CN111333670A - 异吲哚氟硼三吡咯荧光染料及其制备方法 - Google Patents
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Abstract
本发明涉及有机合成和精细化工制备领域,公开了一种异吲哚氟硼三吡咯荧光染料及其制备方法,所述制备方法包括:将异吲哚啉酮、吡咯、溶剂和路易斯酸混合进行第一接触反应,之后加入酸酐或酰氯进行第二接触反应,之后加入三乙胺和三氟化硼乙醚进行第三接触反应;提供了一种新型异吲哚氟硼三吡咯荧光染料的合成路线,通过本发明所合成得到的荧光染料为红光,且具有0.89‑0.99的高荧光量子产率。
Description
技术领域
本发明涉及有机合成和精细化工制备领域,具体地,涉及一种异吲哚氟硼三吡咯荧光染料及其制备方法。
背景技术
氟硼三吡咯荧光染料近年来因高荧光量子产率、高光稳定性、高摩尔吸光系数等优点,备受关注。目前,氟硼三吡咯荧光染料的合成路线较为复杂,反应效率不高,荧光量子产率相对不高,因此很有必要设计开发新型的合成路线来制备高荧光量子产率的氟硼三吡咯荧光染料。
本发明在实验基础上,利用廉价易得的商品化原料异吲哚啉酮与吡咯在三氯氧磷下缩合构建不对称二吡咯后,在酸酐或酰氯存在下促使异吲哚裂解进而构建苯并三吡咯结构,在氟硼配位的基础上探索合成该类具有高荧光量子产率的氟硼三吡咯荧光染料,是本发明亟需解决的问题。
发明内容
本发明的目的是提供一种异吲哚氟硼三吡咯荧光染料及其制备方法,解决了目前,氟硼三吡咯荧光染料的合成路线较为复杂,反应效率不高,以及目前荧光染料的荧光量子产率相对不高的问题。
为了实现上述目的,本发明提供了一种异吲哚氟硼三吡咯荧光染料,所述异吲哚氟硼三吡咯荧光染料的结构式为:
其中,R为CF3、C1-12的直链或者支链烷基、C1-12的直链或者支链环烷基团、异丙基、或芳香基团中的一种。
本发明还提供了一种如上述异吲哚氟硼三吡咯荧光染料的制备方法,所述制备方法包括:
将异吲哚啉酮、吡咯、溶剂和路易斯酸混合进行第一接触反应,之后加入酸酐或酰氯进行第二接触反应,之后加入三乙胺和三氟化硼乙醚进行第三接触反应。
通过上述技术方案,本发明提供了一种异吲哚氟硼三吡咯荧光染料及其制备方法,利用商品化原料异吲哚啉酮与吡咯等吡咯在三氯氧磷下缩合后,加入酸酐或酰氯,进而氟硼配位制备出一类结构新颖的异吲哚氟硼三吡咯荧光染料,该制备方法为“三步一锅”法,工艺简单,反应高效,制得的异吲哚氟硼三吡咯荧光染料具有高荧光量子产率。
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本发明,但并不构成对本发明的限制。在附图中:
图1为异吲哚氟硼三吡咯荧光染料1a的X-射线单晶结构图;
图2为异吲哚氟硼三吡咯荧光染料1a在氘代二甲亚砜中的氢谱;
图3为异吲哚氟硼三吡咯荧光染料1a在氘代二甲亚砜中的碳谱;
图4为异吲哚氟硼三吡咯荧光染料1a的高分辨质谱;
图5为异吲哚氟硼三吡咯荧光染料1b在氘代二甲亚砜中的氢谱;
图6为异吲哚氟硼三吡咯荧光染料1b在氘代二甲亚砜中的碳谱;
图7为异吲哚氟硼三吡咯荧光染料1b的高分辨质谱;
图8为异吲哚氟硼三吡咯荧光染料1a在正己烷中的绝对荧光量子产率测试图;
图9为异吲哚氟硼三吡咯荧光染料1a在二氯甲烷中的绝对荧光量子产率测试图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明提供了一种异吲哚氟硼三吡咯荧光染料,所述异吲哚氟硼三吡咯荧光染料的结构式为:
其中,R为CF3、C1-12的直链或者支链烷基、C1-12的直链或者支链环烷基团、异丙基、或芳香基团中的一种。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,所述芳香基团含有吡咯环、呋喃环、噻吩环或苯环中的一种的官能团。
本发明还提供了一种如上述异吲哚氟硼三吡咯荧光染料的制备方法,所述制备方法包括:
将异吲哚啉酮、吡咯、溶剂和路易斯酸混合进行第一接触反应,之后加入酸酐或酰氯进行第二接触反应,之后加入三乙胺和三氟化硼乙醚进行第三接触反应。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,异吲哚啉酮的结构式为:
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,相对于1mmol的异吲哚啉酮,吡咯的用量为1-1.2mmol。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,第一接触反应的条件包括:温度为 70-150℃,时间为2-100h;
和/或,第二接触反应的条件包括:温度为70-100℃,时间为1-100h;
和/或,第三接触反应的条件包括:温度为0-120℃,时间为30min-100h。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,路易斯酸为四氯化钛、三氯氧磷和三溴氧磷中的一种或多种。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,第一接触反应开始时,体系的pH为 4.0-6.0。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,溶剂为三氯甲烷、1,2-二氯甲烷、二氯甲烷、甲苯、氯苯、邻二氯苯、对二氯苯、间二氯苯、乙腈和乙酸乙酯中的一种或多种。
在本发明的一种优选的实施方式中,为了进一步提高制得的异吲哚氟硼三吡咯荧光染料的荧光量子产率,在氮气保护的条件下,将异吲哚啉酮、吡咯、溶剂和路易斯酸进行混合。
以下将通过实施例对本发明进行详细描述。
