CN104163785A - 一系列含吲哚啉衍生物结构的不对称方酸菁小分子及其应用 - Google Patents
一系列含吲哚啉衍生物结构的不对称方酸菁小分子及其应用 Download PDFInfo
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Abstract
本发明提供一系列新型不对称方酸菁小分子及其运用。通过在方酸四元环两端引入不同的富电芳香单元作为给体单元,设计合成了一系列低带隙的不对称方酸菁小分子光伏材料,其在可见及近红外光区具有强烈的吸收,吸收光谱覆盖400-900nm;其HOMO、LUMO与受体材料PCBM的能级匹配良好,获得高的开路电压,而且这类化合物都具有良好的溶解性和成膜性,使其可应用于低成本的溶液加工本体异质结有机太阳能电池器件。以不对称方酸小分子为给体材料的有机太阳能电池器件性能可达到:白光1.5G(100mw/cm2)照射下,开路电压(Voc)=0.72-1.05V,短路电流(Jsc)=8.80-12.67mA/cm2,填充因子(FF)=0.38-0.55,光电转化效率(PCE)=2.41-6.10%。
Description
一、技术领域
本发明涉及一系列含吲哚啉衍生物结构的不对称方酸菁小分子及制备方法,以及该类方酸菁小分子在有机太阳能电池领域的应用。
二、背景技术
目前,能源危机和环境问题日益严峻,而太阳能作为一种永不枯竭的清洁能源得到了大家的重视。太阳能电池是利用太阳能的重要手段之一,主要分为无机太阳能电池和有机太阳能电池(OPV)。相比于无机太阳能电池,有机太阳能电池具有重量轻、成本低、柔韧性好等显著优点。近几十年来,新型有机光伏材料的设计合成及器件结构的设计优化已经获得了极大进步。由于小分子光伏材料相比于聚合物光伏材料具有确定的分子结构、确定的分子量、易提纯及批次重现性好等优点,其在太阳能电池领域的应用得到了极大关注。为推进有机太阳能电池的实际化应用,研究开发更多有效的新型小分子光伏给体材料对提高太阳能电池器件的效率至关重要。
方酸菁化合物(结构式如下所示)由于其在可见及近红外区有强烈的吸收和优良的光化学和光物理稳定性,已经得到了广泛的应用。Paganiet al.第一次报道了以方酸菁小分子为给体材料的溶液加工的本体异质结有机太阳能电池器件,其光电转换效率达到1.24%(J. Am. Chem. Soc. 2008, 130, 17640-17641.)。之后,方酸菁小分子在有机太阳能电池领域的应用得到了良好的发展。到目前为止,基于溶液加工的方酸菁小分子的本体异质结有机太阳能电池的PCE已高达5.50%(Adv. Energy. Mater. 2011, 1, 184-187.),而以方酸菁小分子为给体材料的双层有机太阳能电池器件的效率则高达6.3%(Nano Lett. 2011, 11, 4261-4264.),这表明方酸菁小分子在太阳能电池领域极富应用前景。一般而言,相较于之前提到的对称型方酸菁小分子(即X=Y,如下所示),不对称方酸菁小分子(即X≠Y)具有更好的溶解性,最重要的是具有更丰富的结构可调性,已经在染料敏化太阳电池、静电复印、近红外增感等光敏应用方面具有较对称型方酸化合物更为优异的性能。但由于不对称方酸菁小分子的合成步骤稍多,且性能相对低下,故在OPV中研究还不广泛。目前检索到的不对称方酸菁小分子在有机太阳能电池领域应用的文献仅有6篇(Angew. Chem. Int. Ed. 2009,48,8776- 8779;Sol. Energy Mater. Sol. Cells 2012,98,224-232;ACS Nano 2012,6,972-978;J. Mater. Chem. 2012,22,6704-6710;Phys. Chem. Chem. Phys. 2012, 14, 8382-8334;Chem. Commun. 2013, 49, 10465-10467.),ACS Nano中报道的材料性能最佳,但光学能隙约在2.0 eV,相对较高,与太阳光谱的匹配不佳。因而设计、合成新型不对称方酸菁光伏材料,对构建新型高效光伏材料具有重要意义。
三、发明内容
本发明的目的之一在于提供一系列新型的含吲哚啉衍生物结构的不对称方酸菁小分子。
本发明提供具有如下通式Ⅰ的不对称方酸菁小分子,X、Y代表不同的富电芳香环单元,
其结构特征在于:
所述X为如下基团1~4中的任意一个,其中R1,R3,R4,R5为氢原子或氟原子或氰基,R2为碳原子数为1-20的直链或支链的烷基或苯烷基。
基团1:
基团2:
基团3:
基团4:
所述Y为如下基团5~8中的任意一个,
基团5:
基团6:
基团7:
基团8:
基团5, 6, 7, 8中R1、R2、R3和R4为相同或不相同的氢原子或氟原子或氰基。
本发明的目的之二在于提供本发明中不对称方酸菁小分子的用途,特别是在有机太阳能电池上的运用。
该有机太阳能电池器件结构如附图7所示,a为本体异质结器件结构,其中MoO3或PEDOT:PSS的厚度为6-8 nm;不对称方酸菁小分子和PCBM的共混薄膜的厚度为20-400 nm;LiF的厚度为0.5-0.8 nm;Al或Ag电极的厚度为60-200 nm。 b为双层器件结构,其中MoO3或PEDOT:PSS的厚度为6-16 nm;不对称方酸菁小分子薄膜的厚度为4-30 nm;PCBM薄膜的厚度为20-60 nm;BCP(化学结构示于图中)的厚度为5-20 nm;Al或Ag电极的厚度为60-200 nm。以上所述的不对称方酸菁小分子薄膜层用作太阳能电池的光活性层。
有益效果:本发明提供的不对称方酸菁小分子材料,用作有机太阳能电池的光活性层,其有益效果为:
(1)在可见及近红外光区有强烈的吸收。相较于文献中报道的不对称方酸菁小分子光伏材料,本发明提供的不对称方酸菁小分子材料的能隙更窄,光谱响应范围更宽(400-900 nm),与太阳光谱更匹配,这将有利于提高光活性层对太阳光的吸收,大大地提高了太阳能电池器件的短路电流(8.80-12.67mA cm-2),从而提高光伏器件的光电转化效率。
(2)合适的HOMO能级和LUMO能级。本发明通过调节方酸中心环两端的给体单元合成的不对称方酸菁小分子材料,其HOMO、LUMO能级与受体材料PCBM的能级匹配性良好,有利于太阳能电池中激子的解离并且提高器件的开路电压(0.72-1.05 V)。
(3)良好的溶解性与成膜性。本发明提供的不对称方酸菁小分子材料在常见的有机溶剂,如氯仿、氯苯、邻二氯苯、甲苯等中有良好的溶解性与成膜性,使其可应用于低成本溶液加工的本体异质结器件。
以上述不对称方酸小分子为给体材料的有机太阳能电池器件性能分别为:白光1.5 G(100 mw/cm2)照射下,开路电压(V oc )=0.72-1.05V,短路电流(J sc )=8.80-12.67 mA/cm2,填充因子(FF)=0.38-0.55,光电转化效率(PCE)=2.41-6.10%。
四、附图说明
图1是实施例1中不对称方酸ASQ-1在氯仿溶液中和固体薄膜的紫外可见吸收光谱。
图2是实施例10中不对称方酸ASQ-10在氯仿溶液中和固体薄膜的紫外可见吸收光谱。
图3是实施例3和17中不对称方酸ASQ-3、ASQ-17在氯仿溶液中紫外可见吸收光谱。
图4是实施例3和17中不对称方酸ASQ-3、ASQ-17在固体薄膜中紫外可见吸收光谱。
图5是实施例1、5、10中不对称方酸 ASQ-1、ASQ-5、ASQ-10本体异质结有机太阳能电池器件的电流-电压曲线。
图6是实施例1、10中不对称方酸 ASQ-1、ASQ-10的本体异质结有机太阳能电池器件的外量子效率图。
图7是有机太阳能电池器件的结构示意图。
五、具体实施方式
实施例1:不对称方酸ASQ-1的制备
(1)化合物3的制备
