CN110872312A - 苯并二吡咯酮氟硼荧光染料及其制备方法 - Google Patents
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- -1 benzodipyrrolidone fluoroboron Chemical compound 0.000 claims abstract description 24
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- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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Abstract
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,涉及一种苯并二吡咯酮氟硼荧光染料及其制备方法。
背景技术
近年来,氟硼荧光染料因结构容易修饰以及优异的光物理化学性质如高荧光量子产率、高光稳定性、高摩尔吸光系数等优点,在生物成像、荧光标记、生物传感、光敏剂等研究领域有广泛的应用前景。利用四配位缺电子的硼原子将自由转动的共轭配体通过配位固定,刚化分子结构,增大分子共轭程度,同时降低分子的振动自由度,激发态快速辐射的能力被提升,使得该类分子大多数都表现为荧光显著增强,通过廉价的三氟化硼乙醚制备新型有机二氟化硼荧光染料具有重要的意义,尤其是一些原料廉价易得、工艺简单的制备。
因此,利用廉价易得的商品化原料异吲哚啉酮与吡咯或其衍生物在三氯氧磷下缩合构建不对称二吡咯,在此基础上利用酰氯捕捉该类二吡咯,进而氟硼配位,合成有实用价值的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苯并二吡咯酮氟硼荧光染料及其制备方法,该制备方法简单、反应高效,且制得的荧光染料光谱可调、具有高荧光量子产率和大摩尔吸光系数。
为了实现上述目的,本发明提供了一种苯并二吡咯酮氟硼荧光染料,所述苯并二吡咯酮氟硼荧光染料的结构式为:
其中,R1、R2、R3、R4、R5各自独立为H、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团、卤素、SR6、OR6、NR6R7、NO2、SO3H、(CH2)nCH2SO3H、(CH2)nCH2OH、(CHOH)nCH2OH、(CH2)nCH2Br、(CH2)nCH2(PPh3)Br、(CH2)nCH2(PPh3)I、(CH2)nCH2(NEt3)Br、(CH2)nCH2(NEt3)I、(CH=CH2)(C6H4)R6或(CH=CH2)(C6H4)OR6中的一种;
R6、R7各自独立为H、CH2COOEt、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团中的一种,且n为正整数。
本发明还提供了一种如上述的苯并二吡咯酮氟硼荧光染料的制备方法,所述制备方法包括:
将式(A)所示的异吲哚啉酮、式(B)所示的吡咯或其衍生物、溶剂、路易斯酸混合,进行第一接触反应;之后加入式(C)所示的酰氯,进行第二触反应;然后依次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,本发明提供了一种苯并二吡咯酮氟硼荧光染料及其制备方法,本发明发展了“一锅法”从商品化原料异吲哚啉酮与吡咯或其衍生物在三氯氧磷下缩合后,加入酰氯,进而氟硼配位制备一类结构新颖的苯并二吡咯酮荧光染料;该制备方法为“三步一锅”法,工艺简单,反应高效;所制备的苯并二吡咯酮荧光染料可通过改变R1-R5修饰衍生其结构,光谱可调、具有高达0.91的荧光量子产率、大摩尔吸光系数,最大吸收波长在420-500nm,最大发射光谱在490-640nm,在生物医学和材料科学等领域具有重要的应用前景。
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为苯并二吡咯酮氟硼荧光染料1a的X-射线单晶结构图;
图2为苯并二吡咯酮氟硼荧光染料1c的X-射线单晶结构图;
图3为苯并二吡咯酮氟硼荧光染料1d的X-射线单晶结构图;
图4为苯并二吡咯酮氟硼荧光染料1e的X-射线单晶结构图;
图5为苯并二吡咯酮氟硼荧光染料1f的X-射线单晶结构图。
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。
本发明提供了一种苯并二吡咯酮氟硼荧光染料,所述苯并二吡咯酮氟硼荧光染料的结构式为:
其中,R1、R2、R3、R4、R5各自独立为H、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团、卤素、SR6、OR6、NR6R7、NO2、SO3H、(CH2)nCH2SO3H、(CH2)nCH2OH、(CHOH)nCH2OH、(CH2)nCH2Br、(CH2)nCH2(PPh3)Br、(CH2)nCH2(PPh3)I、(CH2)nCH2(NEt3)Br、(CH2)nCH2(NEt3)I、(CH=CH2)(C6H4)R6或(CH=CH2)(C6H4)OR6中的一种;
R6、R7各自独立为H、CH2COOEt、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团中的一种,且n为正整数。
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荧光染料的荧光量子产率,所述卤素为F、Cl、Br或I中的一种;
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。
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荧光染料的荧光量子产率,R1、R2和R3各自独立为H、C1-C12的直链或支链烷基、C1-C12的直链或者支链环烷基团、Cl、噻吩基团、呋喃基团、苯环基团、OR6、NR6R7、或SR6中的一种;
R6、R7各自独立为H、CH2COOEt、萘基、噻吩基、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团中的一种。
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荧光染料的荧光量子产率,所述R1、R3各自独立为H或甲基,所述R2各自独立为H或乙基,所述R5各自独立为H或C1-C12的直链或支链烷基。
本发明还提供了一种如上述的苯并二吡咯酮氟硼荧光染料的制备方法,所述制备方法包括:
将式(A)所示的异吲哚啉酮、式(B)所示的吡咯或其衍生物、溶剂、路易斯酸混合,进行第一接触反应;之后加入式(C)所示的酰氯,进行第二触反应;然后依次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荧光染料的荧光量子产率,相对于1mmol所述的异吲哚啉酮,所述吡咯或其衍生物的用量为0.5-1.2mmol。
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℃,反应时间为2-100h;
和/或,第二接触反应的条件包括:温度为0-30℃,反应时间为1-100h;
和/或,第三接触反应的条件包括:温度为0-120℃,反应时间为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荧光染料的荧光量子产率,所述路易斯酸选自四氯化钛、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2.0-6.0。
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荧光染料的荧光量子产率,所述溶剂为三氯甲烷、1,2-二氯甲烷、二氯甲烷、甲苯、氯苯、邻二氯苯、对二氯苯、间二氯苯和乙酸乙酯中的一种或多种。
以下将通过实施例对本发明进行详细描述。
实施例1
苯并二吡咯酮氟硼荧光染料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,TLC跟踪点板,在异吲哚啉酮消耗完全后,在冰水浴下用恒压滴液漏斗缓慢滴加溶解在干燥1,2-二氯乙烷稀释的苯甲酰氯(69μL,0.60mmol),室温搅拌2h;然后往反应体系中加入1mL三乙胺,搅拌10min,再次在冰水浴下缓慢加入三氟化硼乙醚2mL,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=2:1),减压旋蒸,得到苯并二吡咯酮氟硼荧光染料1a固体产物,产率为36%(72mg)。
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,CDCl3)δ10.01(s,1H),8.19(d,J=8.1Hz,1H),8.12-8.05(m,3H),7.62-7.58(m,5H),7.47(t,J=7.8Hz,1H),7.36(s,1H),6.51(s,1H);13C NMR(125MHz,CDCl3)δ163.8,143.7,133.7,132.6,131.4,131.2,130.7,129.0,128.9,127.5,126.7,126.1,124.7,122.4,120.6,116.9,112.2.HRMS(APCI)calcd for C19H13BF2N2O[M+H]+:335.1167,found335.1161。
实施例2
苯并二吡咯酮氟硼荧光染料1b的合成:
按照实施例1的方法进行,不同的是,使用更多当量的苯甲酰氯(69μL,1.20mmol),制备1b的产率为25%(82mg)。
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,CDCl3)δ8.12(d,J=6.9Hz,2H),7.97(d,J=8.1Hz,1H),7.79(d,J=7.5Hz,2H),7.64(q,J=8.4Hz,4H),7.49(d,J=6.9Hz,2H),7.41-7.32(m,4H),7.22(d,J=2.1Hz,1H),6.53(t,J=3.3Hz,1H);13C NMR(125MHz,CDCl3)δ168.5,167.9,144.8,133.4,133.3,132.4,130.9,130.3,129.4,129.0,128.4,128.2,126.3,124.1,121.9,120.0,112.8.HRMS(APCI)calcd for C26H18BF2N2O2[M+H]+:439.1429,found 439.1427。
实施例3
苯并二吡咯酮氟硼荧光染料1c的合成:
按照实施例1的方法进行,不同的是,将等当量的苯甲酰氯换成2,4,6-三甲基苯甲酰氯(0.10mL,0.60mmol),制备1c的产率为33%(93mg)。
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,CDCl3)δ9.95(s,1H),8.15(d,J=7.8Hz,1H),7.49-7.36(m,4H),7.16(d,J=7.2Hz,1H),7.00(s,2H),6.49(s,1H),2.36(s,9H);13C NMR(125MHz,CDCl3)δ165.1,144.1,140.6,137.2,133.4,131.4,131.0,129.6,128.8,127.0,126.6,126.1,124.4,122.6,120.3,116.8,112.1,21.3,19.7.HRMS(APCI)calcd for C22H20BF2N2O[M+H]+:377.1637,found 377.1630。
