CN113880870B - 一种吡啶类氟硼荧光染料化合物及其制备方法 - Google Patents
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 21
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 45
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 36
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 23
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- 125000003118 aryl group Chemical group 0.000 abstract description 8
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- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 abstract description 3
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
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- G01N1/30—Staining; Impregnating ; Fixation; Dehydration; Multistep processes for preparing samples of tissue, cell or nucleic acid material and the like for analysis
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Abstract
本发明公开了一种吡啶类氟硼荧光染料化合物,所述化合物具有如下式I所示的结构:其中:R选自供电子基团或吸电子基团;M选自烷基、芳基中的一种;环Y为芳环;A为碳原子或氮原子;当A为碳原子时,环X为吡啶或喹啉;当A为氮原子时,环X为喹喔啉。该化合物具有较大的斯托克斯位移、在固态下仍有较强荧光。本发明还公开了该化合物的制备方法。
Description
技术领域
本发明涉及荧光染料技术领域。更具体地,涉及一种吡啶类氟硼荧光染料化合物及其制备方法。
背景技术
荧光染料在许多领域是一个非常重要的工具,其中氟硼荧光染料由于其优异的光化学性能而被广泛应用与生物细胞成像、荧光探针、有机发光二极管(OLED)等。因此通过不断设计新的结构,探索新的荧光性能具有重大意义。氟硼二吡咯甲川类荧光分子(BODIPY)优异的光学性质,例如高的荧光的量子产率,尖锐的吸收和发射峰和稳定的光化学性质等等。它在分子探针、荧光染料、发光材料等领域有着十分重要的作用。因此对于氟硼二吡咯甲川类(BODIPY)引起了人们研究热潮。随着BODIPY染料的发展越来越迅速,对其结构及应用性能的要求也越来越多样化。目前,BODIPY染料的发展己经由短波长结构逐渐向长波长转变,科学家在己知结构的基础上,通过不同的修饰,如增加共轭程度,探究取代基效应、而传统的BODIPY染料也存在着很多的缺陷,例如:斯托克斯位移小(Stokes shift<30nm)、固态时只有很弱的荧光甚至没有荧光等。斯托克斯位移太小使得很难通过光学过滤器去除激发光在生物测定的噪声中读取荧光信号。这主要是由于它们在基态和激发态刚性分子之间的结构差异很小,使得它们的斯托克斯位移值很小。由此引起的自身荧光的再吸收也导致了荧光强度的下降。另外,传统的BODIPY染料结构具有很高的平面性,这增强了分子间的堆积作用,在固态时易于发生聚集荧光淬灭现象。
发明内容
针对以上现有技术中存在的不足,本发明的第一个目的在于提供一种吡啶类氟硼荧光染料化合物,该化合物具有较大的斯托克斯位移、在固态下仍有较强的荧光。
本发明的第二个目的在于提供一种吡啶类氟硼荧光染料化合物的制备方法。该方法合成简单,合成效率高,成本较低。
本发明的第三个目的在于提供一种吡啶类氟硼荧光染料化合物在制备发光材料中的应用。
本发明的第四个目的在于提供一种吡啶类氟硼荧光染料化合物在荧光检测中的应用。
为达到上述第一个目的,本发明采用下述技术方案:
一种吡啶类氟硼荧光染料化合物,所述化合物具有如下式I所示的结构:
其中:
R选自供电子基团或吸电子基团;
M选自烷基、芳基中的一种;
环Y为芳环;
A为碳原子或氮原子;
当A为碳原子时,环X为吡啶或喹啉;也即,此时,所述化合物具有如下式I-1或I-2所示的结构:
当A为氮原子时,环X为喹喔啉;也即,此时,所述化合物具有如下式I-3所示的结构:
进一步地,所述供电子基团选自烷氧基、氨基、羟基、二苯胺基、咔唑基、二甲氨基中的一种。示例性的,所述烷氧基包括但不限于为甲氧基,乙氧基,苄氧基等。
进一步地,所述吸电子基团选自醛基、酰胺基、腈基、硝基、卤仿基、季胺基、三氟甲基中的任意一种。
进一步地,所述烷基选自C1-C5的烷基。
进一步地,所述芳基选自苯基、萘基中的一种。
进一步地,所述芳环选自苯环、吡啶、喹啉、咔唑、吩噻嗪中的一种。
为达到上述第二个目的,本发明提供一种吡啶类氟硼荧光染料化合物的制备方法,该方法包括如下步骤:
1)将式II所示的化合物与式III所示的化合物在催化剂、碱存在的条件下进行α-芳基化反应,得式IV所示的化合物;
其中,R选自供电子基团或吸电子基团;
R1选自卤素或类卤基团;优选地,所述卤素选自Cl、Br;所述类卤基团选自OTf、OTs;
环Y为芳环或杂环;
M选自烷基、芳基中的一种;
A为碳原子或氮原子;
当A为碳原子时,环X为吡啶或喹啉;当A为氮原子时,环X为喹喔啉;
2)将式IV所示的化合物在氮气气氛下溶于第二溶剂中,在六甲基二硅氮烷(HMDS)存在的条件下,与三氟化硼乙醚(BF3·Et2O)进行回流反应,得所述吡啶类氟硼荧光染料化合物。
进一步地,步骤1)中,所述催化剂选自醋酸钯、所述碱选自碳酸铯。
进一步地,步骤1)中,反应在同时含有催化剂、催化剂配体、碱、溶剂的条件下进行。
进一步地,所述催化剂配体选自X-Phos,所述溶剂选自无水1,4-二氧六环。
进一步地,步骤1)中,所述反应的温度为95-105℃,时间为10-15h。
进一步地,步骤2)中,所述回流反应的温度为110-115℃,时间为3-5h。
进一步地,步骤2)中,式IV所示的化合物、六甲基二硅氮烷、三氟化硼乙醚的摩尔比为1:2-4:4-6。
进一步地,步骤2)中,所述第二溶剂为甲苯。
进一步地,步骤2)中,将式IV所示的化合物在氮气气氛下溶于第二溶剂中,在0℃温度下,顺序加入六甲基二硅氮烷(HMDS)、三氟化硼乙醚(BF3·Et2O)。此投料顺序,使得该反应能够顺利进行,并高收率得到目标分子。其中,HMDS的作用为碱拔氢,促进酮式发生烯醇化再与二氟化硼配位。
进一步地,步骤2)中,回流反应结束后,还包括后处理的步骤;所述后处理优选包括将反应混合物倒入二氯甲烷中,饱和氯化钠溶液洗涤,并用无水硫酸镁干燥并过滤,减压去除溶剂,使用乙酸乙酯~石油醚作为洗脱剂通过柱层析分离纯化。其中,洗脱剂石油醚~乙酸乙酯体积比为10:1。
如无特殊说明,本发明中使用的原料均可通过市售商购获得。
本发明的有益效果如下:
本发明提供的吡啶类氟硼荧光染料化合物荧光性能优异,具有较大的斯托克斯位移(116nm)、在固态下仍有较强荧光。该化合物的结构中,由于吡啶基团与二氟化硼配位后所形成的缺电子区域,与苯基上的给电子集团形成了较强的“D-A”结构。由于二氟化硼的引入,使得吡啶与含有BF2的六元环处于同一平面,形成更具缺电性的杂环,苯环通过可自由旋转的σ键与共轭体系链接。由于苯环可自由旋转,形成扭曲的分子内电荷转移,使得该分子在聚集态也可以产生较强的荧光。值得注意的是,在上述合成的一系列分子中,具有给电子基团的分子(如二苯胺基),发出的荧光偏黄色,而具有吸电子基团(如三氟甲基)荧光则为蓝色。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出本发明实施例2中的荧光分子在二氯甲烷溶剂中,荧光发射光谱,横坐标为波长,纵坐标为归一化的荧光强度。
图2示出本发明实施例2中氟硼化合物b(环X=吡啶,环Y=苯环,R=H)的核磁共振氢谱。
图3示出本发明实施例2中氟硼化合物b(环X=吡啶,环Y=苯环,R=CF3)的核磁共振氢谱。
图4示出本发明实施例2中氟硼化合物b(环X=吡啶,环Y=苯环,R=NPh2)的核磁共振氢谱。
图5示出本发明实施例2中氟硼化合物b(环X=吡啶,环Y=苯环,R=咔唑)的核磁共振氢谱。
图6示出本发明实施例2中氟硼化合物b(环X=喹啉,环Y=苯环,R=H)的核磁共振氢谱。
图7示出本发明实施例2中氟硼化合物b(环X=喹啉,环Y=苯环,R=NMe2)的核磁共振氢谱。
图8示出本发明实施例2中氟硼化合物b(环X=喹啉,环Y=苯环,R=CF3)的核磁共振氢谱。
图9示出本发明实施例2中氟硼化合物b(环X=喹啉,环Y=苯环,R=NPh2)的核磁共振氢谱。
图10示出本发明实施例2中氟硼化合物b(环X=吡啶,环Y为N-乙基咔唑)的核磁共振氢谱。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
R=H,三氟甲基,二苯胺基,咔唑中的一种。
化合物a的合成:将溴苯(1.3mmol),醋酸钯(0.05mmol)、2-二环己基膦-2',4',6'-三异丙基联苯(X-Phos)(0.05mmol)、碳酸铯(3mmol)加入到反应管中,将体系置于氮气氛围下,加入无水1,4-二氧六环与化合物2-吡啶基乙酸乙酯(1mmol)。将体系置于100℃搅拌10-15h。反应结束后将混合物用硅藻土过滤,乙酸乙酯洗涤,旋干溶剂,柱层析分离纯化后得到化合物a。
目标化合物a(R=H)淡黄色油状液体,产率为95%。1H NMR(400MHz,CDCl3)δ8.57(d,J=4.8Hz,1H),7.61(td,J=7.7,1.8Hz,1H),7.39(d,J=7.4Hz,2H),7.34(t,J=7.4Hz,2H),7.29(dd,J=6.2,3.7Hz,1H),7.24(d,J=7.9Hz,1H),7.16(dd,J=7.4,5.0Hz,1H),5.22(s,1H),4.23(q,J=7.1Hz,2H),1.25(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ171.88,158.88,149.39,137.48,136.77,129.02,128.80,127.64,123.17,122.20,61.41,59.91,14.21.HRMS(ESI)calcd for C16H14F3NO2[M+H]+242.1105,found 242.1124.
目标化合物a(R=CF3)淡黄色油状液体,产率为94%。1H NMR(400MHz,CDCl3)δ8.58(d,J=4.3Hz,1H),7.66–7.61(m,1H),7.61–7.50(m,4H),7.25(d,J=8.3Hz,1H),7.18(dd,J=6.9,5.1Hz,1H),5.26(s,1H),4.24(q,J=7.1Hz,2H),1.25(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ171.04,157.85,149.57,141.37,136.88,129.94(q,J=32.8Hz),129.59,125.54(q,J=3.7Hz),123.03,122.74,122.40,61.58,59.44,14.05.HRMS(ESI)calcd forC15H15NO2[M+H]+310.1049,found 310.1057.
目标化合物a(R=NPh2)黄色固体,产率为92%。1H NMR(400MHz,CDCl3)δ8.61(dd,J=5.1,1.7Hz,1H),7.67(td,J=7.7,1.7Hz,1H),7.34(d,J=8.1Hz,1H),7.29–7.23(m,6H),7.23–7.17(m,1H),7.12(d,J=7.6Hz,4H),7.08–7.03(m,4H),5.20(s,1H),4.27(qd,J=7.1,1.5Hz,2H),1.29(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ171.96,158.96,149.40,149.35,147.65,147.13,136.70,132.21,131.17,129.68,129.26,125.43,124.72,124.49,123.83,123.53,123.03,122.96,122.09,61.29,59.21,14.17.HRMS(ESI)calcd forC27H24N2O2[M+H]+310.5010,found 408.5028.