2 5.00g (12.7mmol)(合成方法见Eur. J. Org. Chem. 2008, 12, 2107–2117.)加入120mL混合溶剂(三乙胺:乙醇=1:8,v/v),加热回流30min。冷却至室温,加入1 1.83g (12.7mmol)(合成方法见J. Am. Chem. Soc. 2007, 129, 10320-10321.),回流反应30min,减压蒸出溶剂,柱层析(PE:EA=8:1),乙醇重结晶得橙黄色晶体2.04g,产率68%。m.p. 187-188℃; 1H NMR (CDCl3, 400MHz, ppm) δ: 8.11 (d, J = 8.4Hz, 1H), 7.89 (d, J = 8.4Hz, 1H), 7.85 (d, J = 8.4Hz, 1H), 7.54 (t, J = 7.6Hz, 1H), 7.38 (t, J = 7.6Hz, 1H), 7.23 (d, J = 8.8Hz, 1H), 5.46 (s, 1H), 4.96 (q, J = 7.2Hz, 2H), 3.94 (t, J = 7.2Hz, 2H), 1.90 (s, 6H), 1.83-1.75 (m, 2H), 1.58 (t, J = 7.2Hz, 3H), 1.50-1.43 (m, 2H), 1.01 (t, J = 7.2Hz, 3H)。
(2)化合物4的制备
3 2.04 g (5.2 mmol) 加入80 mL丙酮中,加热回流至固体全部溶解,滴加6M HCl 30 mL,薄层色谱监测反应,反应完全后,滴加饱和碳酸氢钠水溶液调PH=3~4,黄色沉淀物析出,过滤得橙黄色粉末1.59 g,产率84%。1H NMR (DMSO-d 6 , 400MHz, ppm) δ: 8.06 (d, J = 8.8 Hz, 1H, Ar-H), 7.85 (d, J = 8.0 Hz, 1H, Ar-H), 7.81 (d, J = 8.8 Hz, 1H, Ar-H), 7.45 (t, J = 7.6 Hz, 1H, Ar-H), 7.34 (d, J = 8.8 Hz, 1H, Ar-H), 7.23 (t, J = 7.6 Hz, 1H, Ar-H), 5.45 (s, 1H, =CH-), 3.83 (t, J = 7.2 Hz, 2H, -NCH2-), 1.83 (s, 6H, -CH3), 1.68-1.61 (m, 2H, -CH2-), 1.43-1.34(m, 2H, -CH2-), 0.93 (t, J = 7.6 Hz, 3H, -CH3)。13C NMR (DMSO-d 6 , 100MHz, ppm) δ: 191.7, 190.4, 173.4, 167.5, 140.2, 130.8, 130.0, 129.6, 129.4, 128.0, 127.1, 123.2, 121.8, 110.6, 81.0, 48.8, 41.9, 28.3, 26.3, 19.6, 13.8。ESI-MS m/z: 360.14 [M-H]-。
(3)化合物6的制备
5 0.90 g (5.65 mmol) (合成方法见Tetrahedron Lett. 2004, 45, 4851-4854.),3,5-二甲氧基溴苯1.23 g (5.65 mmol),3%摩尔量的Pd(OAc)2 (38 mg),5%摩尔量的P(t-Bu)3 .HBF4 (81mg),叔丁醇钠0.81g (8.48 mg)加入50 mL甲苯中,110℃加热5 h,过滤,滤液减压旋除溶剂,柱层析(PE),得到浅黄色油状物1.50 g,产率90%。1H NMR (400 MHz, CDCl3, δ): 7.12 (d, J = 7.2 Hz , 1H, ArH), 7.09-7.03 (m, 2H, ArH), 6.76-6.72 (m, 1H, ArH), 6.47 (d, J = 2.0 Hz, 2H, ArH), 6.12 (t, J = 2.0 Hz, 1H, ArH), 4.72-4.67 (m, 1H, CH), 3.84-3.81 (m, 1H, CH), 3.79 (s, 6H, CH3), 2.07-1.81 (m, 4H, CH2), 1.68-1.60 (m, 1H, CH2), 1.55-1.44 (m, 1H, CH2).
(4)化合物7的制备
6 1.50 g (5.07 mmol) 加入60 mL无水二氯甲烷,冰浴下缓慢滴加50 mL含三溴化硼12.7 g (50.7 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入200 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得黄色固体0.98 g,产率72%。1H NMR (400 MHz, CDCl3, δ): 7.14-7.06 (m, 3H, ArH), 6.83-6.78 (m, 1H, ArH), 6.38 (s, 2H, ArH), 6.08 (s, 1H, ArH), 4.64-4.60 (m, 1H, CH), 3.87-3.78 (m, 1H, CH), 2.00-1.88 (m, 4H, CH2), 1.68-1.60 (br, 1H, CH2), 1.44-1.39 (br, 1H, CH2).
(5)ASQ-1的制备
4 1.10 g (3.06 mmol),7 0.98 g (3.67 mmol),80 mL混合溶剂(甲苯:正丁醇=3:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(PE:EA=2:1),重结晶(二氯甲烷:甲醇)得亮黄色晶体ASQ-1 1.3g,产率72%。m.p. 235-237℃. FT-IR: v=1636 cm-1 (C-O). 1H NMR (400 MHz, CDCl3, δ): 12.36 (s, 2H, OH), 8.23 (d, J = 8.8 Hz, 1H, ArH), 7.96 (d, J = 8.0 Hz, 1H, ArH), 7.95 (d, J = 8.8 Hz, 1H, ArH), 7.66 (t, J = 7.2 Hz, 1H, ArH), 7.53 (t, J = 7.6 Hz, 1H, ArH), 7.39 (d, J = 8.8 Hz,2H, ArH), 7.18 (t, J = 7.2 Hz, 2H, ArH), 6.95 (t, J = 7.6 Hz, 1H, ArH), 6.36 (s,2H, ArH), 5.99 (s, 1H, CH), 4.69 (br, 1H, CH), 4.24 (t, J = 7.6 Hz, 2H, CH2), 3.92 (t, J = 7.6 Hz, 1H, CH), 2.04 (s, 6H, CH3),2.01-1.93 (m, 2H, CH2), 1.92-1.84 (m, 2H, CH2),1.71-1.64 (m, 2H, CH2), 1.56-1.46 (m, 2H, CH2), 1.45-1.37 (m, 2H, CH2), 1.04 (t, J = 7.2 Hz, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ): 174.3, 168.6, 168.3, 151.3, 143.1, 137.7, 135.8, 135.0, 131.0, 129.2, 128.8, 127.3, 126.8, 126.4, 124.4, 123.8, 121.7, 121.1, 112.4, 109.4, 103.5, 95.8, 86.5, 67.6, 51.1, 44.5, 43.4, 33.6, 32.8, 28.7, 25.4, 23.3, 19.3, 12.8. HRMS (ESI) m/z: [M+H]+ calcd for C40H39N2O4, 611.2921; found, 611.2919.
实施例2:不对称方酸ASQ-2的制备
(1)化合物8的制备
50 mL三颈瓶中中,加入苯肼2.26 g (20.4 mmol),环己酮1.72 g (20.4 mmol),10 mL自来水,搅拌均匀后,室温下滴加1.4 mL浓硫酸。滴加完毕后,回流反应1 h,冷却至室温,倾出上层清液。三颈瓶中加入50 mL正己烷,升温回流30 min,稍冷后倾出上清液,放置冰箱冷冻,白色固体析出。重复上述操作3-5次,抽滤得白色固体2.69 g,产率77%。
(2) 化合物9的制备
8 3.55 g (20.7 mmol),10% Pd/C 0.70 g, 加入70 mL四氢呋喃中,室温下用氢气气囊向反应液中通入氢气,反应12 h后,抽滤,回收Pd/C,滤液旋干,柱层析(中性氧化铝,PE:EA=100:1)得淡黄色油状物 2.80 g,产率78%。1H NMR (CDCl3, 400 MHz, ppm) δ: 7.04 (d, J = 7.2 Hz, 1H, Ar-H), 7.00 (t, J = 7.6 Hz, 1H, Ar-H), 6.68-6.64 (m, 1H, Ar-H), 6.53 (d, J = 7.6 Hz, 1H, Ar-H), 4.37-4.33 (m, 1H, CH), 3.79-3.74 (m, 1H, CH), 3.77 (br, 1H, NH), 2.00-1.90 (m, 4H, CH2),1.81-1.50 (m, 4H, CH2)。
(3)化合物10的制备
9 2.22 g (12.8 mmol),3,5-二甲氧基溴苯2.78 g (12.8 mmol),3%摩尔量的Pd(OAc)2 (86 mg),5%摩尔量的P(t-Bu)3 .HBF4 (186 mg),1.5倍摩尔量的叔丁醇钠 (1.84g)加入100 mL甲苯中,110℃加热5 h,过滤,滤液减压旋除溶剂,柱层析(PE)得橙黄色油状物2.42 g,产率61%。
(4)化合物11的制备
10 1.01 g (3.25 mmol) 加入40 mL无水二氯甲烷,冰浴下缓慢滴加34 mL含三溴化硼8.15 g (32.5 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌36 h。反应液倾入200 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得白色固体0.87 g,产率86%。
(5)ASQ-2的制备
4 0.68 g (1.88 mmol),11 0.63 g (2.25 mmol),60 mL混合溶剂(甲苯:正丁醇=3:1,v/v),分水回流38 h,减压蒸出溶剂,柱层析(PE:EA=1:1),重结晶(二氯甲烷:甲醇)得绿色晶体0.82 g 产率70%。1H NMR (400 MHz, CDCl3, δ): 12.15 (s, 2H, OH), 8.26 (d, J = 8.4 Hz, 1H, ArH), 8.02 (d, J = 8.8 Hz, 1H, ArH), 8.01 (d, J = 8.0 Hz, 1H, ArH), 7.72 (t, J = 7.2 Hz, 1H, ArH), 7.61 (t, J = 7.6 Hz, 1H, ArH), 7.53-7.46 (m, 3H, ArH), 7.16-7.11 (m, 2H, ArH), 6.45 (s, 2H, ArH), 6.22 (s, 1H, CH), 4.39 (t, J = 7.6 Hz, 2H, CH2),4.37-4.33 (m, 1H, CH), 3.79-3.74 (m, 1H, CH), 2.77 (d, J = 6.4 Hz, 4H, CH2), 2.07 (s, 6H, CH3),1.98-1.89 (m, 6H, CH2),1.58-1.49 (m, 2H, CH2), 1.07 (t, J = 7.2 Hz, 3H, CH3).
实施例3:不对称方酸ASQ-3的制备
(1) 12的制备
吲哚啉 1.10 g (9.22 mmol),3,5-二甲氧基溴苯2.00 g (9.22 mmol),3%摩尔量的Pd(OAc)2 (62 mg),6%摩尔量的P(t-Bu)3 .HBF4 (160 mg),叔丁醇钠 (1.77g, 18.44 mmol)加入100 mL甲苯中,110℃加热10h,过滤,滤液减压旋除溶剂,柱层析(PE:EA=15:1)得无色油状物2.00 g,产率85%。1H NMR (400 MHz, CDCl3, ppm) δ: 7.20 (d, 1H, J=8.0 Hz, Ar), 7.17 (d, 1H, J=7.6 Hz, Ar), 7.09 (t, 1H, J=7.6 Hz, Ar), 6.77 (t, 1H, J=7.6 Hz, Ar), 6.41 (d, 2H, 3 J=2.0 Hz, Ar), 6.12 (t, 1H, 3 J=2.0 Hz, Ar), 3.96 (t, 2H, J=8.4 Hz, -NCH2-), 3.80 (s, 6H, -OCH3), 3.13 (t, 2H, J=8.4 Hz, -CH2-).
(2) 13的制备
12 1.00 g (3.91 mmol) 加入40 mL无水二氯甲烷,冰浴下缓慢滴加40 mL含三溴化硼9.79 g (39.1 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析(CHCl2:CH3OH=50:1)得无色粘稠状液体0.65 g,产率71%。
(3) ASQ-3的制备
4 0.70 g (1.94 mmol),13 0.50 g (2.16 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH=50:1),重结晶(CHCl2:CH3OH=1:6)得绿色金属光泽晶体ASQ-3 0.87 g,产率78%。mp 229-230 °C. 1H NMR (400 MHz, CDCl3, ppm) δ:12.37 (s, 2H, -OH), 8.23 (d, 1H, J=8.4 Hz, Ar), 7.96 (d, 1H, J=8.0 Hz, Ar), 7.95 (d, 1H, J=8.8 Hz, Ar), 7.65 (t, 1H, J=8.0 Hz, Ar), 7.53 (t, 1H, J=8.0 Hz, Ar), 7.44 (d, 1H, J=8.0 Hz, Ar), 7.39 (d, 1H, J=8.8 Hz, Ar), 7.22 (d, 1H, J=7.2 Hz, Ar), 7.19 (t, 1H, J=8.0 Hz, Ar), 6.92 (t, 1H, J=7.2 Hz, Ar), 6.29 (s, 2H, Ar), 5.99 (s, 1H, =CH-), 4.24 (t, 2H, J=7.6 Hz, -NCH2-), 4.07 (t, 2H, J=7.6 Hz, -NCH2-), 3.17 (t, 2H, J=8.4 Hz, -CH2-), 2.04 (s, 6H, -CH3), 1.92-1.84 (m, 2H, -CH2-), 1.56-1.46 (m, 2H, -CH2-), 1.04 (t, 3H, J=7.6 Hz, -CH3); 13C NMR (100 MHz, CDCl3, ppm) δ: 175.59, 169.24, 168.46, 162.88, 152.43, 144.10, 138.63, 136.12, 133.14, 132.09, 130.33, 129.86, 128.26, 127.87, 127.41, 125.56, 125.31, 122.77, 121.82, 113.05, 110.51, 104.29, 96.46, 87.78, 52.23, 52.00, 44.58, 29.83, 27.97, 26.38, 20.31, 13.85. HR-MS (ESI): m/z [M+H] 571.2592, calcd.: 571.2597.
实施例4:不对称方酸ASQ-4的制备
(1) 14的制备
1,2,3,4-四氢喹啉 1.23 g (9.22 mmol),3,5-二甲氧基溴苯2.00 g (9.22 mmol),3%摩尔量的Pd(OAc)2 (62 mg),6%摩尔量的P(t-Bu)3 .HBF4 (160 mg),叔丁醇钠 (1.77g, 18.44 mmol)加入100 mL甲苯中,110℃加热10h,过滤,滤液减压旋除溶剂,柱层析(PE:EA=15:1)得无色油状物2.01 g,产率81%。1H NMR (400 MHz, CDCl3, ppm) δ: 7.05 (d, 1H, J=7.2 Hz, Ar), 6.97 (t, 1H, J=8.0 Hz, Ar), 6.87 (d, 1H, J=8.0 Hz, Ar), 6.74 (t, 1H, J=7.6 Hz, Ar), 6.40 (d, 2H, 3 J=2.4 Hz, Ar), 6.22 (t, 1H, 3 J=2.0 Hz, Ar), 3.76 (s, 6H, -OCH3), 3.62 (t, 2H, J=5.6 Hz, -NCH2-), 2.84 (t, 2H, J=6.4 Hz, -CH2-), 2.05-1.99 (m, 2H, -CH2-).
(2) 15的制备
14 1.00 g (3.70 mmol) 加入40 mL无水二氯甲烷,冰浴下缓慢滴加50 mL含三溴化硼7.41 g (29.6 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析(CHCl2:CH3OH=50:1)得无色粘稠状液体0.78 g,产率86%。
(3) ASQ-4的制备
4 0.92 g (2.56 mmol),15 0.70 g (2.84 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH=50:1),重结晶(CHCl2:CH3OH=1:8)得带金属光泽的金色晶体ASQ-4 1.21 g,产率80%。mp 245-246 °C. 1H NMR (400 MHz, CDCl3, ppm) δ: 8.22 (d, 1H, J=8.4 Hz, Ar), 7.96 (d, 1H, J=8.0 Hz, Ar), 7.95 (d, 1H, J=8.8 Hz, Ar), 7.65 (t, 1H, J=8.0 Hz, Ar), 7.52 (t, 1H, J=7.6 Hz, Ar), 7.39 (d, 1H, J=8.8 Hz, Ar), 7.34 (d, 1H, J=8.4 Hz, Ar), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 6.22 (s, 2H, Ar), 5.98 (s, 1H, =CH-), 4.23 (t, 2H, J=7.6 Hz, -NCH2-), 3.72 (t, 2H, J=6.4 Hz, -NCH2-), 2.73 (t, 2H, J=6.4 Hz, -CH2-), 2.03 (s, 6H, -CH3), 2.03-1.97 (m, 2H, -CH2-), 1.91-1.84 (m, 2H, -CH2-), 1.55- 1.46 (m, 2H, -CH2-), 1.04 (t, 3H, J=7.2 Hz, -CH3); 13C NMR (100 MHz, CDCl3, ppm) δ: 175.49, 169.70, 168.98, 162.46, 156.66, 140.19, 138.66, 136.04, 132.06, 132.04, 130.30, 129.86, 128.73, 128.28, 127.85, 126.44, 125.52, 123.40, 122.76, 110.49, 104.60, 98.09, 87.67, 52.21, 48.36, 44.53, 29.80, 27.12, 26.39, 24.28, 20.31, 13.85. HR-MS (ESI): m/z [M+H] 585.2736, calcd.: 585.2753.
