晶体(c);
步骤三:2,7-双(3,6,7,10,11-五(烷氧基)苯并菲-2-基)芘(Ⅰ)的合成:
在50 ml反应管中以摩尔比b : c: K2CO3 : Pd(PPh3)4 = 3 : 1 : 30 : 0.2称取并加入混合溶剂水3 ml/THF10 ml,在氮气保护下,在70 ℃下反应48 h,反应结束后冷至室温,用二氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析分离提纯,洗脱剂为V二氯甲烷:V石油醚=2:3,用乙酸乙酯和乙醇进行重结晶,得到白色固体(Ⅰ),其中所述R1为-CnH2n+1,n表示碳原子数为6-10的整数,R2为-CnH2n+1,n表示碳原子数为1-10的整数。
3.一种权利要求1所述通式(Ⅰ)中苯并菲-芘-苯并菲盘状液晶三联体化合物作为有机液晶半导体材料的用途。
4.一种权利要求1所述通式(Ⅰ)中苯并菲-芘-苯并菲盘状液晶三联体化合物作为有机光致发光材料的用途。
5.一种权利要求1所述通式(Ⅰ)中苯并菲-芘-苯并菲盘状液晶三联体化合物作为有机场效应晶体管材料的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011382547.4A CN112979434B (zh) | 2020-12-01 | 2020-12-01 | 苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011382547.4A CN112979434B (zh) | 2020-12-01 | 2020-12-01 | 苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112979434A CN112979434A (zh) | 2021-06-18 |
CN112979434B true CN112979434B (zh) | 2022-04-19 |
Family
ID=76344858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011382547.4A Active CN112979434B (zh) | 2020-12-01 | 2020-12-01 | 苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112979434B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115806542A (zh) * | 2021-09-15 | 2023-03-17 | 四川师范大学 | 2,5-双(1,3,4-三氟四(烷氧基)三亚苯基-2-基)噻吩盘状液晶及合成 |
CN115820264A (zh) * | 2021-09-16 | 2023-03-21 | 四川师范大学 | 一种双苯并菲嵌萘盘状液晶化合物的合成及性能研究 |
CN115197712A (zh) * | 2022-05-18 | 2022-10-18 | 东南大学 | 一类含苯并菲的多环芳烃盘状液晶化合物及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200914401A (en) * | 2007-09-29 | 2009-04-01 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in OLEDs |
CN102051184A (zh) * | 2010-12-17 | 2011-05-11 | 北京科技大学 | 一种芘作为刚性核的对称型盘状液晶分子及其制备方法 |
JP2011157359A (ja) * | 2010-02-03 | 2011-08-18 | National Tsinghua Univ | トリフェニレンベースの芳香族化合物およびそれを用いた有機発光ダイオード |
CN104557440A (zh) * | 2015-02-05 | 2015-04-29 | 江西冠能光电材料有限公司 | 一种取代苯并菲衍生物类有机发光二极管材料 |
CN106565433A (zh) * | 2016-10-26 | 2017-04-19 | 北京绿人科技有限责任公司 | 一种有机化合物及其在电致发光器件中的应用 |
-
2020
- 2020-12-01 CN CN202011382547.4A patent/CN112979434B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200914401A (en) * | 2007-09-29 | 2009-04-01 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in OLEDs |
JP2011157359A (ja) * | 2010-02-03 | 2011-08-18 | National Tsinghua Univ | トリフェニレンベースの芳香族化合物およびそれを用いた有機発光ダイオード |
CN102051184A (zh) * | 2010-12-17 | 2011-05-11 | 北京科技大学 | 一种芘作为刚性核的对称型盘状液晶分子及其制备方法 |
CN104557440A (zh) * | 2015-02-05 | 2015-04-29 | 江西冠能光电材料有限公司 | 一种取代苯并菲衍生物类有机发光二极管材料 |