目标化合物a(R=咔唑)黄色固体,产率为80%。1H NMR(400MHz,CDCl3)δ8.62(d,J=4.3Hz,1H),8.11(d,J=7.7Hz,2H),7.66(td,J=7.8,1.7Hz,1H),7.62(d,J=8.4Hz,2H),7.52(d,J=8.4Hz,2H),7.41(d,J=8.0Hz,2H),7.39–7.33(m,3H),7.29–7.22(m,2H),7.21–7.14(m,1H),5.32(s,1H),4.29(q,J=7.1Hz,2H),1.29(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ171.61,158.43,149.62,140.78,137.06,136.93,136.62,130.52,127.13,125.97,123.44,123.15,122.39,120.33,120.03,109.89,61.58,59.45,14.23.
实施例2
R=H,三氟甲基,二苯胺基,二甲胺基,咔唑中的一种。
化合物b的合成:将化合物a(1mmol)在氮气氛围下溶于甲苯中,在0℃下依次加入六甲基二硅氮烷(HMDS)(3mmol)和三氟化硼乙醚(BF3·Et2O)(5mmol)搅拌0.5h,然后在110℃下回流反应3h。停止反应,将反应混合物倒入二氯甲烷中,饱和氯化钠溶液洗涤,并用无水硫酸镁干燥并过滤,减压去除溶剂,柱层析分离纯化后得到目标产物b。
氟硼化合物b(环X=吡啶,R=H)淡黄色固体,产率为95%。1H NMR(400MHz,CDCl3)δ8.17(d,J=5.4Hz,1H),7.51(ddd,J=8.7,7.1,1.6Hz,1H),7.41(t,J=7.3Hz,2H),7.33(ddd,J=6.4,3.9,1.2Hz,1H),7.28–7.22(m,2H),6.92(dd,J=9.8,3.5Hz,1H),6.84(d,J=8.8Hz,1H),4.32(q,J=7.1Hz,2H),1.26(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ162.52,154.85,139.90,138.80,133.34,132.02,128.94,127.44,119.90,116.14,88.52,63.59,14.86.19FNMR(377MHz,CDCl3)δ-141.59,-141.63,-141.67,-141.71.HRMS(ESI)calcd for C15H14BF2NO2[M+H]+290.1157,found 290.1179.
氟硼化合物b(环X=吡啶,R=三氟甲基)淡黄色固体,产率为91%。1H NMR(400MHz,CDCl3)δ8.24(d,J=5.7Hz,1H),7.70(d,J=8.1Hz,2H),7.62(ddd,J=8.7,7.2,1.6Hz,1H),7.44(d,J=8.0Hz,2H),7.10–6.94(m,1H),6.88(d,J=8.7Hz,1H),4.38(q,J=7.1Hz,2H),1.30(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ162.59,154.23,140.36,139.08,137.45,132.39,129.42(q,J=32.4Hz),125.82(q,J=3.7Hz),122.99,119.50,116.64,87.38,63.87,14.76.19F NMR(376MHz,CDCl3)δ-62.49,-141.90,-141.94,-141.98,-142.02.HRMS(ESI)calcd for C16H13BF5NO2[M+H]+357.0963,found 357.0939.
氟硼化合物b(环X=吡啶,R=二苯胺基)黄色固体,产率为89%。1H NMR(400MHz,CDCl3)δ8.16(d,J=5.9Hz,1H),7.54(qd,J=7.1,3.5Hz,1H),7.29–7.23(m,4H),7.14(d,J=7.7Hz,4H),7.09(s,4H),7.02(t,J=7.3Hz,2H),6.97(d,J=8.8Hz,1H),6.94–6.89(m,1H),4.34(q,J=7.1Hz,2H),1.29(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ162.61,154.99,147.78,146.89,139.84,138.78,132.61,129.41,126.79,124.74,123.42,123.15,120.06,116.08,88.05,63.57,14.93.19F NMR(376MHz,CDCl3)δ-141.73,-141.76,-141.81,-141.85.HRMS(ESI)calcd for C27H23BF2N2O2[M+H]+456.2998,found 456.3012.
氟硼化合物b(环X=吡啶,R=咔唑)黄色固体,产率为92%。1H NMR(400MHz,CDCl3)δ8.23(d,J=6.1Hz,1H),8.16(d,J=7.7Hz,2H),7.62(d,J=7.4Hz,3H),7.55–7.47(m,4H),7.44(t,J=7.7Hz,2H),7.30(t,J=7.4Hz,2H),7.07–6.96(m,2H),4.42(q,J=7.1Hz,2H),1.35(t,J=7.0Hz,2H).13C NMR(101MHz,CDCl3)δ167.58,154.99,147.78,146.89,140.80,138.87,133.32,126.79,124.74,127.18,125.92,120.43,120.03,116.25,109.85,94.13,89.02,63.72,14.84.19F NMR(376MHz,CDCl3)δ-141.76,-141.80,-141.84,-141.88.
氟硼化合物b(环X=喹啉,R=H)黄色固体,产率为85%。1H NMR(400MHz,CDCl3)δ8.48(d,J=8.9Hz,1H),7.71–7.62(m,2H),7.56(dd,J=7.9,1.3Hz,1H),7.47–7.39(m,2H),7.37(dt,J=14.8,4.3Hz,2H),7.25(dd,J=5.2,3.1Hz,2H),6.79(d,J=9.2Hz,1H),4.39(q,J=7.1Hz,2H),1.28(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ156.20,139.52,139.04,133.50,132.25,131.75,128.96,128.26,127.57,124.97,124.62,121.79,121.71,121.63,119.16,63.92,14.61.19F NMR(377MHz,CDCl3)δ-129.41,-129.46,-129.51,-129.56.
氟硼化合物b(环X=喹啉,R=二甲胺基)黄色固体,产率为81%。1H NMR(400MHz,CDCl3)δ8.47(dd,J=6.1,2.7Hz,1H),7.65(ddd,J=8.8,5.9,2.4Hz,2H),7.55(dd,J=7.9,1.5Hz,1H),7.38–7.31(m,1H),7.12–7.05(m,2H),6.88(d,J=9.3Hz,1H),6.83–6.75(m,2H),4.40(q,J=7.1Hz,2H),3.00(s,6H),1.31(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ164.47,156.78,149.74,139.54,138.62,132.78,131.54,128.19,124.75,124.59,121.62,120.73,119.60,112.71,90.14,63.79,40.48,14.73.19F NMR(376MHz,CDCl3)δ-129.64,-129.68,-129.74,-129.78.
氟硼化合物b(环X=喹啉,R=三氟甲基)黄色固体,产率为78%。1H NMR(400MHz,CDCl3)δ8.50(dt,J=8.7,2.6Hz,1H),7.77(d,J=9.2Hz,1H),7.70(d,J=8.3Hz,3H),7.61(dd,J=7.9,1.4Hz,1H),7.41(dd,J=11.9,4.5Hz,3H),6.77(d,J=9.2Hz,1H),4.42(q,J=7.1Hz,2H),1.30(t,J=7.1Hz,3H).13C NMR(101MHz,CDCl3)δ164.02,155.66,139.62,139.50,137.59,132.68,132.00,129.65(q,J=32.5Hz),128.39,125.87(q,J=3.7Hz),125.27,124.70,122.88,121.78,118.58,88.99,64.19,14.54.19F NMR(377MHz,CDCl3)δ-62.48,-129.49,-129.54,-129.59,-129.63.