实施例5:不对称方酸ASQ-5的制备
(1)化合物17的制备
16 2.52g (7.06mmol)(合成方法见J. Org. Chem. 1995, 60,2391-2395.)加入20mL混合溶剂(三乙胺:乙醇=1:8,v/v),加热回流30min。滴加1 1.20g (7.06mmol),回流反应15min,减压蒸出溶剂,柱层析(PE:EA=8:1),乙醇重结晶得橙黄色晶体1.98g,产率80%。1H NMR (CDCl3, 400MHz, ppm) δ: 8.17 (d, J = 8.4Hz, 1H), 7.90 (d, J = 8.4Hz, 1H), 7.85 (d, J = 8.4Hz, 1H), 7.76 (t, J = 7.6Hz, 1H), 7.43 (t, J = 7.6Hz, 1H), 7.39 (d, 1H, J=8.8 Hz, Ar), 7.34 (d, 1H, J=8.4 Hz, Ar), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 5.38 (s, 1H), 4.96 (q, J = 7.2Hz, 2H), 3.83 (q, J = 7.2Hz, 2H), 1.49 (t, J = 7.2Hz, 3H), 1.93 (t, J = 7.2Hz, 3H)。
(2)化合物18的制备
17 1.84g (5.24mmol) 加入40mL无水乙醇,回流状态下加入3mL 40% NaOH,反应30min,减压旋除溶剂,残余物溶于20mL水,滴加饱和柠檬酸至PH=3~4,黄色沉淀物析出,过滤得黄色粉末1.02g,产率60%。1H NMR (DMSO-d 6 , 400MHz, ppm)δ: 8.21 (d, J = 8.8 Hz, 1H), 8.01 (d, J = 8.4Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.25 (d, J = 8.8 Hz, 1H), 7.14 (t, J = 7.6 Hz, 1H), 5.38 (s, 1H), 4.57 (q, J = 7.2 Hz, 2H), 1.84 (t, J = 7.2 Hz, 3H)。
(3)ASQ-5的制备
18 0.57g (1.73mmol),7 0.46g (1.73mmol),80mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36h,减压蒸出溶剂,柱层析(CH2Cl2:CH3OH),重结晶(CH2Cl2:CH3OH)得有金属光泽固体0.67g,产率64%。1H NMR (CDCl3, 400MHz, ppm)δ:12.20 (s, 2H), 8.21 (d, J = 8.8Hz, 1H), 7.91(dd, J = 7.6, 8.4Hz, 2H), 7.64 (t, J = 7.4Hz, 1H), 7.46 (t, J = 7.6Hz, 1H), 7.34 (d, 1H, J=8.4 Hz, Ar), 7.23 (d, J = 8.8Hz, 1H), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 5.79 (s, 1H), 5.72(s, 2H), 4.59 (br, 1H, CH), 4.34 (t, J = 7.6 Hz, 2H, CH2), 3.75 (t, J = 7.6 Hz, 1H, CH),1.82-1.71 (m, 2H, CH2), 1.54-1.43 (m, 2H, CH2), 1.40-1.36 (m, 2H, CH2), 1.09 (t, J = 7.2 Hz, 3H, CH3).
实施例6:不对称方酸ASQ-6的制备
(1)ASQ-6的制备
18 0.57g (1.73mmol),11 0.49g (1.73mmol),80mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36h,减压蒸出溶剂,柱层析(CH2Cl2:CH3OH),重结晶(CH2Cl2:CH3OH)得有金属光泽固体0.61g,产率60%。1H NMR (CDCl3, 400MHz, ppm)δ:12.24 (s, 2H), 8.23 (d, J = 8.8Hz, 1H), 7.94(dd, J = 7.6, 8.4Hz, 2H), 7.65 (t, J = 7.4Hz, 1H), 7.47 (t, J = 7.6Hz, 1H), 7.34 (d, 1H, J=8.4 Hz, Ar), 7.23 (d, J = 8.8Hz, 1H), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 5.80 (s, 1H), 5.75 (s, 2H), 4.61 (br, 1H, CH), 4.36 (t, J = 7.6 Hz, 2H, CH2), 3.77 (t, J = 7.6 Hz, 1H, CH),1.82-1.70 (m, 2H, CH2), 1.59-1.43 (m, 4H, CH2), 1.41-1.36 (m, 2H, CH2), 0.99 (t, J = 7.2 Hz, 3H, CH3).
实施例7:不对称方酸ASQ-7的制备
(1)ASQ-7的制备
18 0.57g (1.73mmol),13 0.39g (1.73mmol),80mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36h,减压蒸出溶剂,柱层析(CH2Cl2:CH3OH),重结晶(CH2Cl2:CH3OH)得有金属光泽固体0.72g,产率78%。1H NMR (CDCl3, 400MHz, ppm)δ:12.14 (s, 2H), 8.17 (d, J = 8.8Hz, 1H), 7.94 (dd, J = 7.6, 8.4Hz, 2H), 7.70 (t, J = 7.4Hz, 1H), 7.57 (t, J = 7.6Hz, 1H), 7.37 (d, 1H, J=8.4 Hz, Ar), 7.26 (d, J = 8.8Hz, 1H), 7.16-7.11 (m, 2H, Ar), 7.11 (t, 1H, J=7.6 Hz, Ar), 5.92 (s, 1H), 5.75 (s, 2H), 4.55 (br, 2H, CH), 4.37 (t, J = 7.6 Hz, 2H, CH2), 3.77 (br, 2H, CH), 0.99 (t, J = 7.2 Hz, 3H, CH3).
实施例8:不对称方酸ASQ-8的制备
(1)ASQ-8的制备
18 0.57g (1.73mmol),15 0.42g (1.73mmol),80mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36h,减压蒸出溶剂,柱层析(CH2Cl2:CH3OH),重结晶(CH2Cl2:CH3OH)得有金属光泽固体0.71g,产率75%。1H NMR (CDCl3, 400MHz, ppm)δ:12.20 (s, 2H), 8.18 (d, J = 8.8Hz, 1H), 7.99 (dd, J = 7.6, 8.4Hz, 2H), 7.77 (t, J = 7.4Hz, 1H), 7.56 (t, J = 7.6Hz, 1H), 7.47 (d, 1H, J=8.4 Hz, Ar), 7.36 (d, J = 8.8Hz, 1H), 7.19-7.15 (m, 2H, Ar), 7.11 (t, 1H, J=7.6 Hz, Ar), 5.93 (s, 1H), 5.65 (s, 2H), 4.65 (br, 2H, CH), 4.47 (t, J = 7.6 Hz, 2H, CH2), 3.77 (m, 2H, CH), 1.78 (m, 2H, CH), 0.99 (t, J = 7.2 Hz, 3H, CH3).
实施例9:不对称方酸ASQ-9的制备
(1)化合物19的制备
2,3,3-三甲基-3H-吲哚10.00 g (62.9 mmol) 加入120 mL CH3NO2,搅拌溶解后加入碘代正丁烷34.7 g (188.7 mmol),加热至80℃反应36 h。反应液缓慢倾入350 mL无水乙醚中,析出红色油状物,再用无水乙醚沉降洗涤,减压抽滤得黄白色粉末15.44 g,产率72%。m.p.133-134℃.
(2)化合物20的制备
19 10.00g (29.2 mmol) 加入60mL混合溶剂(三乙胺:乙醇=1:8,v/v),加热回流30min。
冷却至室温,加入1 4.12g (24.2 mmol),回流反应30min,减压蒸出溶剂,柱层析(PE:EA=8:1),乙醇重结晶得黄色固体8.13 g,产率66%。
(3)化合物21的制备
20 1.00 g (2.94 mmol) 加入20 mL丙酮中,加热回流至固体全部溶解,滴加6M HCl 7 mL,薄层色谱监测反应,反应完全后,滴加蒸馏水水,黄色沉淀物析出,过滤得黄色粉末0.87 g,产率94%。1H NMR (CDCl3, 400MHz, ppm)
δ: 8.14 (br, 1H, Ar-H), 7.29-7.34 (m, 2H, Ar-H), 7.16 (t, J = 7.6 Hz, 1H, Ar-H), 6.97 (d, J = 7.6 Hz, 1H, Ar-H), 5.68 (s, 1H, =CH-), 3.92 (br, 2H, -NCH2-), 1.74-1.81 (m, 2H, -CH2), 1.67 (s, 6H, -CH3), 1.42-1.52 (m, 2H, -CH2-), 1.03 (t, J = 7.6 Hz, 3H, -CH3)。
(4)ASQ-9的合成
21 0.95 g (3.06 mmol),7 0.98 g (3.67 mmol),80 mL混合溶剂(甲苯:正丁醇=3:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(PE:EA=2:1),重结晶(二氯甲烷:甲醇)得亮黄色晶体ASQ-9 1.20g,产率70%. 1H NMR (400 MHz, CDCl3, δ): 12.36 (s, 2H, OH), 7.95 (d, J = 8.8 Hz, 1H, ArH), 7.66 (t, J = 7.2 Hz, 1H, ArH), 7.53 (t, J = 7.6 Hz, 1H, ArH), 7.39 (d, J = 8.8 Hz,2H, ArH), 7.18 (t, J = 7.2 Hz, 2H, ArH), 6.95 (t, J = 7.6 Hz, 1H, ArH), 6.36 (s,2H, ArH), 5.99 (s, 1H, CH), 4.69 (br, 1H, CH), 4.24 (t, J = 7.6 Hz, 2H, CH2), 3.92 (t, J = 7.6 Hz, 1H, CH), 2.04 (s, 6H, CH3),2.01-1.93 (m, 2H, CH2), 1.92-1.84 (m, 2H, CH2),1.71-1.64 (m, 2H, CH2), 1.56-1.46 (m, 2H, CH2), 1.45-1.37 (m, 2H, CH2), 1.04 (t, J = 7.2 Hz, 3H, CH3).
实施例10:不对称方酸ASQ-10的制备
(1)ASQ-10的制备
21 0.54g (1.73mmol),11 0.49g (1.73mmol),80mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36h,减压蒸出溶剂,柱层析(CH2Cl2:CH3OH),重结晶(CH2Cl2:CH3OH)得有金属
光泽固体0.62g,产率62%。1H NMR (CDCl3, 400MHz, ppm)δ:12.24 (s, 2H), 7.94(dd, J = 7.6, 8.4Hz, 2H), 7.65 (t, J = 7.4Hz, 1H), 7.47 (t, J = 7.6Hz, 1H), 7.34 (d, 1H, J=8.4 Hz, Ar), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 5.80 (s, 1H), 5.75 (s, 2H), 4.61 (br, 1H, CH), 4.36 (t, J = 7.6 Hz, 2H, CH2), 3.77 (t, J = 7.6 Hz, 1H, CH),1.82-1.70 (m, 2H, CH2), 1.59-1.43 (m, 4H, CH2), 1.41-1.36 (m, 2H, CH2), 0.99 (t, J = 7.2 Hz, 3H, CH3).
实施例11:不对称方酸ASQ-11的制备
(1) ASQ-11的制备
21 0.62 g (1.98 mmol),13 0.50 g (2.20 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流38 h,反应过程中有沉淀析出,抽滤的黄绿色固体,柱层析(PE:EA=1:1),重结晶(二氯甲烷:甲醇)得绿色细小晶体ASQ-11 0.85 g,产率83%。1H NMR (400 MHz, CDCl3, ppm) δ:12.37 (s, 2H, -OH), 7.44 (dd, 2H, J=8.0 Hz, Ar), 7.39 (t, 1H, J=8.0 Hz, Ar), 7.30 (d, 1H, J=7.6 Hz, Ar), 7.22-7.12 (m, 3H, Ar), 6.93 (t, 1H, J=7.2 Hz, Ar), 6.29 (s, 2H, Ar), 5.93 (s, 1H, =CH-), 4.11-4.04 (m, 4H, -NCH2-), 3.17 (t, 2H, J=8.4 Hz, -CH2-), 1.86-1.79 (m, 2H, -CH2-), 1.77 (s, 6H, -CH3), 1.53-1.43 (m, 2H, -CH2-), 1.03 (t, 3H, J=7.2 Hz, -CH3);13C NMR (100 MHz, CDCl3, ppm) δ: 173.88, 170.42, 170.34, 163.00, 152.75, 144.06, 142.62, 141.61, 133.18, 128.26, 127.40, 125.63, 125.33, 122.56, 121.88, 113.14, 110.72, 104.59, 96.39, 87.76, 52.00, 50.33, 44.28, 29.46, 27.98, 26.60, 20.34, 13.84.
实施例12:不对称方酸ASQ-12的制备
(1) ASQ-12的制备
21 0.80 g (2.56 mmol),15 0.70 g (2.84 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH=50:1),重结晶(CHCl2:CH3OH=1:8)得带金属光泽的金色晶体ASQ-4 1.08 g,产率79%。1H NMR (400 MHz, CDCl3, ppm) δ: 12.24 (s, 2H), 7.96 (d, 1H, J=8.0 Hz, Ar), 7.95 (d, 1H, J=8.8 Hz, Ar), 7.65 (t, 1H, J=8.0 Hz, Ar), 7.52 (t, 1H, J=7.6 Hz, Ar), 7.39 (d, 1H, J=8.8 Hz, Ar), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 6.22 (s, 2H, Ar), 5.98 (s, 1H, =CH-), 4.23 (t, 2H, J=7.6 Hz, -NCH2-), 3.72 (t, 2H, J=6.4 Hz, -NCH2-), 2.73 (t, 2H, J=6.4 Hz, -CH2-), 2.03 (s, 6H, -CH3), 2.03-1.97 (m, 2H, -CH2-), 1.91-1.84 (m, 2H, -CH2-), 1.55- 1.46 (m, 2H, -CH2-), 1.04 (t, 3H, J=7.2 Hz, -CH3).
实施例13:不对称方酸ASQ-13的制备
(1)化合物22的制备
2-甲基苯并[b]噻唑10.00 g (62.9 mmol) 加入100 mL CH3NO2,搅拌溶解后加入碘代正丁烷24.70 g (134.2 mmol),加热至80℃反应36 h。反应液缓慢倾入350 mL无水乙醚中,析出灰绿色固体,再用无水乙醚沉降洗涤,减压抽滤得浅黄色粉末13.20 g,产率59%。m.p.177-178℃.
(2)化合物23的制备
22 5.00g (15.0 mmol) 加入40mL混合溶剂(三乙胺:乙醇=1:8,v/v),加热回流30min。冷却至室温,加入1 2.13g (12.5 mmol),回流反应2 h后,析出固体,10 h后停止反应,抽滤得黄色沉淀,乙醇重结晶得黄色固体2.13 g,产率52%。
(3)化合物24的制备
23 1.00 g (3.03 mmol) 加入40 mL丙酮中,加热回流至固体全部溶解,滴加3M HCl 5 mL,薄层色谱监测反应,反应完全后,滴加蒸馏水水,黄色沉淀物析出,过滤得黄色粉末0.81 g,产率90%。1H NMR (DMSO-d 6 , 400MHz, ppm) δ: 7.47 (d, J = 7.2 Hz, 1H, Ar-H), 7.20 (t, J = 7.2 Hz, 1H, Ar-H), 7.07 (d, J = 8.0 Hz, 1H, Ar-H), 6.95 (t, J = 7.6 Hz, 1H, Ar-H), 5.76 (s, 1H, =CH-), 3.87 (t, J = 7.2 Hz, 2H, -NCH2-), 1.57-1.65 (m, 2H, -CH2), 1.35-1.45 (m, 2H, -CH2-), 0.96 (t, J = 7.6 Hz, 3H, -CH3)。
(4) ASQ-13的制备
24 0.92 g (3.06 mmol),7 0.98 g (3.67 mmol),80 mL混合溶剂(甲苯:正丁醇=3:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(PE:EA=2:1),重结晶(二氯甲烷:甲醇)得亮黄色晶体ASQ-13 1.15g,产率68%。1H NMR (400 MHz, CDCl3, δ): 12.36 (s, 2H, OH), 7.96 (d, J = 8.0 Hz, 1H, ArH), 7.95 (d, J = 8.8 Hz, 1H, ArH), 7.66 (t, J = 7.2 Hz, 1H, ArH), 7.53 (t, J = 7.6 Hz, 1H, ArH), 7.39 (d, J = 8.8 Hz,1H, ArH), 7.18 (t, J = 7.2 Hz, 2H, ArH), 6.95 (t, J = 7.6 Hz, 1H, ArH), 6.36 (s,2H, ArH), 5.99 (s, 1H, CH), 4.69 (br, 1H, CH), 4.24 (t, J = 7.6 Hz, 2H, CH2), 3.92 (t, J = 7.6 Hz, 1H, CH), 2.01-1.93 (m, 2H, CH2), 1.92-1.84 (m, 2H, CH2),1.71-1.64 (m, 2H, CH2), 1.56-1.46 (m, 2H, CH2), 1.45-1.37 (m, 2H, CH2), 1.04 (t, J = 7.2 Hz, 3H, CH3).
实施例14:不对称方酸ASQ-14的制备
(1)ASQ-14的制备
24 0.57 g (1.88 mmol),11 0.63 g (2.25 mmol),60 mL混合溶剂(甲苯:正丁醇=3:1,v/v),分水回流38 h,减压蒸出溶剂,柱层析(PE:EA=1:1),重结晶(二氯甲烷:甲醇)得绿色晶体0.74 g 产率70%。1H NMR (400 MHz, CDCl3, δ): 12.15 (s, 2H, OH), 8.01 (d, J = 8.0 Hz, 1H, ArH), 7.72 (t, J = 7.2 Hz, 1H, ArH), 7.61 (t, J = 7.6 Hz, 1H, ArH), 7.53-7.46 (m, 3H, ArH), 7.16-7.11 (m, 2H, ArH), 6.45 (s, 2H, ArH), 6.22 (s, 1H, CH), 4.39 (t, J = 7.6 Hz, 2H, CH2), 4.37-4.33 (m, 1H, CH), 3.79-3.74 (m, 1H, CH), 2.77 (d, J = 6.4 Hz, 4H, CH2),1.98-1.89 (m, 6H, CH2),1.58-1.49 (m, 2H, CH2), 1.07 (t, J = 7.2 Hz, 3H, CH3).
实施例15:不对称方酸ASQ-15的制备
(1)ASQ-15的制备
24 0.60 g (1.99 mmol),13 0.50 g (2.20 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(PE:EA=1:1),重结晶(二氯甲烷:甲醇)得绿色晶体 0.88 g,产率87%。1H NMR (400 MHz, CDCl3, ppm) δ: 7.75 (d, 1H, J=8.0 Hz, Ar), 7.52 (t, 1H, J=8.4 Hz, Ar), 7.41-7.36 (m, 3H, Ar), 7.21 (d, 1H, J=7.2 Hz, Ar), 7.18 (t, 1H, J=8.0 Hz, Ar), 6.90 (t, 1H, J=7.2 Hz, Ar), 6.23 (s, 2H, Ar), 6.09 (s, 1H, =CH-), 4.31 (t, 2H, J=8.0 Hz, -NCH2-), 4.02 (t, 2H, J=8.0 Hz, -NCH2-), 3.16 (t, 2H, J=8.0 Hz, -CH2-), 1.90-1.82 (m, 2H, -CH2-), 1.56-1.47 (m, 2H, -CH2-), 1.05 (t, 3H, J=7.2 Hz, -CH3).
实施例16:不对称方酸ASQ-16的制备
(1) ASQ-16的制备
24 0.77 g (2.56 mmol),15 0.70 g (2.84 mmol),100 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH=50:1),重结晶(CHCl2:CH3OH=1:8)得带金属光泽的金色晶体ASQ-16 1.11 g,产率83%。1H NMR (400 MHz, CDCl3, ppm) δ: 7.96 (d, 1H, J=8.0 Hz, Ar), 7.95 (d, 1H, J=8.8 Hz, Ar), 7.65 (t, 1H, J=8.0 Hz, Ar), 7.52 (t, 1H, J=7.6 Hz, Ar), 7.39 (d, 1H, J=8.8 Hz, Ar), 7.15-7.12 (m, 2H, Ar), 7.00 (t, 1H, J=7.6 Hz, Ar), 6.22 (s, 2H, Ar), 5.98 (s, 1H, =CH-), 4.23 (t, 2H, J=7.6 Hz, -NCH2-), 3.72 (t, 2H, J=6.4 Hz, -NCH2-), 2.73 (t, 2H, J=6.4 Hz, -CH2-), 2.03 (s, 6H, -CH3), 2.03-1.97 (m, 2H, -CH2-), 1.91-1.84 (m, 2H, -CH2-), 1.55- 1.46 (m, 2H, -CH2-), 1.04 (t, 3H, J=7.2 Hz, -CH3).
实施例17:不对称方酸ASQ-17的制备
(1) 化合物25的制备
5,6-二氟吲哚啉 0.40 g (2.58 mmol),3,5-二甲氧基溴苯0.58 g (2.71 mmol),3%摩尔量的Pd(OAc)2 (17 mg),6%摩尔量的P(t-Bu)3 .HBF4 (45 mg),叔丁醇钠 (0.50 g,5.16 mmol)加入40 mL甲苯中,110℃加热12h,过滤,滤液减压旋除溶剂,柱层析(PE:CH2Cl2=5:1)得白色晶体0.45 g,产率60%。1H NMR (400 MHz, CDCl3, ppm) δ: 6.96-6.91 (m, 2H, Ar), 6.33 (d, 2H, J=20 Hz, Ar), 6.15 (t, 1H, J=2.0 Hz, Ar), 3.97 (t, 2H, J=8.4 Hz, -NCH2-), 3.85 (s, 6H, -OCH3), 3.07 (t, 2H, J=8.4 Hz, -CH2-).
(2) 化合物26的制备
25 0.34 g (1.17 mmol) 加入34 mL无水二氯甲烷,冰浴下缓慢滴加10 mL含三溴化硼1.76 g (7.01 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得黄色固体0.30 g,产率97%。
(3) 化合物ASQ-17的制备
4 0.37 g (1.02 mmol),26 0.30 g (1.14 mmol),60 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH),重结晶(CHCl2:CH3OH)得亮绿色细小晶体ASQ-17 0.47 g,产率76%。1H NMR (400 MHz, CDCl3, ppm) δ: 8.24 (d, 1H, J=8.8 Hz, Ar), 7.98 (d, 2H, J=8.8 Hz, Ar), 7.67 (t, 1H, J=7.2 Hz, Ar), 7.55 (t, 1H, J=7.2 Hz, Ar), 7.42 (d, 1H, J=8.8 Hz, Ar), 7.23 (q, 1H, Ar), 7.01 (t, 1H, J=8.8 Hz, Ar), 6.21 (s, 2H, Ar), 6.05 (s, 1H, =CH-), 4.28 (t, 2H, J=7.6 Hz, -NCH2-), 4.09 (t, 2H, J=8.0 Hz, -NCH2-), 3.12 (t, 2H, J=8.0 Hz, -CH2-), 2.04 (s, 6H, -CH3), 1.91-1.85 (m, 2H, -CH2-), 1.55-1.49 (m, 2H, -CH2-), 1.05 (t, 3H, J=7.2 Hz, -CH3).
实施例18:不对称方酸ASQ-18的制备
(1) 化合物27的制备
6-氟-1,2,3,3a,4,8b-六氢环戊[b]吲哚啉 0.46 g (2.58 mmol),3,5-二甲氧基溴苯0.58 g (2.71 mmol),3%摩尔量的Pd(OAc)2 (17 mg),6%摩尔量的P(t-Bu)3 .HBF4 (45 mg),叔丁醇钠 (0.50 g,5.16 mmol)加入40 mL甲苯中,110℃加热12h,过滤,滤液减压旋除溶剂,柱层析(PE:CH2Cl2=5:1)得油状物0.53 g,产率65%。
(2) 化合物28的制备
25 0.37 g (1.17 mmol) 加入34 mL无水二氯甲烷,冰浴下缓慢滴加10 mL含三溴化硼1.76 g (7.01 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得黄色粘稠物0.30 g,产率91%。
(3) ASQ-18的制备
18 0.33 g (1.02 mmol),28 0.33 g (1.14 mmol),60 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH),重结晶(CHCl2:CH3OH)得固体ASQ-18 0.40 g,产率66%。1H NMR (400 MHz, CDCl3, ppm) δ: 8.16 (m, 3H, Ar), 7.67 (m, 2H, Ar), 7.32 (d, 1H, J=7.2 Hz, Ar), 7.06 (d, 1H, J=7.2 Hz, Ar), 6.48 (m, 2H, Ar), 6.39 (s, 1H, =CH-), 6.05 (s, 2H, Ar), 4.38 (t, 2H, J=7.6 Hz, -NCH2-), 4.01 (t, 1H, J=8.0 Hz, -NCH2-), 3.17 (t, 1H, J=8.0 Hz, -CH-), 1.51-1.45 (m, 2H, -CH2-), 1.25-1.16 (m, 4H, -CH2-), 1.09 (t, 3H, J=7.2 Hz, -CH3).
实施例19:不对称方酸ASQ-19的制备
(1) 化合物29的制备
2,3,4,4a,9,9a-六氢-1H-6-氰基咔唑 0.51 g (2.58 mmol),3,5-二甲氧基溴苯0.58 g (2.71 mmol),3%摩尔量的Pd(OAc)2 (17 mg),6%摩尔量的P(t-Bu)3 .HBF4 (45 mg),叔丁醇钠 (0.50 g,5.16 mmol)加入40 mL甲苯中,110℃加热12h,过滤,滤液减压旋除溶剂,柱层析(PE:CH2Cl2)得固体0.47 g,产率55%。
(2) 化合物30的制备
29 0.39 g (1.17 mmol) 加入34 mL无水二氯甲烷,冰浴下缓慢滴加10 mL含三溴化硼1.76 g (7.01 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得黄白色粘稠物0.31 g,产率86%。
(3) ASQ-19的制备
21 0.32 g (1.02 mmol),30 0.35 g (1.14 mmol),60 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH),重结晶(CHCl2:CH3OH)得固体ASQ-19 0.42 g,产率69%。1H NMR (400 MHz, CDCl3, ppm) δ: 8.92 (d, J=8.0 Hz, 1H, Ar), 8.02 (t, J=7.6 Hz, 1H, Ar), 7.80 (s, 1H, Ar), 7.37 (m, 2H, Ar), 7.24 (d, 1H, J=7.2 Hz, Ar), 6.70 (d, 1H, J=7.2 Hz, Ar), 6.32 (s, 1H, =CH-), 6.15 (s, 2H, Ar), 4.03 (t, 2H, J=7.6 Hz, -NCH2-), 3.72 (t, 1H, J=8.0 Hz, -NCH2-), 2.97 (t, 1H, J=8.0 Hz, -CH-), 2.33 (t, 2H, J=7.2 Hz, -CH2-), 2.03 (t, 2H, J=7.2 Hz, -CH2-), 1.51-1.45 (m, 2H, -CH2-), 1.40-1.33 (m, 2H, -CH2-), 1.25-1.16 (m, 4H, -CH2-), 0.97 (t, 3H, J=7.2 Hz, -CH3).
实施例20:不对称方酸ASQ-20的制备
(1) 化合物31的制备
5,7-二氟-1,2,3,4-四氢喹啉 0.44 g (2.58 mmol),3,5-二甲氧基溴苯0.58 g (2.71 mmol),3%摩尔量的Pd(OAc)2 (17 mg),6%摩尔量的P(t-Bu)3 .HBF4 (45 mg),叔丁醇钠 (0.50 g,5.16 mmol)加入40 mL甲苯中,110℃加热12h,过滤,滤液减压旋除溶剂,柱层析(PE:CH2Cl2)得固体0.58 g,产率73%。
(2) 化合物32的制备
31 0.36 g (1.17 mmol) 加入34 mL无水二氯甲烷,冰浴下缓慢滴加10 mL含三溴化硼1.76 g (7.01 mmol) 的无水二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入160 mL冰水中,用二氯甲烷萃取,水洗涤,饱和碳酸氢钠水溶液洗涤,干燥,浓缩,柱层析得粘稠物0.28 g,产率85%。
(3) ASQ-20的制备
24 0.31 g (1.02 mmol),32 0.32 g (1.14 mmol),60 mL混合溶剂(甲苯:正丁醇=1:1,v/v),分水回流36 h,减压蒸出溶剂,柱层析(CHCl2:CH3OH),重结晶(CHCl2:CH3OH)得固体ASQ-20 0.41 g,产率72%。1H NMR (400 MHz, CDCl3, ppm) δ: 8.61 (d, J=8.0 Hz, 1H, Ar), 8.23 (t, J=7.6 Hz, 1H, Ar), 7.74 (t, J=7.6 Hz, 1H, Ar), 7.48 (m, 1H, Ar), 7.26 (d, 1H, J=8.0 Hz, Ar), 6.61 (s, 1H, Ar), 6.32 (s, 1H, Ar), 6.10 (s, 1H, =CH-), 5.97 (s, 2H, Ar), 4.70 (t, 2H, J=7.6 Hz, -NCH2-), 3.06 (t, 2H, J=7.6 Hz, -NCH2-), 2.94 (t, 2H, J=7.2 Hz, -CH2-), 2.53 (m, 2H, -CH2-), 2.03 (t, 2H, J=7.2 Hz, -CH2-), 1.71-1.56 (m, 2H, -CH2-), 0.90 (t, 3H, J=7.2 Hz, -CH3).
实施例21:不对称方酸ASQ-21的制备
(1) 化合物33 的制备
向盛有乙腈 120mL和碘化钾10.02g(60 mmol)的反应瓶中滴加α-溴甲苯3.6mL(30 mmol),室温避光反应24h,反应完毕后过滤浓缩后的深褐色液体,不经纯化直接投入下一步。
(2) 化合物34 的制备
1,1,2-三甲基-1H-苯并[e]吲哚0.21 g (1.0 mmol) 加入5 mL 乙腈,搅拌溶解后加入33的乙腈溶液2mL,回流24 h。反应液缓慢倾入50 mL无水乙醚中,析出褐色沉淀,减压抽滤,用无水乙醚洗涤2次,减压抽滤得黄色粉末0.38 g,产率88%。m.p.: 167-168℃。
(3) 化合物35的制备
34 1.20 g (2.8 mmol) 加入45 mL混合溶剂(三乙胺:乙醇=1:8,v/ v),加热回流30 min。冷却至室温,加入1 0.43 g (2.6 mmol),室温反应96 h,有黄色沉淀析出,过滤,乙醇重结晶得橙黄色晶体0.57g,产率48%。m.p. 187-188℃; FT-IR: 2957-2856 cm-1 (-CH3, -CH2), 1702 cm-1(C=O); 1H NMR (CDCl3, 400MHz, ppm) δ: 8.15 (d, J = 8.4 Hz, 1H, Ar-H), 7.87 (d, J = 8.0 Hz, 1H, Ar-H), 7.79 (d, J = 8.8 Hz, 1H, Ar-H), 7.58 (dt, 3 J= 7.6 Hz, 4 J = 1.2 Hz, 1H, Ar-H), 7.40 (t, J = 7.2 Hz, 1H, Ar-H), 7.36 (t, J = 6.8 Hz, 2H, Ar-H), 7.33 (t, J = 6.8 Hz, 1H, Ar-H), 7.23 (d, J = 6.8 Hz, 2H, Ar-H), 7.16 (d, J = 7.2 Hz, 1H, Ar-H), 5.49 (s, 1H, =CH-), 5.16 (s, 2H, N-CH2-), 4.89 (q, J = 7.2 Hz, 2H, -OCH2-), 1.99 (s, 6H, -CH3), 1.53 (t, J = 7.2 Hz, 3H, -CH3).
