CN112300158A - 基于萘酸酐的发光盘状液晶的合成与性质 - Google Patents
基于萘酸酐的发光盘状液晶的合成与性质 Download PDFInfo
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- CN112300158A CN112300158A CN202011374036.8A CN202011374036A CN112300158A CN 112300158 A CN112300158 A CN 112300158A CN 202011374036 A CN202011374036 A CN 202011374036A CN 112300158 A CN112300158 A CN 112300158A
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- -1 naphthalene anhydride Chemical class 0.000 title claims abstract description 26
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title claims description 9
- 238000003786 synthesis reaction Methods 0.000 title claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 125000005561 phenanthryl group Chemical group 0.000 claims abstract description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 10
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005605 benzo group Chemical group 0.000 claims abstract description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 117
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 36
- 239000003480 eluent Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 238000010898 silica gel chromatography Methods 0.000 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 23
- 229960001701 chloroform Drugs 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 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 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 claims description 3
- BYVCTYDTPSKPRM-UHFFFAOYSA-N naphthalene-1-carbonyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(OC(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 BYVCTYDTPSKPRM-UHFFFAOYSA-N 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
- 239000001257 hydrogen Substances 0.000 description 31
- 229910052739 hydrogen Inorganic materials 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 31
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical class N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- IFUBKTZNWPJKGD-UHFFFAOYSA-N 4-(3,4-didodecoxyphenyl)-1,2-didodecoxybenzene Chemical group C(CCCCCCCCCCC)OC=1C=C(C=CC1OCCCCCCCCCCCC)C1=CC(=C(C=C1)OCCCCCCCCCCCC)OCCCCCCCCCCCC IFUBKTZNWPJKGD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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- 238000005442 molecular electronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