实施例1
异吲哚氟硼三吡咯荧光染料1a的合成:
在氮气保护下,取异吲哚啉酮(100mg,0.75mmol)和吡咯(58μL, 0.83mmol)溶于无水氯苯(30mL)中,加入三氯氧磷(68μL,0.75mmol);反应混合液加热至110摄氏度下搅拌6h后,保持此温度下加入三氟乙酸酐 (48μL,0.34mmol),继续搅拌6h;然后向反应混合物体系中加入1.5mL三乙胺,10分钟后再缓慢加入三氟化硼乙醚3mL,继续搅拌2h;反应混合物转移到分液漏斗中,加入二氯甲烷和水萃取,分离有机相,相应的水相用二氯甲烷萃取三次,合并有机层;水洗有机相,无水硫酸钠干燥,静置,过滤,真空下浓缩溶剂。将所得粗产物利用柱层析分离技术分离(淋洗液用石油醚 /二氯甲烷=3:1),减压旋蒸,得到异吲哚氟硼三吡咯荧光染料1a固体产物,产率为28%(48mg);
用二氯甲烷和正己烷重结晶,其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,DMSO-d6)δ11.54(brs,1H),9.78(brs,1H),8.23(d,J=8.0Hz, 1H),7.72–7.34(m,5H),6.57(s,1H),6.36(s,1H),6.17–6.08(m,2H),4.26(s, 2H).13C NMR(126MHz,DMSO-d6)δ156.1,151.2,135.6,135.4,132.7,132.2, 132.0,131.6,130.9,130.2,129.8,129.7,129.2,128.2,127.9,127.7,126.1,121.4, 121.3,121.0,119.0,116.9,114.6,114.2,112.2,79.2,40.4.HRMS(APCI)calcd for C26H19BF5N4O[M+H]+:509.1572,found 509.1567。
实施例2
异吲哚氟硼三吡咯荧光染料1b的合成:
按照实施例1的方法进行,不同的是,将三氟乙酸酐换成等当量的苯甲酰氯(40μL,0.34mmol),制备得到的异吲哚氟硼三吡咯荧光染料1b的产率为32%(56mg);
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,DMSO-d6)δ11.52(s,1H),8.81(s,1H),8.21(d,J=7.9Hz,1H),7.71–7.60(m,5H),7.55– 7.37(m,7H),6.57(s,1H),6.38(d,J=3.4Hz,1H),6.24(d,J=7.9Hz,1H), 6.17(d,J=3.6Hz,1H),4.34–4.29(m,2H);13CNMR(75MHz,DMSO-d6)δ166.4,151.2,137.6,135.8,134.1,132.5,132.1,131.7,131.7,131.7,131.2,130.2, 129.7,129.5,129.3,128.1,127.7,127.7,127.6,127.2,126.1,121.7,121.3,121.1, 119.3,114.3,112.2,110.3,40.5.HRMS(APCI)calcd forC31H24BF2N4O[M+ H]+:517.2011,found 517.1974。
实施例3
异吲哚氟硼三吡咯荧光染料1c的合成:
按照实施例1的方法进行,不同的是,将三氟乙酸酐换成等当量的异丙基酰氯(33μL,0.34mmol),制备得到的异吲哚氟硼三吡咯荧光染料1c的产率为21%(34mg);
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,CDCl3)δ10.82 (s,1H),8.03(d,J=7.6Hz,1H),7.71–7.26(m,8H),7.11(t,J=7.5Hz,1H), 6.44(s,1H),6.24(s,1H),6.14(d,J=7.7Hz,1H),6.07(s,1H),5.48(s,1H), 4.31–4.24(m,1H),4.14–4.09(m,1H),1.93–1.89(m,1H),0.80(t,J=6.0Hz, 6H).13C NMR(75MHz,CDCl3)δ176.7,151.1,137.3,136.4,134.3,133.6, 133.4,132.7,132.3,131.8,131.6,130.6,129.9,129.8,128.3,127.5,125.6,123.6, 122.2,121.8,120.9,119.7,114.5,112.5,41.5,35.4,19.3.HRMS(APCI)calcd for C28H26BF2N4O[M+H]+:483.2168,found 483.2155。
检测例1
对实施例1制得的异吲哚氟硼三吡咯荧光染料1a进行X-射线单晶衍射表征,具体结果如图1所示。
检测例2
实施例1-3中制得的异吲哚氟硼三吡咯荧光染料在不同有机溶剂中的最大吸收波长(λabs max/nm)、摩尔吸光系数(lgεmax)、最大发射波长(λem max/nm)、荧光量子产率(φ)和斯托克斯位移(Stokes Shift/cm-1)如表1所示:
表1
通过上述实施例1-3可知,本发明提供了一种商品化原料异吲哚啉酮与吡咯在三氯氧磷下缩合后,加入酸酐或酰氯,进而氟硼配位制备一类结构新颖的异吲哚氟硼三吡咯荧光染料。该制备方法为“三步一锅”法,反应高效,工艺相对简单。所制备的异吲哚氟硼三吡咯荧光染料具有高荧光量子产率 (0.89-0.99)、大摩尔吸光系数,最大吸收波长在524-572nm,最大发射光谱在580-630nm,在生物医学和材料科学等领域具有重要的应用前景。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (10)