(4) 化合物36的制备
35 3.20 g (7.6 mmol) 加入120 mL丙酮中,加热回流至固体全部溶解,滴加6M HCl 45 mL,TLC监测至反应完全,后滴加饱和碳酸氢钠水溶液调pH=3~4,有大量黄绿色沉淀析出,过滤所得固体用120mL二氯甲烷:乙醇=9:1(v/v)溶解后滴加至600mL正己烷中,搅拌过夜,抽滤得橙黄色粉末1.59 g,产率84%。m.p.:163℃。
(5) ASQ-21的制备
35 270 mg (0.1 mmol),7 395 mg (0.1 mmol),30 mL混合溶剂(甲苯:正丁醇=3:1, v/v)加入三颈瓶中,分水回流反应24 h,减压蒸出溶剂,柱层析(DCM),得亮金色固体515 mg,收率75%。1H NMR (CDCl3, 400 MHz, ppm) δ: 12.40 (br, 2H, -OH), 8.24 (d, J = 8.4Hz, 1H, Ar-H), 7.92 (d, J = 8.4 Hz, 1H, Ar-H), 7.86 (d, J = 8.4 Hz, 1H, Ar-H), 7.64 (td, 3 J = 6.8 Hz, 4 J = 1.2 Hz, 1H, Ar-H), 7.49 (t, J = 7.2 Hz, 1H, Ar-H), 7.38-7.28 (m, 5H, Ar-H), 7.22-7.14 (m, 4H, Ar-H), 6.94 (t, J = 7.6 Hz, 1H, Ar-H), 6.34 (s, 2H, Ar-H), 6.02 (s, 1H, -CH=), 5.43 (s, 2H, -CH2-Ar), 4.68 (td, 1H, 3 J = 8.8 Hz, 4 J = 2.8 Hz, N-CH-CH2), 3.90 (t, 1H, J = 7.2 Hz, CH-CH-CH2), 2.11 (s, 6H, -CH3), 2.04-1.37 (m, 6H, CH2-CH2-CH2).
实施例22:不对称方酸ASQ-22的制备
(1) 化合物37的制备
4-氟苯肼盐酸盐1.00 g (6.2 mmol),环戊酮0.52 g (6.2 mmol),异丙醇31 mL加入带支管的反应管中,彻底脱气,室温下滴加脱气的浓硫酸0.7 mL,滴加完毕后升温至100℃反应1 h。反应完毕后将反应液倾入100 mL水中,二氯甲烷萃取(3×30 mL),有机相合并干燥,过滤,减压除去溶剂,柱层析(PE:DCM=1:1),得白色固体0.67 g,收率62%。
(2) 化合物38的制备
37 0.75 g (4.3 mmol) 加入两颈瓶中,加入25 mL四氢呋喃,溶解完毕后加入0.20 g Pd/C催化剂,通入氢气搅拌反应24 h。反应完毕后过滤滤除Pd/C,取滤液减压蒸出溶剂,柱层析(PE to PE:DCM=1:1),得无色油状液体0.46 g,收率61 %。1H NMR (CDCl3, 400 MHz, ppm) δ: 6.76 (dd, 3 J = 8.4 Hz, 4 J = 2.0 Hz, 1H, Ar-H), 6.69 (td, 3 J = 8.8 Hz, 4 J = 2.4 Hz, 1H, Ar-H), 6.50 (q, J = 4.4Hz, 1H, Ar-H), 4.40 (td, 3 J = 7.6 Hz, 4 J = 2.4 Hz, N-CH-), 3.76 (t, J = 8.8 Hz, 1H, CH-CH-CH2), 2.01-1.51 (m, 6H, -CH2-).
(3) 化合物39的制备
38 0.63 g (3.6 mmol),3,5-二甲氧基溴苯0.78 g (3.6 mmol),醋酸钯 24 mg (0.11 mmol),四氟硼酸三叔丁基膦 52 mg(0.18 mmol),叔丁醇钠 0.55 g (5.76 mmol) 加入50 mL甲苯中,110℃反应12 h,过滤,滤液减压旋除溶剂,柱层析(PE:EA=200:1)得白色固体0.91 g,产率81 %。1H NMR (CDCl3, 400 MHz, ppm) δ: 6.96 (q, J = 4.4 Hz, 1H, Ar-H), 6.82 (dd, 3 J = 8.0 Hz, 4 J = 2.4 Hz,1H, Ar-H), 6.73 (td, 3 J = 8.8 Hz, 4 J = 2.8 Hz, 1H, Ar-H), 6.41 (d, J = 2.0 Hz, 2H, Ar-H), 6.10 (t, J = 2.0 Hz, 1H, Ar-H), 4.68 (td, 3 J = 8.0 Hz, 4 J = 2.8 Hz, N-CH-), 3.82 (t, J = 7.6 Hz, 1H, CH-CH-CH2), 3.79 (s, 6H, -OCH3), 2.07-1.43 (m, 6H, -CH2-).
(4) 化合物40的制备
390.97 g (3.1 mmol) 加入25 mL二氯甲烷,冰浴下缓慢滴加35 mL含三溴化硼7.5 g (30 mmol) 的二氯甲烷溶液,滴加完毕后,自然升温至室温,搅拌24 h。反应液倾入100 mL冰水中,用二氯甲烷萃取(3×30mL),水洗,饱和碳酸氢钠水溶液洗,水洗,过滤,干燥,浓缩,柱层析(DCM:CH3OH=100:1)得黄绿色固体0.69 g,产率78 %。
(5) ASQ-22的制备
36 490 mg (1.7 mmol),40 670 mg (1.7 mmol),40 mL混合溶剂(甲苯:正丁醇=3:1, v/v) 加入三颈瓶中,分水回流反应24 h,减压蒸出溶剂,柱层析(DCM; PE:EA=5:1),重结晶(DCM:CH3OH) 得亮金色固体490 mg,收率 45%。1H NMR (CDCl3, 400 MHz, ppm) δ: 12.40 (br, 2H, -OH), 8.24 (d, J = 8.4Hz, 1H, Ar-H), 7.92 (d, J = 8.0 Hz, 1H, Ar-H), 7.86 (d, J = 8.8 Hz, 1H, Ar-H), 7.64 (td, 3 J = 8.0 Hz, 4 J = 1.2 Hz, 1H, Ar-H), 7.50 (t, J = 7.6 Hz, 1H, Ar-H), 7.38-7.28 (m, 5H, Ar-H), 7.20 (d, 2H, J = 7.2 Hz, Ar-H), 6.88-6.83 (m, 2H, Ar-H), 6.28 (s, 2H, Ar-H), 6.03 (s, 1H, -CH=), 5.44 (s, 2H, -CH2-Ar), 4.68 (td, 1H, 3 J = 8.0 Hz, 4 J = 2.8 Hz, N-CH-CH2), 3.88 (t, 1H, J = 7.6 Hz, CH-CH-CH2), 2.11 (s, 6H, -CH3), 2.04-1.37 (m, 6H, CH2-CH2-CH2).
实施例23:以不对称方酸小分子为给体材料的有机太阳能电池器件的制备
(1) 本体异质结器件结构如图7a所示 以不对称方酸菁小分子(给体材料)与PCBM(受体材料)的不同质量比配成20 mg/mL的氯仿溶液,通过旋涂方式在经MoO3修饰过的ITO玻璃基板上制备出薄膜,然后真空蒸镀LiF和Al制备阴极。白光1.5 G(100 mW/cm2)照射下,测试其光电转换效率。
(2) 双层器件结构如图7b所示 在经MoO3修饰过的ITO玻璃基板上旋涂方酸菁小分子的氯仿溶液,再依次蒸镀C60层、BCP层以及Al电极层。白光1.5 G(100 mW/cm2)照射下,测试其光电转换效率。
实施例24:以不对称方酸小分子为给体材料的有机太阳能电池器件的光电转换效率表
Claims (2)
1.一系列具有通式Ⅰ结构的不对称方酸菁小分子,X、Y代表不同富电芳香环单元,
其结构特征在于:
所述X为如下基团1~4中的任意一个,其中R1,R3,R4,R5为氢原子 或氟原子 或氰基,R2为碳原子数为1-20的直链或支链的烷基 或苯烷基;
基团1:
基团2:
基团3:
基团4:
所述Y为如下基团5~8中的任意一个,
基团5:
基团6:
基团7:
基团8:
基团5, 6, 7, 8中R1、R2、R3和R4为相同或不相同的氢原子 或氟原子 或氰基。
2.如权利要求1中所述任一不对称方酸菁小分子在制备光电功能器件中的应用,其特征在于所述光电功能器件为有机太阳能电池。
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CN115108966A (zh) * | 2022-06-23 | 2022-09-27 | 西南医科大学 | 苯并吲哚方酸菁金属离子探针及其制备方法与应用 |
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