本发明涉及含萘酸酐的盘状液晶衍生物,包括9,10,13,14‑四(十二烷氧基)‑4H,6H‑苯并[de]菲基[9,10‑g]异戊烯‑4,6‑二酮,2,3,12,13‑四(十二烷氧基)苯并[g]ch‑6,7‑二羧酸二丁酯,9,10,13,14‑四(十二烷氧基)‑5‑辛基‑4H‑苯并[de]菲基[9,10‑g]异喹啉‑4,6(5H)‑二酮,5‑(4‑丁基苯基)‑9,10,13,14‑四(十二烷氧基)‑4H‑苯并[de]菲基[9,10‑g]异喹啉‑4,6(5H)‑二酮以及2,3,6,7‑四(十二烷基氧基)‑10H苯并[de]苯并[4,5]咪唑并[1,2‑b]菲[9,10‑g]异喹啉‑10‑酮的盘状液晶化合物,其特征在于具有(A1)(A2)(A3)(A4)(A5)所示的结构。上述通式(A1)(A2)(A3)(A4)化合物在一定的温度范围内能自组装成六方柱状液晶中间相,通式(A5)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。
Description
技术领域
本发明涉及一种基于萘酸酐构建的发光盘状液晶化合物及其制备方法。
背景技术
目前,盘状液晶是一类独特的具有显著的电导和光电导性能的。是一种具有π键共轭的平面盘状分子,早期主要应用于相位补偿薄膜中,由于其一维分子间柱状堆积,使其能够自组装成柱状结构,尤其是六方柱状相。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,盘状液晶在分子电子学、光电学、光电导性、光伏和电致发光装置等领域的应用中,盘状液晶被认为是有前途的有机半导体。然而,在过去几年中,已经有大量的文献报道了聚合物基发光液晶,但是,基于小分子的发光液晶尚未得到广泛报道,报道了的只有氟,噻吩和1,3,4-恶二唑(OXD)衍生物。
发明内容
基于此提供了一种基于萘酸酐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偶联得到的。以4-溴-1,8-萘酐为原料,与硼酸二频哪醇酯发生Suzuki偶联后进行关环。因此通过简单的取代,偶联反应,合成我们想要的含酰亚胺结构和苯并菲的化合物。不仅合成路线简短,且含有苯并菲液晶基元,本系列的化合物含有液晶基元,合成既具有液晶性又具有发光性能的萘酸酐的衍生物。可以在较宽的温度范围内形成稳定的六方柱状相,是一种良好的介晶体。同时该类化合物具有良好的发光性能。
此外,还有必要提供萘酸酐衍生物的盘状液晶化合物的制备方法。
一种由萘酸酐构建的盘状液晶化合物, 9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1), 2,3,12,13-四(十二烷氧基)苯并[g] ch-6,7-二羧酸二丁酯(A2), 9,10,13,14-四(十二烷氧基)-5-辛基-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A3), 5-(4-丁基苯基)-9,10,13,14-四(十二烷氧基)-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A4)以及2,3,6,7-四(十二烷基氧基)-10H苯并[de]苯并[4,5]咪唑并[1,2-b]菲[9,10-g]异喹啉-10-酮(A5)的盘状液晶化合物,其特征在于具有以下所示的结构:
一种权利要求1(A1)(A2)(A3) (A4) (A5)的化合物,其制备方法为。
步骤一:中间体2-溴-3',4,4',5-四(十二烷氧基)-1,1'-联苯(b)制备:
以式a所示的化合物为原料,将其与溴单质以1:1的摩尔比在250ml圆底烧瓶中称取,加入150ml三氯甲烷,套上恒压滴液漏斗,往其中加入三氯甲烷(20ml)和溴单质,将圆底烧瓶放入室温的环境中,恒压滴液漏斗中的溶液控制在2秒每滴,每隔15分钟点板跟踪,反应完毕,加入亚硫酸氢钠终止反应,过滤,用旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:2),用乙醇、乙酸乙酯重结晶,得产物b,其中R为-C12H25。
步骤二:中间体4,4,5,5-四甲基-2-(3',4,4',5-四(烷氧基)-[1,1'-联苯] -2-基)-1,3,2-二氧杂硼烷(c)的合成:
其中,R是C12H25;
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四(烷氧基)-1,1'-联苯(b):双戊酰二硼: CH3COOK: PdCl2(dppf)= 1 : 1.5 : 0.05 : 3称取并加入1,4-二氧六环25 ml,在氩气保护下,在90 ℃下反应24h,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=1:3),用乙酸乙酯和甲醇进行重结晶,得到白色固体 (c)。
步骤三:中间体为(C1) (C2) (C3) (C4)化合物的制备:
化合物C1的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 正溴丁烷:K2CO3 = 1 : 3: 5 的摩尔比称取,并加入丁醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取,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),得到淡黄色油状液体;
化合物C2的制备: 在100ml的圆底烧瓶中以4-溴-1,8-萘酐: 正辛胺= 1 : 3 的摩尔比称取,并加入乙醇(40ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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),用乙醇和甲醇进行重结晶,得到黄绿色针状晶体;
化合物C3的制备: 在50ml的圆底烧瓶中以4-溴-1,8-萘酐: 正丁基苯胺= 1 : 1.2的摩尔比称取,并加入乙醇(20ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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;
化合物C4的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 邻苯二胺= 1 : 1.1的摩尔比称取,并加入醋酸(4ml),冷凝回流6h,冷却至室温,加入乙醇,过滤,通过硅胶柱层析(洗脱剂:三氯甲烷),用甲苯和乙醇进行重结晶,得到黄色固体。
步骤四:中间体为(B1)(B2)(B3)(B4)化合物的制备:
其中,R是CnH2n+1,n表示碳原子数为12;
在50 ml反应管中以摩尔比c :化合物C(C= C1, C2, C3, C4): K2CO3 : Pd(PPh3)4 = 1: 1.2 : 30 : 0.1称取并加入混合溶剂水(3 ml)/THF(10 ml),在氩气保护下,在70 ℃下反应24 h,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:二氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到B1为白色固体,B2为黄色固体,B3为黄色固体,B4为黄色固体。
步骤五:化合物(A1)(A3) (A4) (A5)的合成:
其中,R是CnH2n+1,n表示碳原子数为12;
在100ml的圆底烧瓶中以化合物B(B= B1, B2, B3,B4) : FeCl3 = 1 : 3 的摩尔比称取,并加入三氯甲烷(60ml),硝基甲烷(5ml)、在室温下反应,每隔5min点板跟踪反应,反应完毕,加入甲醇终止反应,用三氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:三氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到A1为橙色固体,A3为黄色固体,A4为橙色固体,A5为橙黄色固体。
步骤五:化合物(A2)的合成:
在25ml的圆底烧瓶中以9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1): 正溴丁烷= 1 : 3 的摩尔比称取,并加入乙醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取, 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=1:1.5),用乙酸乙酯和甲醇进行重结晶,得到黄绿色固体。
上述基于萘酸酐构建的化合物及其制备方法,其合成路线简单快捷且条件温和,该类化合物是以4-溴-1,8-萘酐为原料,经过偶联关环后得到,通过稠合的方式将多个芳基连在一起,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,其可以在较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,在液晶材料方面有很高的应用价值。
萘酸酐衍生物是有着高效黄色发光同时也具有空穴传输特征的材料,通过研究不同萘酸酐衍生物,可以有效的提高其光学性、电化学性等。
附图说明。
图1实施例1中所获R为C12H25的中间体a的核磁氢谱。
图2实施例1中所获R为C12H25的中间体b的核磁氢谱。
图3实施例1中所获R为C12H25的中间体c的核磁氢谱。
图4实施例4中所获R为C12H25的化合物A1的核磁氢谱。
图5实施例2中所获R为C12H25的中间体C1的核磁氢谱。
图6实施例3中所获R为C12H25的中间体B1的核磁氢谱。
图7实施例4中所获R为C12H25的化合物A2的核磁氢谱。
图8实施例2中所获R为C12H25的中间体C2的核磁氢谱。
图9实施例3中所获R为C12H25的中间体B2的核磁氢谱。
图10实施例4中所获R为C12H25的化合物A3的核磁氢谱。
图11实施例2中所获R为C12H25的中间体C3的核磁氢谱。
图12实施例3中所获R为C12H25的中间体B3的核磁氢谱。
图13实施例4中所获R为C12H25的化合物A4的核磁氢谱。
图14实施例2中所获R为C12H25的中间体C4的核磁氢谱。
图15实施例3中所获R为C12H25的中间体B4的核磁氢谱。
图16实施例4中所获R为C12H25的化合物A5的核磁氢谱。
图17实施例4中所获R为C12H25的化合物A1的DSC曲线图。
图18实施例4中所获R为C12H25的化合物A2的DSC曲线图。
图19实施例4中所获R为C12H25的化合物A3的DSC曲线图。
图20实施例4中所获R为C12H25的化合物A4的DSC曲线图。
图21实施例4中所获R为C12H25的化合物A5的DSC曲线图。
图22实施例4中所获R为C12H25的化合物A1的POM曲线图。
图23实施例4中所获R为C12H25的化合物A2的POM曲线图。
图24实施例4中所获R为C12H25的化合物A3的POM曲线图。
图25实施例4中所获R为C12H25的化合物A4的POM曲线图。
图26实施例4中所获R为C12H25的化合物A5的POM曲线图。
图27实施例4中所获R为C12H25的化合物(A1)(A2)(A3) (A4) (A5)的紫外-可见吸收图。
图28实施例5中所获R为C12H25的化合物(A1)(A2)(A3) (A4) (A5)的溶液荧光发射光谱图。
图29实施例5中所获R为C12H25的化合物(A1)(A2)(A3) (A4) (A5)的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。