CN106565433A (zh) * | 2016-10-26 | 2017-04-19 | 北京绿人科技有限责任公司 | 一种有机化合物及其在电致发光器件中的应用 |
Non-Patent Citations (4)
Title |
---|
1,3,6,8-tetraphenylpyrene derivatives: Towards fluorescent liquid-crystalline columns?;de Halleux, V;《 ADVANCED FUNCTIONAL MATERIALS》;20040730;第14卷(第07期);第649-659页 * |
Core, Shell, and Surface-Optimized Dendrimers for Blue Light-Emitting Diodes;Tianshi Qin,等;《Journal of the American Chemical Society》;20110104;第133卷(第05期);第1301-1303页 * |
盘状液晶中间体单羟基苯并菲简便合成;赵可清;《有机化学》;20100326;第29卷(第12期);第2017-2020页 * |
芘及苯并菲盘状有机分子的合成、自组装及光电性能研究;弥永胜;《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》;20160531;B014-14页 * |
Also Published As
Publication number | Publication date |
---|---|
CN112979434A (zh) | 2021-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112979434B (zh) | 苯并菲-芘-苯并菲盘状液晶三联体化合物的制备方法 | |
Wu et al. | Synthesis of the anionic fluororeceptors based on thiourea and amide groups and recognition property for α, ω-dicarboxylate | |
CN111825598A (zh) | 含咔唑的盘状液晶化合物及其制备方法 | |
CN109096313B (zh) | 一种三聚茚基咔咯-卟啉-富勒烯星型化合物的制备方法 | |
CN112409323A (zh) | 一种类石墨烯共轭杂环苯并菲盘状液晶的制备方法及介晶性 | |
CN109879870B (zh) | 基于苯并噻二唑新型功能材料的合成及其应用 | |
CN107001926B (zh) | 双(二芳基亚甲基)-二氢并苯类化合物的聚集诱导发光和聚集促进光致变色 | |
CN112409374B (zh) | 一种刚性核直连的类石墨烯苯并菲盘状液晶的制备方法及介晶性 | |
CN112047922A (zh) | 一种基于二苯甲酮和苯并噻吩的发光材料及其制备方法和应用 | |
Devi et al. | Mechano-responsive luminescent emissions of an organic molecular crystal: effects of aromatic stacking interactions and solid state packing | |
KR20200061058A (ko) | 비스플루오로술포닐 이미드 알칼리 금속염의 제조방법 및 이에 의해 제조된 비스플루오로술포닐 이미드 알칼리 금속염 | |
CN112409325A (zh) | 双苯并菲并噻吩盘状液晶化合物的合成与发光性 | |
CN111253366B (zh) | 苯基苯并噻吩类棒状液晶化合物及其制备方法 | |
CN111763212A (zh) | 一种有机纳米格及其制备方法 | |
CN106167708A (zh) | 2,3‑二酰亚胺苯并菲盘状液晶分子及其制备方法 | |
CN114853654B (zh) | 一种吡咯环掺杂的bisanthene的制备方法 | |
CN114436805B (zh) | 一种基于蒽醌化合物及其制备方法和应用 | |
KR101671770B1 (ko) | 마이크로파를 이용한 5-아세트옥시메틸푸르푸랄의 신규한 제조방법 | |
CN117964651B (zh) | 一种窄谱带圆偏振发光分子及其制备方法和应用 | |
Roques et al. | Towards a better understanding of photo-excited spin alignment processes using silole diradicals | |
CN118085886A (zh) | 一种三联苯并菲盘状液晶化合物的制备方法 | |
CN117467119A (zh) | 一种离子型氮杂苯并菲共聚物弹性体及其制备方法 | |
Wang et al. | Disk-shaped symmetric hexa-substituted triphenylene derivatives: Synthesis, physical properties and self-assembly | |
CN115477572A (zh) | 一种三氟甲基三氟苯并菲盘状液晶化合物的制备方法 | |
CN116836180A (zh) | 一种氮、氧杂稠环芳烃及其合成方法和应用 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |