CN106380468A - 一种邻菲咯啉衍生物及其制备方法与应用 - Google Patents

一种邻菲咯啉衍生物及其制备方法与应用 Download PDF

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CN106380468A
CN106380468A CN201610733655.9A CN201610733655A CN106380468A CN 106380468 A CN106380468 A CN 106380468A CN 201610733655 A CN201610733655 A CN 201610733655A CN 106380468 A CN106380468 A CN 106380468A
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phenanthroline derivatives
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罗书平
陈南雨
孙圆圆
金海明
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种如式(I)所示的邻菲咯啉衍生物，所述化合物的制备方法为：将式(IV)所示的化合物溶于有机溶剂中，降温至‑120～‑10℃滴加烷基锂的正己烷溶液，滴完后控温‑20～50℃反应3～20h，反应液于‑80～50℃经淬灭剂淬灭，淬灭完后反应液后处理得到所述的邻菲咯啉衍生物；所述的邻菲咯啉衍生物可作为配体与金属形成配合物，作为光敏剂应用。

Description

一种邻菲咯啉衍生物及其制备方法与应用
本申请为 申请号201410241884X，申请日2014年05月30日，名称为一种邻菲咯啉衍生物及其制备方法与应用专利申请的分案申请
(一)技术领域
本发明涉及一种邻菲咯啉衍生物物及其制备方法，以及作为配体在金属配合物中的应用。
(二)背景技术
1,10-邻菲咯啉是一种常用的双齿氮配体，能与大多数金属形成稳定的配合物，在金属催化、光电材料、生物探针和抗癌药物等等领域中有着广泛应用。其也是一种重要的有机合成中间体，大量的1,10-邻菲咯啉衍生物被合成出来，用于调控配合物的物理化学性能和催化性能。
4,7-二芳香基-1,10-邻菲咯啉可增强配合物荧光强度，使其具有良好的发光性能和光学活性，已大量应用于OLED、光电转换等器件中。美国普林斯顿大学汤普森等在专利US2005/042699(CN101076904)中报道了2,9位为二烷基或二芳基取代的4,7-二芳香基-1,10-邻菲咯啉的合成及其作为有机光敏光电器件的激子阻挡层材料。日本株式会社半导体能源所野村亮二等在专利JP2005/012436(CN1980928)中报道了4,7-二(芳香基乙烯基)取代的啡咯啉衍生物的合成及其作为电子注入材料的应用。德国默克专利有限公司的凯蒂尔格玛纳森等在专利GB2007/050768(CN101574017)中报道了2,9位为二(芳香基乙烯基)取代的啡咯啉的合成及其组装的OLED器件。
(三)发明内容
本发明目的是提供一种新的邻菲咯啉衍生物，同时提供其制备方法，以及作为含氮的二齿配体在金属配合物中的应用。
本发明采用的技术方案如下：
一种如式(I)所示的邻菲咯啉衍生物：
式(I)中，R1为C2～C6的烷基，优选为异丙基；
R2为-COOH或其金属盐、-SR3、-C(OH)Ph、-C(O)C6H4COOH、-CHO或-P(OR4)2，优选为-COOH；其中，所述的-SR3中，R3为C1～C6的烷基或苯基；所述的-P(OR4)2中，R4为C1～C6的烷基或苯基；
Ar为苯、萘、噻吩、呋喃或噻吩并[3,2-b]噻吩，优选为苯基。
进一步，本发明所述的邻菲咯啉衍生物，特别优选为式(III)所示的化合物：
本发明还提供了一种邻菲咯啉衍生物的制备方法，所述的制备方法为：将式(IV)所示的化合物溶于有机溶剂中，降温至-120～-10℃滴加烷基锂的正己烷溶液，滴完后控温-20～50℃反应3～20h，反应液于-80～50℃经淬灭剂淬灭，淬灭完后反应液后处理得到所述的邻菲咯啉衍生物；所述的式(IV)所示化合物中，Ar为苯、萘、噻吩、呋喃或噻吩并[3,2-b]噻吩，X为氯、溴或碘；所述的烷基锂为C2～C6的烷基锂；所述的淬灭剂为CO2、R3SSR3、PhCHO、邻苯二甲酸酐、DMF或P(OR4)3，其中，所述的R3SSR3中，R3为C1～C6的烷基或苯基，所述的P(OR4)3中，R4为C1～C6的烷基或苯基。