实施例1。
R为C12H25的中间体b的制备:
以3,3',4,4'-四(十二烷氧基)-1,1'-联苯(3.29 g,3.7 mmol)为原料,将其与溴(0.59g,3.7 mmol)单质以1:1摩尔比在250ml圆底烧瓶中称取,加入150ml三氯甲烷,套上恒压滴液漏斗,往其中加入三氯甲烷(20ml)和溴单质,将圆底烧瓶放入室温的环境中,恒压滴液漏斗中的溶液控制在2秒每滴,每隔15分钟点板跟踪,反应完毕,加入亚硫酸氢钠终止反应,过滤,用旋干。过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:2),用乙醇、乙酸乙酯重结晶,得产物b(3.5g,产率97 %);
核磁氢谱1H NMR(CDCl3, TMS, 400 MHz), δ:7.10(s, 1H, ArH), 6.94(s, 1H,ArH), 6.89 (s, 2H, ArH), 6.84 (s, 1H, ArH), 3.96-4.04 (m, 8H, OCH2), 1.80—1.84 (m, 8H, CH2), 1.42-1,47 (m, 8H, CH2), 1.26-1.32 (m, 64H, CH2), 0.88 (t, J=7.2Hz, 12H, CH3)。
R为C12H25的中间体c的制备:
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四(烷氧基)-1,1'-联苯:双戊酰二硼(b): CH3COOK: PdCl2(dppf)= 1(1.2 g) : 1.5(0.53 g) : 0.05(0.06 g) : 3(0.4 g)称取并加入1,4-二氧六环25 ml,在氩气保护下,在90 ℃下反应24h,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=1:3),用乙酸乙酯和甲醇进行重结晶,得到白色固体 (c)(1.27 g,产率53 %);
核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 7.21 (s, 1H, ArH), 6.92 (s, 1H,ArH), 6.85 (s, 3H, ArH), 4.00 - 4.05 (m, 8H, OCH2), 1.80-1.85 (m, 8H, CH2),1.26-1.50 (m, 72H, CH2), 1.19 (s, 12H, CH3 ), 0.88 (t, J = 8.0 Hz, 12H, CH3)。
实施例2。
本实施例提供的化合物是中间体(C1) (C2) (C3) (C4), 其制备反应如下:
化合物C1的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 正溴丁烷:K2CO3 = 1(500mg, 1.8mmol) : 3(4mL) : 5(1.25g, 9.02mmol) 的摩尔比称取,并加入丁醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取, 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),得到淡黄色油状液体(583.3mg, 产率79%);
核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.48 (d, J = 8.0 Hz , 1H, ArH),8.05 (d, J = 8.0 Hz , 1H, ArH), 7.86 (d, J = 8.0 Hz , 1H, ArH), 7.82 (d, J =8.0 Hz , 1H, ArH), 7.63 (t, J = 8.0 Hz, 1H, ArH), 4.29 (t, J = 8.0 Hz, 4H,OCH2), 1.78-1.71 (m, 4H, CH2), 1.50-1.40 (m, 4H, CH2), 0.96 (t, J = 8.0 Hz,6H, CH3);
化合物C2的制备: 在100ml的圆底烧瓶中以4-溴-1,8-萘酐: 正辛胺= 1(1g,3.61mmol) : 3(3mL, 10.83mmol) 的摩尔比称取,并加入乙醇(40ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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),用乙醇和甲醇进行重结晶,得到黄绿色针状晶体(820mg, 产率59%);
核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.65 (d, J = 4.0 Hz , 1H, ArH),8.55 (d, J = 8.0 Hz , 1H, ArH), 8.40 (d, J = 8.0 Hz , 1H, ArH), 8.03 (d, J =8.0 Hz , 1H, ArH), 7.83 (t, J = 8.0 Hz, 1H, ArH), 4.14 (t, J = 8.0 Hz, 2H,OCH2), 1.75-1.68 (m, 2H, CH2), 1.41-1.26 (m, 10H, CH2), 0.86 (t, J = 4.0 Hz,3H, CH3);
化合物C3的制备: 在50ml的圆底烧瓶中以4-溴-1,8-萘酐: 正丁基苯胺= 1(500mg,1.8mmol) : 1.2(323.16mg, 2.17mmol)的摩尔比称取,并加入乙醇(20ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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(522mg, 产率86%);
