CN108892683B - 一种2,6-二碘代bodipy衍生物及其制备方法和应用 - Google Patents
一种2,6-二碘代bodipy衍生物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及有机合成化学技术领域,具体涉及一种2,6‑二碘代BODIPY衍生物及其制备方法和应用。本发明化合物(III)可与多种纳米材料(如金属有机框架材料。共价有机框架材料等)发生反应,从而实现对纳米材料的表面修饰,赋予纳米材料新的功能;此外该化合物分子的系间窜越效率大大增强,使BODIPY的光动力性质大大提高,使化合物(III)具有易于扩展、易于修饰的良好特性。本发明通过选择有效的还原剂、设置相应的反应条件,可由化合物(II)反应得到化合物(III),且产率高达42%。本发明还提供了化合物(III)在纳米材料修饰中的应用。
Description
技术领域
本发明涉及有机合成化学技术领域,具体涉及一种2,6-二碘代BODIPY衍生物及其制备方法和应用。
背景技术
4-硼杂-3a,4a-二氮杂-4,4-二氟-s-引达省,通常称为BODIPY,其紫外吸收峰尖锐,摩尔吸光系数大、荧光量子产率很高,荧光几乎不受溶剂极性和pH的影响。这使得BODIPY广泛用作活细胞荧光染料和生物大分子的荧光标记试剂。BODIPY的2,6-位能通过亲核取代反应方便地引入碘原子,通过重原子效应增强系间窜越,从而增加三线态寿命,使得BODIPY有望作为光敏剂用于光动力治疗。
通过对BODIPY母核的修饰,可以优化BODIPY的荧光性质,并提供活性位点便于进一步的分子修饰。但BODIPY的经典合成方法基于苯甲醛与吡咯的缩合反应,产率低、分离困难、操作复杂,甚至与某些活泼官能团(如氨基、碘等)不兼容,极大地限制了BODIPY的相关研究与应用。
发明内容
为了解决上述问题,本发明提供了一种2,6-二碘代BODIPY衍生物及其制备方法和应用。
本发明通过以下技术方案实现:
本发明第一个方面,提供一种2,6-二碘代BODIPY衍生物,其化学结构式如下:
由于化合物(II)中-NO2活性较低,很难与纳米材料进行反应,从而限制了化合物(II)的使用;与-NO2相比,-NH2活性更高,因而将-NO2还原成-NH2,可能更有利于BODIPY衍生物在纳米材料修饰中的应用。然而由于化合物(II)结构较为复杂,还原剂能力过强或过弱,都无法得到目标产物化合物(III)。通过大量实验,本发明最终利用甲酸铵、氯化亚锡或水合肼为还原剂,在各自相应的反应条件下可有效制备得到目标产物化合物(III)。
甲酸铵、氯化亚锡或水合肼分别作为还原剂参与反应时,不同的反应溶剂、反应温度和反应时间都会影响化合物(III)的产率。
优选地,当还原剂为甲酸铵时,化合物(II)与甲酸铵的摩尔比为1:(10-50);反应溶剂为二氯甲烷、四氢呋喃、二氧六环、甲苯、甲醇、乙醇中的一种或多种;必要辅料为钯碳,钯的含量为2-10%;反应温度为25-100℃;反应时间为1-6h。只有在该反应条件下,以甲酸铵作为还原剂才可有效制备得到化合物(III),本发明人还发现在甲酸铵参与反应时,反应体系中还需加入钯碳,反应才可顺利进行。
优选地,当还原剂为氯化亚锡时,所述氯化亚锡为无水氯化亚锡或二水氯化亚锡;化合物(II)与氯化亚锡的摩尔比为1:5-20;反应溶剂为水、二氯甲烷、三氯甲烷、甲醇、乙醇、异丙醇、甲苯中的一种或多种,优选为二氯甲烷、甲醇、异丙醇三元混合反应溶剂;所述必要辅料为盐酸,浓度为0.1~12mol/L加热温度为25-100℃;反应时间为6-24h。只有在该反应条件下,以氯化亚锡作为还原剂才可有效制备得到化合物(III),本发明人还发现在氯化亚锡参与反应时,反应体系中还需加入盐酸,反应才可顺利进行。
优选地,当还原剂为水合肼时,化合物(II)与水合肼的摩尔比为1:50-200;反应溶剂为水、二氯甲烷、乙二醇、甲醇、乙醇、四氢呋喃、二氧六环、甲苯中的一种或多种;所述必要辅料为钯碳,钯的含量为2-10%;加热温度为25-100℃;反应时间为12-48h。只有在该反应条件下,以水合肼作为还原剂才可有效制备得到化合物(III),本发明人还发现在水合肼参与反应时,反应体系中还需加入钯碳,反应才可顺利进行。
(b)将步骤(a)得到的化合物(I)、碘、碘酸水溶液加入到反应溶剂中加热0-2h,反应结束后将反应物蒸发除去溶剂后,色谱分离得到化合物(II)。
进一步优选地,步骤(a)所述反应溶剂为二氯甲烷、乙二醇、甲醇、乙醇、甲苯、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种;所述有机弱碱选自三乙胺、二异丙基乙胺、苯胺、二乙胺、乙胺中的一种或多种;反应温度为25-100℃,优选为45-80℃;所述对硝基苯甲酰氯、2,4-二甲基吡咯、有机弱碱、三氟化硼乙醚合物的摩尔比为1:(1-3):(2-8):(2-8)。
进一步优选地,步骤(b)所述反应溶剂选自水、乙二醇、甲醇、乙醇、甲苯中的一种或多种;碘酸水溶液的浓度为(5~20)%;反应温度为25-100℃,优选为40-80℃;化合物(I)、碘的摩尔比为1:(1-3)。
本发明第三个方面,提供以上所述2,6-二碘代BODIPY衍生物在纳米材料修饰中的应用。
本发明第四个方面,提供一种共价有机框架材料修饰材料,由以上所述化合物(III)修饰得到。
本发明第五个方面,提供以上所述共价有机框架材料修饰材料的制备方法,包括以下步骤:
将化合物(III)溶于有机溶剂中,加入预先制备的COF LZU-1,超声分散均匀;再加入乙酸水溶液,转入聚四氟乙烯反应釜中,在70-80℃下保温2-6h;冷却至室温后,高速离心分离,沉淀用有机溶剂洗涤至上层清液无色,再用乙醚洗涤1次,干燥,即得;
所述有机溶剂选自甲醇、乙醇、四氢呋喃、二氧六环、N,N-二甲基甲酰胺中的一种或多种;优选地,乙酸水溶液的浓度为0.5~5mol/L;优选地,反应温度为60~100℃;优选地,反应时间为2~12h;在这样的条件下,化合物(III)能成功修饰到COF LZU-1纳米材料上。
所述COF LZU-1用如下方法制备:均苯三甲醛(20mg)、对苯二胺(20mg)、三氟乙酸(720μL)溶于乙醇(8mL),得深红色溶液。转入聚四氟乙烯反应釜中,120℃保温12h。冷却后,12000rpm离心30min,沉淀用乙醇和三乙胺体积比为16:1的混合溶液洗涤2次,再用乙醚洗涤1次,40℃干燥得棕黄色粉末。在这样的条件下,COF LZU-1的粒径为纳米尺度。
本发明第六个方面,提供以上所述共价有机框架材料修饰材料在制备光动力学治疗药品或仪器中的应用。
本发明取得有益效果:
(1)本发明化合物(III)可与多种纳米材料(如金属有机框架材料、共价有机框架材料等)发生反应,从而实现对纳米材料的表面修饰,赋予纳米材料新的功能;此外该化合物分子的系间窜越效率大大增强,使BODIPY的光动力性质大大提高,使化合物(III)具有易于扩展、易于修饰的良好特性。
(2)本发明通过选择有效的还原剂、设置相应的反应条件,可由化合物(II)反应得到化合物(III),且产率高达42%。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1化合物(I)的1H NMR谱。
图2化合物(I)的13C NMR谱。
图3化合物(II)的1H NMR谱。
图4化合物(II)的13C NMR谱。
图5化合物(III)的1H NMR谱。
图6化合物(III)的13C NMR谱。
图7 COF LZU-1、COF LZU-1-BODIPY、COF LZU-1-BODIPY-2I的粉末X射线衍射。
图8 COF LZU-1、COF LZU-1-BODIPY-2I、化合物(III)的UV-Vis光谱。
图9 COF LZU-1、COF LZU-1-BODIPY、化合物(IV)的UV-Vis光谱。
图10 COF LZU-1-BODIPY-2I的扫描电镜照片。
图11 COF LZU-1-BODIPY的扫描电镜照片。
图12 COF LZU-1-BODIPY-2I的透射电镜照片。
图13 COF LZU-1-BODIPY的透射电镜照片。
图14 COF LZU-1-BODIPY-2I诱导的DPBF的UV-Vis光谱。
图15 COF LZU-1-BODIPY诱导的DPBF的UV-Vis光谱。
图16 DPBF最大吸收峰的吸光度随光照时间的变化曲线。
具体实施方式
应该指出,以下详细说明都是示例性的,旨在对本发明提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本发明的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作和/或它们的组合。
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案,以下将结合具体的实施例详细说明本发明的技术方案。
实施例1
(a)化合物(I)的合成
4-硝基苯甲酰氯(1.0g)、2,4-二甲基吡咯(1.0g)溶于二氯甲烷(25mL),45℃加热1h。加入三乙胺(2.5mL),继续45℃加热15min。加入三氟化硼乙醚合物(2.5mL),45℃加热3h。混合物旋蒸除去溶剂,中性氧化铝柱色谱分离,洗脱剂二氯甲烷。紫红色固体,产量0.8g,产率40%
1H NMR(400MHz,CDCl3)δ8.39(d,J=8.7Hz,2H),7.54(d,J=8.7Hz,2H),6.02(s,2H),2.57(s,6H),1.36(s,6H).
13C NMR(101MHz,CDCl3)δ156.69,148.35,142.54,141.96,138.34,130.64,129.66,124.37,121.86,14.70,14.67.
MALDI-TOF MS,Calcd.For[M],369.146,Found,369.703.
Anal.Calcd.For C19H18BF2N3O2(%):C,61.82;H,4.91;N,11.38,Found:C,61.65;H,5.00;N,11.28.
(b)化合物(II)的合成
将化合物(I)(0.2g)、碘单质(0.34g)、碘酸(10%,2mL)加入到乙醇(100mL)中,60℃加热0.5h。混合物旋蒸除去溶剂,中性氧化铝柱色谱分离,洗脱剂二氯甲烷。深红色粉末,产量0.22g,产率65%。
1H NMR(400MHz,CDCl3)δ8.42(d,J=8.6Hz,2H),7.53(d,J=8.5Hz,2H),2.66(s,6H),1.38(s,6H).
13C NMR(101MHz,CDCl3)δ158.06,148.63,144.72,141.58,137.82,130.53,129.56,124.66,86.49,17.36,16.19.
MALDI-TOF MS,Calcd.For[M],620.939,Found,621.267.
Anal.Calcd.For C19H16BF2I2N3O2(%):C,36.75;H,2.60;N,6.77,Found:C,36.99;H,2.50;N,7.12.