本发明制备方法，所述的有机溶剂可以为苯、甲苯、四氢呋喃、1,4-二氧六环、乙醚、C4～C8的烷烃中的一种或者两种以上的混合溶剂，优选为苯、环己烷、乙醚或四氢呋喃；所述有机溶剂的体积用量以式(IV)所示的化合物的质量计可以为10～100mL/g。
本发明制备方法，所述的式(IV)所示化合物与烷基锂的投料物质的量比可以为1:1～20，优选为1:4～10；式(IV)所示化合物与淬灭剂的投料物质的量比可以为1:1～1000，优选为1:2～10。
本发明制备方法，当所述的淬灭剂为R3SSR3、PhCHO、邻苯二甲酸酐、DMF或P(OR4)3时，推荐先将所述的淬灭剂溶于乙醚，再以淬灭剂的乙醚溶液的形式用于反应液的淬灭。
本发明制备方法中，淬灭完后，所述的反应液后处理方法为：淬灭完全后反应液加入水，二氯甲烷萃取三次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥即得所述的邻菲咯啉衍生物。
本发明所述的邻菲咯啉衍生物作为含氮的二齿配体，可与金属形成配合物，如可与金属铜形成铜配合物，作为光敏剂的应用。
本发明与现有技术相比，提供了一种新的邻菲咯啉衍生物，其热稳定性好，负载性能好，能通过羧酸等官能团与各种材料的表面继续链接，有利于电子传输。该类含氮二齿配体可广泛与各种金属进行配位，并可稳定地负载于各种材料上，因此可以作为配体等应用于化学催化、光电材料等领域。
(四)具体实施方式：
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：
实施例1 2,9-二(正己基)-4,7-二(4-羧基苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-溴苯基)-1,10-啡咯啉(0.200g，0.4mmol)和苯(10mL)，负78摄氏度滴加正己基锂的正己烷溶液(0.7mL，1.6mmol)，升至室温反应5h，冷却至负78摄氏度通入二氧化碳气体(2mmol)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到147mg产物，收率73％，H NMR(CDOD，ppm):0.94(6H，t，J＝7.1Hz)，1.26-1.48(8H，m)，1.55-1.61(4H，m)，2.01-2.07(4H，m),3.46(4H,t,J＝7.9Hz)，7.78(4H，d，J＝8.2Hz)，8.06(2H,s),8.09(2H，s)，8.25(4H，d，J＝8.2Hz)。
实施例2 2,9-二(异丙基)-4,7-二2,2’(5-羧基噻吩基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二2,2’(5-氯噻吩基))-1,10-啡咯啉(0.166g，0.4mmol)和环己烷(10mL)，负120摄氏度滴加异丙基锂的正己烷溶液(2.5mL，3.2mmol)，升温至负10摄氏度反应6h，负10摄氏度通入二氧化碳气体(400mmol)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到138mg产物，收率67％，H NMR(CDOD，ppm):1.65(12H，d，J＝7.0Hz)，3.83-3.88(2H，m)，7.73(2H，d，J＝3.8Hz)，7.97(2H，d，J＝3.8Hz),8.21(2H,s),8.56(2H，s)。
实施例3 2,9-二(异丙基)-4,7-二(4-醛基苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-氯苯基)-1,10-啡咯啉(0.160g，0.4mmol)和乙醚(15mL)，负78摄氏度滴加异丙基锂的正己烷溶液(1.5mL，2.0mmol)，升至室温反应5h，冷却至负78摄氏度滴入DMF的乙醚溶液(浓度10wt％，5mL)，滴完后于50摄氏度反应10小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到40mg产物，收率21％，H NMR(CDCl3，ppm):1.53(12H，d，J＝7.0Hz)，4.15-4.18(2H，m)，7.46-7.65(8H，m)，7.73-7.84(4H，m)，9.32(2H，br)。