核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.69 (d, J = 8.0 Hz , 1H, ArH),8.62 (d, J = 8.0 Hz , 1H, ArH), 8.45 (d, J = 8.0 Hz , 1H, ArH), 8.07 (d, J =8.0 Hz , 1H, ArH), 7.87 (t, J = 8.0 Hz, 1H, ArH), 7.36 (d, J = 8.0 Hz , 1H,ArH), 7.21 (d, J = 8.0 Hz , 1H, ArH), 2.69 (t, J = 8.0 Hz, 2H, CH2), 1.71-1.63 (m, 2H, CH2), 1.46-1.37 (m, 2H, CH2), 0.95 (t, J = 8.0 Hz, 3H, CH3);
化合物C4的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 邻苯二胺= 1(200mg,0.72mmol) : 1.1(85.87mg, 0.79mmol)的摩尔比称取,并加入醋酸(4ml),冷凝回流6h,冷却至室温,加入乙醇,过滤,通过硅胶柱层析(洗脱剂:三氯甲烷),用甲苯和乙醇进行重结晶,得到黄色固体(176.1mg, 产率70%);
核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.94-8.83 (m, 1H, ArH), 8.70-8.58(m, 2H, ArH), 8.55-8.50 (m, 1H, ArH), 8.09 (t, J = 8.0 Hz, 1H, ArH), 7.93-7.86 (m, 2H, ArH), 7.52-7.47 (m, 2H, ArH)。
实施例3。
本实施例提供的化合物是中间体(B1)(B2)(B3)(B4), 其制备反应如下:
其中,R是CnH2n+1,n表示碳原子数为12;
在50 ml反应管中以摩尔比c :化合物C(C= C1, C2, C3, C4): K2CO3 : Pd(PPh3)4 = 1: 1.2 : 30 : 0.1称取并加入混合溶剂水(3 ml)/THF(10 ml),其中C1(100mg,0.25mmol), C2(91.6mg, 0.236mmol), C3(100mg, 0.30mmol), C4(80mg, 0.23mmol)在氩气保护下,在70 ℃下反应24 h,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:二氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到B1为白色固体(200.2mg, 产率80%),B2为黄色固体(159.2mg, 产率68%),B3为黄色固体(252.6mg, 产率84%),B4为黄色固体(159mg, 产率84%);
B1的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 7.94-7.91 (m, 2H, ArH), 7.85(d, J = 8.0 Hz , 1H, ArH), 7.37 (t, J = 8.0 Hz , 1H, ArH), 7.24 (d, J = 4.0Hz , 1H, ArH), 7.04 (s, 1H, ArH), 6.79 (s, 1H, ArH), 6.61-6.57 (m, 2H, ArH),6.41 (s, 1H, ArH), 4.29 (t, J = 4.0 Hz , 2H, OCH2), 4.11 (t, J = 4.0 Hz, 2H,OCH2), 3.97 (t, J = 8.0 Hz, 2H, OCH2), 3.83 (t, J = 4.0 Hz, 2H, OCH2), 3.37-3.22 (m, 4H, OCH2), 1.90-1.70 (m, 12H, CH2), 1.49-1.43 (m, 8H, CH2), 1.36-1.25(m, 68H, CH2), 0.97 (t, J = 8.0 Hz, 6H, CH3), 0.90-0.86 (m, 12H, CH3);
B2的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.51(d, J = 8.0 Hz , 1H, ArH),8.47 (d, J = 8.0 Hz , 1H, ArH), 8.04 (d, J = 8.0 Hz , 1H, ArH), 7.56-7.50 (m,2H, ArH), 7.05 (s, 1H, ArH), 6.88 (s, 1H, ArH), 6.61 (d, J = 8.0 Hz , 1H,ArH), 6.56 (d, J = 8.0 Hz , 1H, ArH), 6.38 (s, 1H, ArH), 4.18-4.11 (m, 4H,OCH2), 4.00 (t, J = 8.0 Hz, 2H, OCH2), 3.80 (t, J = 4.0 Hz, 2H, OCH2), 3.40-3.29 (m, 2H, OCH2), 1.89 (t, J = 4.0 Hz, 2H, CH2), 1.82 (t, J = 8.0 Hz, 2H,CH2), 1.73-1.67 (m, 4H, CH2), 1.51 (t, J = 8.0 Hz, 2H, CH2), 1.44(t, J = 8.0Hz, 4H, CH2), 1.36-1.25 (m, 78H, CH2), 0.87 (t, J = 4.0 Hz, 15H, CH3);