(c)化合物(III)的合成
以甲酸铵为还原剂
化合物(II)(0.5g)、甲酸铵(1.5g)、钯碳(钯含量10%,50mg),加入到二氯甲烷(40mL)中。25℃搅拌2h。混合物旋蒸除去溶剂,碱性氧化铝柱色谱分离,洗脱剂二氯甲烷。橙红色粉末,产量0.1g,产率21%。
以氯化亚锡为还原剂
(1)化合物(II)(0.5g)溶于二氯甲烷(60mL)、甲醇(60mL)、异丙醇(12mL)的混合溶剂,加入氯化亚锡(2.3g)、盐酸(0.2mol/L,12mL)。55℃加热12h。混合物旋蒸除去溶剂,碱性氧化铝柱色谱分离,洗脱剂二氯甲烷。橙红色粉末,产量0.2g,产率42%。
(2)化合物(II)(0.5g)溶于二氯甲烷(60mL)、甲醇(60mL)、异丙醇(12mL)的混合溶剂,加入氯化亚锡(2.3g)、盐酸(12mol/L,0.2mL)。55℃加热12h。混合物旋蒸除去溶剂,碱性氧化铝柱色谱分离,洗脱剂二氯甲烷。橙红色粉末,产量0.16g,产率34%。
以水合肼为还原剂
化合物(II)(0.5g)溶于四氢呋喃(30mL)和乙醇(30mL)的混合溶剂中,加入钯碳(钯含量10%,0.4g)和水合肼(3.0mL),70℃加热24h。混合物旋蒸除去溶剂,碱性氧化铝柱色谱分离,洗脱剂二氯甲烷。橙红色粉末,产量0.17g,产率36%。
以硼氢化钠为还原剂
化合物(II)(0.5g)溶于乙醇(100mL)中,加入硼氢化钠(0.5g),搅拌下室温反应。薄层色谱(TLC)追踪反应至24h,未见有化合物(III)产生。
以还原铁粉为还原剂
化合物(II)(0.5g)溶于乙醇(100mL)中,加入铁粉(0.5g)、盐酸(12mol/L,5mL),70℃加热。薄层色谱(TLC)追踪反应至72h,未见有化合物(III)产生。
以锡粉为还原剂
化合物(II)(0.5g)溶于甲醇(100mL)中,加入锡粉(0.5g)、盐酸(12mol/L,5mL),70℃加热。薄层色谱(TLC)追踪反应至72h,未见有化合物(III)产生。
化合物(III)的相关波谱学数据:
1H NMR(400MHz,CDCl3)δ6.97(d,J=8.3Hz,2H),6.79(d,J=8.3Hz,2H),3.90(bs,2H),2.63(s,6H),1.51(s,6H).
13C NMR(101MHz,CDCl3)δ156.26,147.59,145.42,142.49,131.95,128.89,124.22,115.59,85.35,17.28,15.99.
MALDI-TOF MS,Calcd.For[M],590.965,Found,590.999;Calcd.For[M-F],571.967,Found,572.010.
Anal.Calcd.For C19H18BF2I2N3(%):C,38.61;H,3.07;N,7.11,Found:C,38.87;H,2.95.;N,7.42.