实施例4 2,9-二(异丙基)-4,7-二(4-(二乙氧膦基)苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-溴苯基)-1,10-啡咯啉(0.200g，0.4mmol)和乙醚(15mL)，负78摄氏度滴加异丙基锂的正己烷溶液(1.5mL，2.0mmol)，升至室温反应5h，冷却至负78摄氏度滴入亚磷酸三乙酯的乙醚溶液(浓度10wt％，5mL)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到87mg产物，收率33％，H NMR(CDCl3，ppm):1.34-1.39(12H，m)，1.53(6H，d，J＝6.9Hz)，3.60-3.72(2H，m)，4.10-4.18(8H，m)，7.42-7.63(8H，m)，7.71-7.82(4H，m)。
实施例5 2,9-二(异丙基)-4,7-二(4-(苯基羟基次甲基)苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-溴苯基)-1,10-啡咯啉(0.200g，0.4mmol)和乙醚(15mL)，负78摄氏度滴加异丙基锂的正己烷溶液(1.5mL，2.0mmol)，升至室温反应5h，冷却至负78摄氏度滴入苯甲醛的乙醚溶液(浓度10wt％，5mL)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到129mg，收率51％，H NMR(CDCl3，ppm):1.50(12H，d，J＝7.0Hz)，3.58-3.67(2H，m)，5.94(2H，s)，7.27-7.58(16H，m)，7.68-7.70(4H，m)，7.82(2H，s)。
实施例6 2,9-二(异丙基)-4,7-二(4-正丙硫基苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-溴苯基)-1,10-啡咯啉(0.200g，0.4mmol)和乙醚(15mL)，负78摄氏度滴加异丙基锂的正己烷溶液(1.5mL，2.0mmol)，升至室温反应5h，冷却至负78摄氏度滴入正丙二硫醚的乙醚溶液(浓度10wt％，5mL)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到122mg产物，收率54％，H NMR(CDCl3，ppm):1.00-1.07(6H，m)，1.53(12H，d，J＝7.0Hz)，1.55-1.59(4H，m)，3.26-3.31(4H，m)，3.62-3.96(2H，m)，7.40-7.44(2H，m)，7.48-7.59(8H，m)7.80-7.84(2H，m)。
实施例7 2,9-二(异丙基)-4-(4-羧基苯基)-7-苯基-1,10-啡咯啉的制备
50mL Schlenk反应管加入4-(4-溴苯基)-7-苯基-1,10-啡咯啉(0.207g，0.5mmol)和THF(10mL)，负78摄氏度滴加异丙基锂的正己烷溶液(2.5mL，3.2mmol)，升至室温反应6h，冷却至负78摄氏度通入二氧化碳气体(200mmol)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到121mg产物，收率64％，H NMR(CDOD，ppm):1.43(12H，d，J＝7.0Hz)，3.41-3.60(2H，m)，7.60-7.70(7H，m)，7.80-7.82(2H，m),8.06-8.17(4H,m)。
实施例8 2,9-二(异丙基)-4,7-二(4-邻羧基苯甲酰基苯基)-1,10-啡咯啉的制备
50mL Schlenk反应管加入4,7-二(4-溴苯基)-1,10-啡咯啉(0.201g，0.4mmol)和乙醚(10mL)，负78摄氏度滴加异丙基锂的正己烷溶液(2.5mL，3.2mmol)，升至室温反应6h，冷却至负78摄氏度滴入邻苯二甲酸酐的乙醚溶液(浓度10wt％，5mL)，反应半小时后加入水10mL，盐酸中和，用二氯甲烷萃取3次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥得到132mg产物，收率46％，H NMR(CDOD，ppm):1.53(12H，d，J＝7.0Hz)，1.93(2H，br)，3.59-3.67(2H，m)，7.19(2H，d，J＝8.2Hz)，7.35-7.41(4H，m),7.43-7.55(4H,m),7.70(2H，d，J＝8.2Hz)7.82(2H，s)，7.91(2H，m)，8.04(2H，m)，8.19(2H，m)。
实施例9 2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉的铜(I)络合物制备