B3的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.55(d, J = 8.0 Hz , 1H, ArH),8.51 (d, J = 8.0 Hz , 1H, ArH), 8.09 (d, J = 8.0 Hz , 1H, ArH), 7.56 (s, 1H,ArH), 7.35 (d, J = 8.0 Hz , 2H, ArH), 7.21 (d, J = 8.0 Hz , 2H, ArH), 7.07(s, 1H, ArH), 6.91 (s, 1H, ArH), 6.61 (d, J = 8.0 Hz , 1H, ArH), 6.58 (d, J =8.0 Hz , 1H, ArH), 6.43 (d, J = 4.0 Hz , 1H, ArH), 4.13 (t, J = 4.0 Hz, 2H,OCH2), 4.02 (t, J = 8.0 Hz, 2H, OCH2), 3.82 (t, J = 4.0 Hz, 2H, OCH2), 3.43(t, J = 8.0 Hz, 2H, OCH2), 2.69 (t, J = 8.0 Hz, 2H, CH2), 1.92-1.82 (m, 6H,CH2), 1.73-1.66 (m, 4H, CH2), 1.53-1.47 (m, 6H, CH2), 1.41-1.25 (m, 68H, CH2),0.95 (t, J = 8.0 Hz, 3H, CH3), 0.89-0.86 (m, 12H, CH3);
B4的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 8.83 (d, J = 8.0 Hz , 1H,ArH), 8.67 (d, J = 8.0 Hz , 1H, ArH), 8.57 (t, J = 4.0 Hz , 1H, ArH), 8.05(d, J = 8.0 Hz, 1H, ArH), 7.90 (t, J = 4.0 Hz , 1H, ArH), 7.64 (t, J = 8.0 Hz, 1H, ArH), 7.57 (d, J = 8.0 Hz , 1H, ArH), 7.49-7.46 (m, 2H, ArH), 7.08 (s,1H, ArH), 6.93 (s , 1H, ArH), 6.63 (d, J = 12.0 Hz , 1H, ArH), 6.57 (d, J =8.0 Hz , 1H, ArH), 6.42 (s , 1H, ArH), 4.14 (t, J = 8.0 Hz , 2H, OCH2), 4.03(t, J = 8.0 Hz , 2H, OCH2), 3.79 (t, J = 8.0 Hz , 2H, OCH2), 3.40-3.30 (m, 2H,OCH2), 1.93-1.84 (m, 4H, CH2), 1.70-1.63 (m, 2H, CH2), 1.53-1.47 (m, 4H, CH2),1.41-1.08 (m, 70H, CH2), 0.88-0.84 (m, 12H, CH3)。
实施例4。
本实施例提供的化合物是通式(A1)(A2)(A3)(A4)(A5)的化合物, 其制备反应如下。
化合物(A1)(A3)(A4)(A5)的制备反应如下:
其中,R是CnH2n+1,n表示碳原子数为12;
在100ml的圆底烧瓶中以化合物B(B= B1, B2, B3,B4) : FeCl3 = 1: 3的摩尔比称取,其中B1(150mg, 0.12mmol), B2(134mg, 0.11mmol), B3(150mg, 0.12mmol), B4(100mg,0.10mmol)并加入三氯甲烷(60ml),硝基甲烷(5ml)、在室温下反应,每隔5min点板跟踪反应,反应完毕,加入甲醇终止反应,用三氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:三氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到A1为橙色固体(103mg, 70%),A3为黄色固体(117.8mg, 88%),A4为橙色固体(136.7mg, 91%),A5为橙黄色固体(90.1mg, 65%);
A1的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 9.47(s, 1H, ArH), 9.17 (d, J =8.0 Hz , 1H, ArH), 8.61 (d, J = 4.0 Hz , 1H, ArH), 8.05 (s, 1H, ArH), 7.93(s, 1H, ArH), 7.82 (t, J = 4.0 Hz, 3H, ArH), 4.34-4.22 (m, 6H, OCH2), 4.11(t, J = 8.0 Hz, 2H, OCH2), 2.00-1.92 (m, 8H, CH2), 1.61-1.52 (m, 8H, CH2),1.45-1.27 (m, 64H, CH2), 0.92-0.86 (m, 12H, CH3);
A3的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 9.61 (s, 1H, ArH), 9.16 (d, J= 8.0 Hz , 1H, ArH), 8.63 (d, J = 8.0 Hz , 1H, ArH), 8.18 (s, 1H, ArH), 8.10(s, 1H, ArH), 7.89 (s, 1H, ArH), 7.86 (s, 1H, ArH), 7.81 (t, J = 8.0 Hz, 1H,ArH), 4.33-4.26 (m, 8H, OCH2), 4.17 (t, J = 8.0 Hz, 2H, OCH2), 1.99-1.89 (m,8H, CH2), 1.79 (t, J = 8.0 Hz, 2H, CH2), 1.59-1.50 (m, 10H, CH2), 1.45-1.27(m, 72H, CH2), 0.88 (t, J = 8.0 Hz, 15H, CH3);
A4的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 9.64(s, 1H, ArH), 9.21 (d, J =8.0 Hz , 1H, ArH), 8.68 (d, J = 4.0 Hz , 1H, ArH), 8.21 (s, 1H, ArH), 8.08(s, 1H, ArH), 7.90 (s, 1H, ArH), 7.87-7.83 (m, 2H, ArH), 7.39 (d, J = 8.0 Hz, 2H, ArH), 7.29 (d, J = 8.0 Hz , 2H, ArH), 4.33 (t, J = 8.0 Hz, 2H, OCH2),4.28 (t, J = 8.0 Hz, 2H, OCH2), 4.22 (t, J = 8.0 Hz, 2H, OCH2), 4.17 (t, J =8.0 Hz, 2H, OCH2), 2.72 (t, J = 8.0 Hz, 2H, CH2), 2.02-1.90 (m, 8H, CH2),1.72-1.56 (m, 14H, CH2), 1.45-1.27 (m, 62H, CH2), 0.97 (t, J = 8.0 Hz, 3H,CH3), 0.89-0.86 (m, 12H, CH3);
A5的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 9.48 (s, 1H, ArH), 8.97 (d, J= 8.0 Hz , 1H, ArH), 8.77 (d, J = 8.0 Hz , 1H, ArH), 8.54 (d, J = 4.0 Hz, 1H,ArH), 8.10 (s, 1H, ArH), 7.92-7.88 (m, 2H, ArH), 7.78 (t, J = 8.0 Hz , 1H,ArH), 7.69 (s, 1H, ArH), 7.65 (s, 1H, ArH), 7.47 (t, J = 4.0 Hz , 2H, ArH),4.28-4.17 (m, 8H, OCH2), 2.01-1.95 (m, 8H, CH2), 1.65-1.56 (m, 8H, CH2), 1.45-1.28 (m, 64H, CH2), 0.88 (d, J = 8.0 Hz, 12H, CH3);
化合物(A2)的制备反应如下:
在25ml的圆底烧瓶中以9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1): 正溴丁烷= 1(100mg, 0.09mmol) : 3(4mL) 的比称取,并加入乙醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取, 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=1:1.5),用乙酸乙酯和甲醇进行重结晶,得到黄绿色固体(76.6mg, 产率70%);
A2的核磁氢谱1H NMR (CDCl3, TMS, 400 MHz) δ: 9.00 (d, J = 4.0 Hz , 2H,ArH), 8.15 (s, 1H, ArH), 8.03 (d, J = 8.0 Hz , 1H, ArH), 7.97 (s, 1H, ArH),7.90 (s, 1H, ArH), 7.87 (s, 1H, ArH), 7.63 (t, J = 8.0 Hz , 1H, ArH), 4.40-4.35 (m, 4H, OCH2), 4.32-4.24 (m, 6H, OCH2), 4.13 (t, J = 8.0 Hz, 2H, OCH2),2.00-1.89 (m, 8H, CH2), 1.82-1.77 (m, 4H, CH2), 1.63-1.54 (m, 8H, CH2), 1.51-1.27 (m, 68H, CH2), 1.02-0.97 (m, 6H, CH3), 0.88 (t, J = 8.0 Hz, 12H, CH3)。
Claims (5)
1.一种由萘酸酐构建的盘状液晶化合物, 9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1), 2,3,12,13-四(十二烷氧基)苯并[g] ch-6,7-二羧酸二丁酯(A2), 9,10,13,14-四(十二烷氧基)-5-辛基-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A3), 5-(4-丁基苯基)-9,10,13,14-四(十二烷氧基)-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A4)以及2,3,6,7-四(十二烷基氧基)-10H苯并[de]苯并[4,5]咪唑并[1,2-b]菲[9,10-g]异喹啉-10-酮(A5)的盘状液晶化合物,其特征在于具有以下所示的结构:
2.一种权利要求1(A1)(A2)(A3) (A4) (A5)的化合物,其制备方法为:
步骤一:中间体2-溴-3',4,4',5-四(十二烷氧基)-1,1'-联苯(b)制备:
以式a所示的化合物为原料,将其与溴单质以1:1的摩尔比在250ml圆底烧瓶中称取,加入150ml三氯甲烷,套上恒压滴液漏斗,往其中加入三氯甲烷(20ml)和溴单质,将圆底烧瓶放入室温的环境中,恒压滴液漏斗中的溶液控制在2秒每滴,每隔15分钟点板跟踪,反应完毕,加入亚硫酸氢钠终止反应,过滤,用旋干,通过硅胶柱层析(洗脱剂:V二氯甲烷:V石油醚=1:2),用乙醇、乙酸乙酯重结晶,得产物b,其中R为-C12H25;