实施例2
化合物III对COF LZU-1的表面修饰
化合物III(10.6mg)溶于乙醇(5mL)中,加入COF LZU-1(5mg),超声分散均匀;再加入乙酸水溶液(50μL,3mol/L),转入聚四氟乙烯反应釜中,75℃保温4h。冷却后,12000rpm离心30min,沉淀用乙醇洗涤至上层清液无色,再用乙醚洗涤1次,40℃干燥得橙黄色粉末COFLZU-1-BODIPY-2I。
所述COF LZU-1用如下方法制备:均苯三甲醛(20mg)、对苯二胺(20mg)、三氟乙酸(720μL)溶于乙醇(8mL),得深红色溶液。转入聚四氟乙烯反应釜中,120℃保温12h。冷却后,12000rpm离心30min,沉淀用乙醇+三乙胺(v/v=16:1)溶液洗涤2次,再用乙醚洗涤1次,40℃干燥得棕黄色粉末。
化合物III中存在的碘原子通过重原子效应可以增强光动力性质。为了证实这一点,通过对化合物I的直接还原制备了不含碘的BODIPY分子(化合物IV)并通过类似的方法对COF LZU-1进行表面修饰,得COF LZU-1-BODIPY
如图7所示的粉末X射线衍射,证明表面修饰不改变COF LZU-1的晶态结构。
将COF LZU-1、COF LZU-1-BODIPY、COF LZU-1-BODIPY-2I、化合物III、化合物IV加入到DMF中,测定其紫外-可见吸收光谱。如图8,与COF LZU-1相比,COF LZU-1-BODIPY-2I在530nm处的吸收峰证明化合物III对COF LZU-1的成功修饰。化合物III的含量进一步通过标准曲线法测定,测得含量为0.136mmol/g。如图9,与COF LZU-1相比,COF LZU-1-BODIPY在500nm处的吸收峰证明化合物IV对COF LZU-1的成功修饰。化合物IV的含量进一步通过标准曲线法测定,测得含量为0.155mmol/g。
COF LZU-1-BODIPY-2I、COF LZU-1-BODIPY的扫描电镜(SEM)照片如图10、图11所示,比例尺200nm。COF LZU-1-BODIPY-2I、COF LZU-1-BODIPY的粒径~100nm,为典型的纳米材料。
COF LZU-1-BODIPY-2I、COF LZU-1-BODIPY的透射电镜(TEM)照片如图12、图13所示,比例尺100nm。COF LZU-1-BODIPY-2I、COF LZU-1-BODIPY的粒径~100nm,为典型的纳米材料。
综上,利用化合物III中存在的氨基官能团,实现了对COF纳米材料的表面修饰,体现了化合物III易于扩展、易于修饰的良好特性。
实施例3
重原子增强的光动力性能
将COF LZU-1-BODIPY-2I分散到磷酸盐生理盐水缓冲溶液(PBS)中,利用专一性单线态氧捕获剂DPBF评价其光动力性能。
取COF LZU-1-BODIPY-2I PBS分散液(2mL,按BODIPY计浓度为10μmol/L),加入DPBF/DMF溶液(1mmol/L,100μL),用绿光LED灯(功率密度40mW/cm2)照射不同时间,监测DPBF的UV-Vis光谱(图14)。用同样的方法评价相同浓度的COF LZU-1-BODIPY的光动力性能(图15)。并以DPBF的最大吸收峰吸光度A与初始吸光度A0的比A/A0为纵坐标,光照时间为横坐标作图(图16)。
实验发现,DPBF的最大吸收峰吸光度随光照时间的延长而降低,表明COF LZU-1-BODIPY-2I、COF LZU-1-BODIPY均具有光动力性质。但COF LZU-1-BODIPY-2I诱导的DPBF吸光度降低速度显著快于COF LZU-1-BODIPY。
综上,COF LZU-1-BODIPY-2I具有优异的光动力性质,有望成为光动力治疗的候选材料。重要的是,化合物III中重原子的引入大幅增强了BODIPY诱导产生单线态氧的能力。将化合物III修饰在具有良好水分散性和生物相容性的COF材料上,改善了BODIPY的水溶性差的不足,扩展了BODIPY光敏剂的应用范围。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (3)
2.权利要求1所述的2,6-二碘代 BODIPY 衍生物修饰的共价有机框架材料的制备方法,其特征在于,包括以下步骤: 将化合物(III)溶于有机溶剂中,加入预先制备的 COFLZU-1,超声分散均匀;再加入乙酸水溶液,转入聚四氟乙烯反应釜中,在 70-80℃下保温2-6h;冷却至室温后,高速离心分离,沉淀用有机溶剂洗涤至上层清液无色,再用乙醚洗涤1 次,干燥,即得;
所述有机溶剂选自甲醇、乙醇、四氢呋喃、二氧六环、N,N-二甲基甲酰胺中的一种或多种;所述乙酸水溶液的浓度为 0.5~5 mol/L。
3.权利要求 1 所述的2,6-二碘代 BODIPY 衍生物修饰的共价有机框架材料在制备光动力学治疗药品或仪器中的应用。
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