氟硼化合物b(环X=喹啉,R=二苯胺基)黄色固体,产率为79%。1H NMR(400MHz,CDCl3)δ8.48(d,J=8.9Hz,1H),7.76(d,J=9.3Hz,1H),7.71–7.64(m,1H),7.64–7.56(m,1H),7.39(t,J=7.4Hz,1H),7.29(dd,J=8.4,7.4Hz,4H),7.20–7.16(m,4H),7.13–7.02(m,6H),6.96(d,J=9.2Hz,1H),4.43(q,J=7.1Hz,2H),1.34(t,J=7.1Hz,3H).13CNMR(101MHz,CDCl3)δ164.30,156.37,147.64,147.05,139.56,138.97,132.84,131.71,129.35,128.25,126.77,124.92,124.76,123.20,123.17,121.76,121.69,119.36,89.81,63.90,14.68.19FNMR(376MHz,CDCl3)δ-129.68,-129.72,-129.78,-129.82.
氟硼化合物b(环X=吡啶,环Y为N-乙基咔唑)黄色固体,产率为83%。1H NMR(400MHz,Chloroform-d)δ8.19(d,J=5.2Hz,1H),8.06(d,J=7.7Hz,1H),7.97(s,1H),7.51–7.39(m,4H),7.32(d,J=8.3Hz,1H),7.27–7.17(m,1H),6.90(t,J=6.6Hz,1H),6.84(d,J=8.7Hz,1H),4.39(d,J=7.3Hz,2H),4.35(d,J=7.0Hz,2H),1.47(t,J=7.2Hz,3H),1.26(t,J=7.0Hz,3H).19F NMR(376MHz,CDCl3)δ-129.65,-129.67,-129.73,-129.78.
所合成的氟硼化合物激发/发射光谱以及stokes位移数据如下表1所示。与经典的荧光分子BODIPY(20-30nm)相比,均具有较大的stokes位移(62-116nm),在进一步应用方面可避免了自吸收带来的影响。
表1
氟硼化合物b | 激发波长(nm) | 发射波长(nm) | Stokes位移(nm) |
环X=吡啶,R=H | 375 | 483 | 108 |
环X=吡啶,R=CF3 | 384 | 490 | 106 |
环X=吡啶,R=NPh2 | 372 | 461 | 89 |
环X=吡啶,R=咔唑 | 380 | 496 | 116 |
环X=喹啉,R=H | 426 | 492 | 66 |
环X=喹啉,R=NMe | 428 | 517 | 89 |
环X=喹啉,R=CF | 425 | 487 | 62 |
环X=喹啉,R=NPh2 | 426 | 530 | 104 |
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (6)
1.一种吡啶类氟硼荧光染料化合物,其特征在于,所述化合物具有如下式I所示的结构:
;
其中:
R选自二苯胺基、咔唑基、二甲氨基、三氟甲基中的一种;
M选自烷基,所述烷基选自C1-C5的烷基;
环Y为苯环;
A为碳原子;
环X为吡啶或喹啉。
2.一种吡啶类氟硼荧光染料化合物,其特征在于,所述化合物具有如下式所示的结构:
或/>。
3.如权利要求1所述的吡啶类氟硼荧光染料化合物的制备方法,其特征在于,包括如下步骤:
1)将式II所示的化合物与式III所示的化合物在催化剂、碱存在的条件下进行α-芳基化反应,得式IV所示的化合物,其中,所述催化剂选自醋酸钯;
II、/> III、/> IV;
其中,R选自二苯胺基、咔唑基、二甲氨基、三氟甲基中的一种;
R1选自卤素;
环Y为苯环;
M选自烷基,所述烷基选自C1-C5的烷基;
A为碳原子;
环X为吡啶或喹啉;
2)将式IV所示的化合物在氮气气氛下溶于第二溶剂中,在六甲基二硅氮烷存在的条件下,与三氟化硼乙醚进行回流反应,得所述吡啶类氟硼荧光染料化合物;其中,第二溶剂选自甲苯。
4.根据权利要求3所述的制备方法,其特征在于,步骤1)中,所述反应的温度为90-105℃,时间为10-15h。
5.根据权利要求3所述的制备方法,其特征在于,步骤2)中,所述回流反应的温度为110-115℃,时间为3-5h。
6.根据权利要求3所述的制备方法,其特征在于,步骤2)中,式IV所示的化合物、六甲基二硅氮烷、三氟化硼乙醚的摩尔比为1:2-4:4-6。
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