步骤二:中间体4,4,5,5-四甲基-2-(3',4,4',5-四(烷氧基)-[1,1'-联苯] -2-基)-1,3,2-二氧杂硼烷(c)的合成:
其中,R是C12H25;
在100 ml反应管中以摩尔比2-溴-3',4,4' ,5-四(烷氧基)-1,1'-联苯(b):双戊酰二硼: CH3COOK: PdCl2(dppf)= 1 : 1.5 : 0.05 : 3称取并加入1,4-二氧六环25 ml,在氩气保护下,在90 ℃下反应24h,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=1:3),用乙酸乙酯和甲醇进行重结晶,得到白色固体 (c)。
3.步骤三:中间体为(C1) (C2) (C3) (C4)化合物的制备:
化合物C1的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 正溴丁烷:K2CO3 = 1 : 3 :5 的摩尔比称取,并加入丁醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取,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),得到淡黄色油状液体;
化合物C2的制备: 在100ml的圆底烧瓶中以4-溴-1,8-萘酐: 正辛胺= 1 : 3 的摩尔比称取,并加入乙醇(40ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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),用乙醇和甲醇进行重结晶,得到黄绿色针状晶体;
化合物C3的制备: 在50ml的圆底烧瓶中以4-溴-1,8-萘酐: 正丁基苯胺= 1 : 1.2的摩尔比称取,并加入乙醇(20ml),冷凝回流10h,冷却至室温,用二氯甲烷进行萃取, 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;
化合物C4的制备: 在25ml的圆底烧瓶中以4-溴-1,8-萘酐: 邻苯二胺= 1 : 1.1的摩尔比称取,并加入醋酸(4ml),冷凝回流6h,冷却至室温,加入乙醇,过滤,通过硅胶柱层析(洗脱剂:三氯甲烷),用甲苯和乙醇进行重结晶,得到黄色固体;
步骤四:中间体为(B1)(B2)(B3)(B4)化合物的制备:
其中,R是CnH2n+1,n表示碳原子数为12;
在50 ml反应管中以摩尔比c :化合物C(C= C1, C2, C3, C4): K2CO3 : Pd(PPh3)4 = 1 :1.2 : 30 : 0.1称取并加入混合溶剂水(3 ml)/THF(10 ml),在氩气保护下,在70 ℃下反应24 h,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:二氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到B1为白色固体,B2为黄色固体,B3为黄色固体,B4为黄色固体;
步骤五:化合物(A1)(A3) (A4) (A5)的合成:
在100ml的圆底烧瓶中以化合物B(B= B1, B2, B3,B4) : FeCl3 = 1 : 3 的摩尔比称取,并加入三氯甲烷(60ml),硝基甲烷(5ml)、在室温下反应,每隔5min点板跟踪反应,反应完毕,加入甲醇终止反应,用三氯甲烷进行萃取,有机相用无水MgSO4干燥,过滤,旋干,通过硅胶柱层析(洗脱剂:三氯甲烷 + 石油醚),用乙酸乙酯和乙醇进行重结晶,得到A1为橙色固体,A3为黄色固体,A4为橙色固体,A5为橙黄色固体;
步骤五:化合物(A2)的合成:
在25ml的圆底烧瓶中以9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1): 正溴丁烷= 1 : 3 的摩尔比称取,并加入乙醇(4ml),冷凝回流24h,冷却至室温,用二氯甲烷进行萃取, 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=1:1.5),用乙酸乙酯和甲醇进行重结晶,得到黄绿色固体。
4.一种权利要求1所述中9,10,13,14-四(十二烷氧基)-4H,6H-苯并[de]菲基[9,10-g]异戊烯-4,6-二酮(A1), 9,10,13,14-四(十二烷氧基)-5-辛基-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A3), 5-(4-丁基苯基)-9,10,13,14-四(十二烷氧基)-4H-苯并[de]菲基[9,10-g]异喹啉-4,6(5H)-二酮(A4)以及2,3,6,7-四(十二烷基氧基)-10H苯并[de]苯并[4,5]咪唑并[1,2-b]菲[9,10-g]异喹啉-10-酮(A5)作为有机液晶半导体材料。
5.一种权利要求1所述中2,3,12,13-四(十二烷氧基)苯并[g] ch-6,7-二羧酸二丁酯(A2)作为有机光致发光材料的用途。
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CN106167708A (zh) * | 2016-07-22 | 2016-11-30 | 四川师范大学 | 2,3‑二酰亚胺苯并菲盘状液晶分子及其制备方法 |
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