2.根据权利要求1所述的异吲哚氟硼三吡咯荧光染料,其中,所述芳香基团含有吡咯环、呋喃环、噻吩环或苯环中的一种的官能团。
3.一种如权利要求1或2所述异吲哚氟硼三吡咯荧光染料的制备方法,其特征在于,所述制备方法包括:
将异吲哚啉酮、吡咯、溶剂和路易斯酸混合进行第一接触反应,之后加入酸酐或酰氯进行第二接触反应,之后加入三乙胺和三氟化硼乙醚进行第三接触反应。
5.根据权利要求3所述的制备方法,其中,相对于1mmol的异吲哚啉酮,吡咯的用量为1-1.2mmol。
6.根据权利要求3所述的制备方法,其中,第一接触反应的条件包括:温度为70-150℃,时间为2-100h;
和/或,第二接触反应的条件包括:温度为70-100℃,时间为1-100h;
和/或,第三接触反应的条件包括:温度为0-120℃,时间为30min-100h。
7.根据权利要求3所述的制备方法,其中,路易斯酸为四氯化钛、三氯氧磷和三溴氧磷中的一种或多种。
8.根据权利要求7所述的制备方法,其中,第一接触反应开始时,体系的pH为4.0-6.0。
9.根据权利要求3所述的制备方法,其中,溶剂为三氯甲烷、1,2-二氯甲烷、二氯甲烷、甲苯、氯苯、邻二氯苯、对二氯苯、间二氯苯、乙腈和乙酸乙酯中的一种或多种。
10.根据权利要求3所述的制备方法,其中,在氮气保护的条件下,将异吲哚啉酮、吡咯、溶剂和路易斯酸进行混合。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5573909A (en) * | 1992-05-13 | 1996-11-12 | Molecular Probes, Inc. | Fluorescent labeling using microparticles with controllable stokes shift |
JP2000047379A (ja) * | 1998-07-27 | 2000-02-18 | Kansai Paint Co Ltd | ポジ型可視光感光性樹脂組成物及びその用途 |
CN102702768A (zh) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | 一种新型红光bodipy荧光染料及其制备方法和应用 |
CN104403663A (zh) * | 2014-12-11 | 2015-03-11 | 华东理工大学 | 一种检测内源性h2s的荧光探针及其制备方法和应用 |
US20170233414A1 (en) * | 2016-02-12 | 2017-08-17 | Oregon Health & Science University | Derivatives of bodipy |
-
2019
- 2019-12-12 CN CN201911274625.6A patent/CN111333670B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5573909A (en) * | 1992-05-13 | 1996-11-12 | Molecular Probes, Inc. | Fluorescent labeling using microparticles with controllable stokes shift |
JP2000047379A (ja) * | 1998-07-27 | 2000-02-18 | Kansai Paint Co Ltd | ポジ型可視光感光性樹脂組成物及びその用途 |
CN102702768A (zh) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | 一种新型红光bodipy荧光染料及其制备方法和应用 |
CN104403663A (zh) * | 2014-12-11 | 2015-03-11 | 华东理工大学 | 一种检测内源性h2s的荧光探针及其制备方法和应用 |
US20170233414A1 (en) * | 2016-02-12 | 2017-08-17 | Oregon Health & Science University | Derivatives of bodipy |
Non-Patent Citations (4)
Title |
---|
CHANGJIANG YU等: ""Red to Near-Infrared Isoindole BODIPY Fluorophores: Synthesis, Crystal Structures, and Spectroscopic and Electrochemical Properties"", 《J. ORG. CHEM.》 * |
CHANGJIANG YU等: "Isoindole-BODIPY Dyes as Red to Near-Infrared Fluorophores", 《CHEM. EUR. J.》 * |
WANLE SHENG等: "Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C–H bond activation", 《CHINESE CHEMICAL LETTERS》 * |
WEI MIAO等: "Functionalized BODIPYs as Fluorescent Molecular Rotors for Viscosity Detection", 《FRONTIERS IN CHEMISTRY》 * |
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