在50mL Schlenk反应管加入4,5-双二苯基膦-9,9-二甲基氧杂蒽(59mg，0.1mmol)、六氟磷酸四乙腈铜(I)(37mg，0.1mmol)和二氯甲烷(10mL)，室温搅拌3小时，加入2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉(51mg，0.1mmol)，室温搅拌反应过夜，加入乙醚20mL析出固体，过滤干燥得91mg产物，收率70％。
实施例10 2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉的铜(I)络合物在光解水制氢中的应用
在无氧容器中，加入实施例9制得的的铜络合物(4.5mg，3.5μmol)，Fe3(CO)12(2.6mg，5μmol)，THF/Et3N/H2O(4:3:1，体积比)混合溶剂10mL，150W氙灯照射40小时，获得57.8mL氢气。
实施例11 2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉的铜(I)络合物在纳米二氧化钛上负载
在100圆底反应瓶加入4,5-双二苯基膦-9,9-二甲基氧杂蒽(59mg，0.1mmol)、六氟磷酸四乙腈铜(I)(37mg，0.1mmol)和二氯甲烷(10mL)，室温搅拌3小时，加入2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉(51mg，0.1mmol)，搅拌反应6小时后加入TiO2(3g)，室温搅拌过夜，过滤，乙醇洗涤两次，干燥得3.1g固体。
实施例12 纳米二氧化钛负载2,9-二(异丙基)-4,7-二(4-羧基苯基)-1,10-啡咯啉铜(I)络合物在太阳能染料光敏电池中的应用。
在无氧容器中，加入实施例11制得的固体(50mg)，Fe3(CO)12(2.6mg，5μmol)，THF/Et3N/H2O(4:3:1，体积比)混合溶剂10mL，150W氙灯照射80小时，获得41.5mL氢气。

Claims (8)

1.一种如式(I)所示的邻菲咯啉衍生物：
式(I)中，R1为C2～C6的烷基；
R2为-COOH或其金属盐、-SR3、-C(OH)Ph、-C(O)C6H4COOH、-CHO或-P(OR4)2；其中，所述的-SR3中，R3为C1～C6的烷基或苯基；所述的-P(OR4)2中，R4为C1～C6的烷基或苯基；
Ar为苯、萘、噻吩、呋喃或噻吩并[3,2-b]噻吩。
2.如权利要求1所述的邻菲咯啉衍生物，其特征在于所述的R1为异丙基，R2为-C(O)C6H4COOH，Ar为苯基。
3.如权利要求1所述的邻菲咯啉衍生物的制备方法，其特征在于所述的制备方法为：将式(IV)所示的化合物溶于有机溶剂中，降温至-120～-10℃滴加烷基锂的正己烷溶液，滴完后控温-20～50℃反应3～20h，反应液于-80～50℃经淬灭剂淬灭，淬灭完后反应液后处理得到所述的邻菲咯啉衍生物；所述的式(IV)所示化合物中，Ar为苯、萘、噻吩、呋喃或噻吩并[3,2-b]噻吩，X为氯、溴或碘；所述的烷基锂为C2～C6的烷基锂；所述的淬灭剂为CO2、R3SSR3、PhCHO、邻苯二甲酸酐、DMF或P(OR4)3，其中，所述的R3SSR3中，R3为C1～C6的烷基或苯基，所述的P(OR4)3中，R4为C1～C6的烷基或苯基；
4.如权利要求3所述的邻菲咯啉衍生物的制备方法，其特征在于所述的有机溶剂为苯、甲苯、四氢呋喃、1,4-二氧六环、乙醚、C4～C8的烷烃中的一种或者两种以上的混合溶剂。
5.如权利要求3所述的邻菲咯啉衍生物的制备方法，其特征在于所述的式(IV)所示化合物与烷基锂的投料物质的量比为1:1～20。
6.如权利要求3所述的邻菲咯啉衍生物的制备方法，其特征在于所述的式(IV)所示化合物与淬灭剂的投料物质的量比为1:1～1000。
7.如权利要求3所述的邻菲咯啉衍生物的制备方法，其特征在于淬灭完后，所述的反应液后处理方法为：淬灭完全后反应液加入水，二氯甲烷萃取三次，合并的萃取液干燥浓缩后，所得浓缩物经硅胶柱层析分离，洗脱剂为二氯甲烷和甲醇体积比1:0.05～5的混合液，收集含目标化合物的洗脱液，浓缩干燥即得所述的邻菲咯啉衍生物。
8.如权利要求1所述的邻菲咯啉衍生物作为配体与金属形成配合物作为光敏剂的应用。
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Application publication date: 20170208