CN106905355A - 一类近红外碘代氟硼二吡咯光敏剂及其制备方法 - Google Patents
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Abstract
本发明涉及一类近红外碘代氟硼二吡咯光敏剂及其制备方法，使用三聚茚醛和碘代BODIPY衍生物在对甲苯磺酸和哌啶催化作用下发生Knoevenagel缩合反应合成，其最大吸收和发射波长均在680nm以上，在近红外光照射下，可以深度穿透生物组织，可作为优越的近红外光敏剂应用于肿瘤、癌症光动力学治疗。此外，该类化合物具有摩尔消光系数高、光稳定性好等优异的光物理性能，在激光染料、生物医学等领域有潜在应用价值。
Description
技术领域
本发明属于有机化合物合成技术领域，具体涉及一类近红外碘代氟硼二吡咯光敏剂及其制备方法。
背景技术
近年来，由于对各种癌症的非侵害性治疗，光动力疗法PDT越来越受到人们的关注。光动力疗法是依靠光敏剂结合特殊的光辐射产生单线态氧，单线态氧是一种细胞毒素剂，能够通过细胞损伤、脉管系统损伤或免疫系统响应根除肿瘤。氟硼二吡咯(BODIPY)衍生物作为一类新型的荧光染料，相比其他染料展示出优越的光物理性能，结构灵活易修饰有助于更好地调节其光学性能。然而由于BODIPY是强荧光染料，很难发生有效的系间窜越，通常并不能应用于光动力治疗，大部分研究的BODIPY染料的最低能量吸收带也不在生物窗口内。
与过渡金属类似，重原子碘、溴等同样具有重原子效应，也能有效提高ISC能力。氟硼二吡咯类化合物有多个活性位点，可对其结构进行修饰引入官能团改变其光物理特质，如对其中2，6位进行碘化修饰，碘原子的引入能够改变单重态及三重态的光物理性质。根据重原子效应，碘原子的引入，提高激发三重态的性质，通过与周围氧分子发生能量及电子交换，把氧分子转化成具有强氧化性的氧负离子，可用于杀死癌细胞。2005年Nagano课题组报道对简单的氟硼二吡咯进行双碘代修饰[Yogo T.，Urano Y.，Ishitsuka Y.，et al.HighlyEfficient and Photostable Photosensitizer Based on BODIPY Chromophore[J].J.Am.Chem.Soc.，2005，127：12162-12163.]，荧光从70％降至2％，ISC大大增强。产生1O2的量子产率ΦΔ为传统染料玫瑰红(Rose Bengal，RB；在甲醇中的ΦΔ为0.76)的1.6倍，并将其运用于细胞内的光动力研究。
目前大多数近红外氟硼二吡咯类染料合成步骤多、难度大、溶解性差，限制了其在生物、环境、医学等领域的进一步应用。三聚茚(truxene)是一个三重对称性平面刚性的稠环芳烃，具有大的刚性共轭结构和较高的光、热稳定性，且是一类结构易修饰的有机光电材料。因此，可通过Suzuki、Sonogashira以及溴代反应，在三聚茚上引入噻吩基团和溴原子，并使用Knoevenagel缩合反应将带有不同取代基的三聚茚基团稼接到BDOIPY上，利用碘的重原子效应和4-(N，N-二甲基)-苯氨的pH响应，合成一类结构新颖、制备方法简单、性能优良的新型近红外氟硼二吡咯光敏剂。
发明内容
发明目的：针对现有技术中存在的不足，本发明的目的是提供一类近红外碘代氟硼二吡咯光敏剂。本发明的另一目的是提供一种上述近红外碘代氟硼二吡咯类光敏剂的制备方法。
技术方案：为了实现上述发明目的，本发明采用的技术方案为：
本发明的一类近红外碘代氟硼二吡咯光敏剂，其结构式如下：
式中，R为溴代三聚茚、碘代三聚茚等。
一种制备上述一类近红外碘代氟硼二吡咯光敏剂及其制备方法，步骤如下：
1)在配备有Dean-Stark装置的圆底烧瓶中加入碘代BODIPY、相应的三聚茚和对甲苯磺酸，然后溶于25mL甲苯和2mL哌啶，混合物加热到140℃回流，TLC检测原料反应完全，收集溶剂直到蒸干。其中，相应的芳醛、对甲苯磺酸和碘代氟硼二吡咯衍生物的摩尔比为1∶1∶1。
2)将反应物冷至室温，减压除去溶剂，残留物经硅胶柱层析分离提纯，得到目标产物。
具体化学反应式如下：
上述步骤(1)中，相应的三聚茚醛、对甲苯磺酸与碘代BODIPY的摩尔比为1∶1∶1。
上述步骤(1)中，加入的甲苯和哌啶的用量分别是25mL和2mL。
上述步骤(1)中，催化剂为对甲苯磺酸和哌啶。
上述步骤(2)中，柱层析分离洗脱剂为石油醚∶二氯甲烷＝7∶3。
本发明的有益效果
与现有技术相比，本发明的一类近红外吸收碘代BODIPY光敏剂及其制备方法具有的优点有：(1)该类化合物的吸收和发射波长在680nm以上，对正常的生物组织细胞损害低，可以深度的穿透生物组织，有利于非侵害性的光动力疗法PDT；(2)反应条件更易控制，污染少，且产品的收率高；(3)分子易修饰、摩尔吸光系数大。
附图说明
图1是化合物A的紫外-可见吸收光谱图；
图2是化合物A的荧光发射光谱图；
图3是化合物B的紫外-可见吸收光谱图；
图4是化合物B的荧光发射光谱图。
具体实施方式
下面结合具体附图对本发明做进一步的说明。
用1H-NMR、UV-Vis谱及ESI MASS表征并证实近红外BODIPY类荧光染料的结构。检测所用仪器为：Bruker ARX600型核磁共振仪(TMS为内标，氘代氯仿为溶剂)，岛津UV-3100型紫外-可见分光光度计(扫描范围300～900nm，光路狭缝2nm)，美国Thermo ELECTRONCORPORATION质谱工作站，荧光光谱用美国Amico Bowman Series 2LuminescenceSpectrometer测试。
实施例1
圆底烧瓶中配备有分水器，将2，6-二碘代BODIPY(123.6mg，0.20mmol)，2-醛基-6，10-二溴三聚茚(0.138g，0.2mmol)和对甲苯磺酸(40mg)溶于25mL甲苯和2mL哌啶，混合物加热到140℃回流，收集溶剂直到蒸干。将反应物浓缩，硅胶柱层析，洗脱剂为(石油醚∶CH2Cl2＝1∶1)，得到绿色固体A(113.7mg，28.79％)。Esi-MS：calcd forC102H99BBr4F2I2N21975.1597，found：1974.27598(M-)；1H NMR：(600MHz，CDCl3)δ8.36(t，J＝7.80Hz，3H)，8.33(s，1H)，8.19(t，J＝9.00Hz，4H)，7.92(s，1H)，7.89(s，1H)，7.79(d，J＝7.20Hz，2H)，7.69(s，2H)，7.59(d，J＝1.80Hz，2H)，7.53-7.50(m，4H)，7.37-7.35(m，2H)，703(s，2H)，3.02-2.92(m，12H)，2.40(s，3H)，2.29-2.26(m，4H)，2.15-2.06(m，14H)，1.53(s，6H)，0.30-0.21(m，36H)；UV-vis：315nm，357nm，409nm，682nm(图1)；EmissionWavelength：710nm(图2)。
实施例2
圆底烧瓶中配备有分水器，将2，6-二碘代BODIPY(185.4mg，0.30mmol)，2-醛基-6，10-二碘三聚茚(237.7mg，0.30mmol)和对甲苯磺酸(50mg)溶于25mL甲苯和2mL哌啶，混合物加热到140℃回流，收集溶剂直到蒸干。将反应物浓缩，硅胶柱层析，洗脱剂为(石油醚/CH2Cl2＝7∶3)，得到绿色固体B(89.7mg，13.82％)。Esi-MS：calcd forC102H99BF2I6N22163.16，found：2163.15(M+)；1H NMR：(600MHz，CDCl3)δ8.36(t，J＝9.00Hz，4H)，8.07(t，J＝9.00Hz，4H)，7.91(s，1H)，7.88(s，1H)，7.80-7.77(m，4H)，7.73-7.69(m，6H)，7.56(d，J＝8.40Hz，2H)，7.03(s，2H)，3.01-2.90(m，12H)，2.40(s，3H)，2.28-2.25(m，4H)，2.15-2.05(m，14H)，1.53(s，6H)，0.29-0.21(m，36H)；UV-vis：319nm，358nm，407nm，683nm(图3)；Emission Wavelength：710nm(图4)。
Claims (6)
1.一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于，其结构通式如下：
式中，R为溴代三聚茚、碘代三聚茚等。
2.权利要求1所述一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于：以相应的三聚茚醛和碘代氟硼二吡咯为原料，在对甲苯磺酸和哌啶的催化作用下合成目标化合物，步骤如下：
1)在无水条件下，在配备有Dean-Stark装置的圆底烧瓶中加入2，6-二碘代氟硼二吡咯、相应的芳醛和对甲苯磺酸，然后溶于甲苯和哌啶中，混合物加热到140℃回流，TLC检测反应原料点消失，收集溶剂直到蒸干。其中，相应的芳醛、对甲苯磺酸和碘代氟硼二吡咯衍生物的摩尔比为1∶1∶1。
2)将反应物冷至室温，减压蒸干溶剂，硅胶柱层析分离提纯，得到目标产物。
3.根据权利要求2所述的一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于，步骤1)中，相应的芳醛、对甲苯磺酸和碘代氟硼二吡咯衍生物的摩尔比为1∶1∶1。
4.根据权利要求2所述的一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于，步骤1)中，溶剂为甲苯。
5.根据权利要求2所述的一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于，步骤1)中，甲苯与哌啶的体积比为12.5∶1。
6.根据权利要求2所述的一类近红外碘代氟硼二吡咯光敏剂及其制备方法，其特征在于，步骤2)中，使用硅胶柱层析分离提纯，洗脱剂为体积比7∶3的石油醚-二氯甲烷。
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