实施例4
苯并二吡咯酮氟硼荧光染料1d的合成:
按照实施例1的方法进行,不同的是,将等当量的苯甲酰氯换成对甲氧基苯甲酰氯(81μL,0.60mmol),制备1d的产率为29%(79mg)。
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,CDCl3)δ9.98(s,1H),8.19(d,J=8.1Hz,1H),8.13-8.05(m,3H),7.60(t,J=7.2Hz,1H),7.46(d,J=7.5Hz,1H),7.32(s,1H),7.23(s,1H),7.10(d,J=9.0Hz,2H),6.50-6.48(m,1H),3.94(s,3H);13C NMR(75MHz,CDCl3)δ163.4,143.4,142.3,133.3,132.4,131.2,130.8,126.3,125.5,124.5,122.9,122.5,120.4,116.1,114.5,114.1,111.9,55.6.HRMS(APCI)calcd for C20H16BF2N2O2[M+H]+:365.1273,found 365.1268。
实施例5
苯并二吡咯酮氟硼荧光染料1e的合成:
按照实施例1的方法进行,不同的是,将等当量的苯甲酰氯换成对硝基苯甲酰氯(111mg,0.60mmol),制备1e的产率为35%(79mg)。
其核磁数据和高分辨质谱数据如下:1H NMR(500MHz,CDCl3)δ10.08(s,1H),8.46(d,J=4.8Hz,2H),8.27(d,J=4.8Hz,3H),8.03(d,J=4.5Hz,1H),7.68(s,1H),7.57(s,1H),7.48(s,1H),7.34(s,1H),6,56(s,1H);13C NMR(125MHz,CDCl3)δ159.1,149.5,145.8,136.7,134.4,131.9,131.2,129.7,129.6,127.8,127.6,125.2,124.2,122.2,120.6,118.5,112.9.HRMS(APCI)calcd for C19H13BF2N3O3[M+H]+:380.1018,found 380.1009。
实施例6
苯并二吡咯酮氟硼荧光染料1f的合成:
按照实施例1的方法进行,不同的是,将吡咯(58μL,0.83mmol)更换为2,4-二甲基吡咯(75μL,0.83mmol),同时将等当量的苯甲酰氯换成对硝基苯甲酰氯(111mg,0.60mmol),制备1f的产率为37%(113mg)。
其核磁数据和高分辨质谱数据如下:1H NMR(300MHz,CDCl3)δ9.43(s,1H),8.43(d,J=8.4Hz,2H),8.25(d,J=8.1Hz,2H),8.08(d,J=8.1Hz,1H),8.01(d,J=7.8Hz,1H),7.64(t,J=7.5Hz,1H),7.49(t,J=7.8Hz,1H),6.09(s,1H),2.49(s,3H),2.41(s,3H);13C NMR(75MHz,CDCl3)δ160.0,157.5,149.2,147.6,138.1,136.8,134.7,131.7,129.8,129.4,127.0,126.7,124.1,120.3,118.9,114.6,107,8,15.0,13.6.HRMS(APCI)calcd forC21H17BF2N3O3[M+H]+:408.1331,found 408.1300。
检测例1
对实施例1-6制得的苯并二吡咯酮氟硼荧光染料进行X-射线单晶衍射表征,具体结果如图1-5所示。
检测例2
将实施例1-6中制得的苯并二吡咯酮氟硼荧光染料1a-f分别在不同的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1-6可知,本发明提供了一种商品化原料异吲哚啉酮与吡咯或其衍生物在三氯氧磷下缩合后,加入酰氯,进而氟硼配位制备一类结构新颖的苯并二吡咯酮荧光染料。该制备方法为“三步一锅”法,工艺简单,反应高效;所制备的苯并二吡咯酮荧光染料可通过改变R1-R5修饰衍生其结构,光谱可调、具有高达0.91的荧光量子产率、大摩尔吸光系数,最大吸收波长在420-500nm,最大发射光谱在490-640nm,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)
1.一种苯并二吡咯酮氟硼荧光染料,其特征在于,所述苯并二吡咯酮氟硼荧光染料的结构式为:
其中,R1、R2、R3、R4、R5各自独立为H、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团、卤素、SR6、OR6、NR6R7、NO2、SO3H、(CH2)nCH2SO3H、(CH2)nCH2OH、(CHOH)nCH2OH、(CH2)nCH2Br、(CH2)nCH2(PPh3)Br、(CH2)nCH2(PPh3)I、(CH2)nCH2(NEt3)Br、(CH2)nCH2(NEt3)I、(CH=CH2)(C6H4)R6或(CH=CH2)(C6H4)OR6中的一种;
R6、R7各自独立为H、CH2COOEt、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团、芳香基团中的一种,且n为正整数。
2.根据权利要求1所述的苯并二吡咯酮氟硼荧光染料,其中,所述卤素为F、Cl、Br或I中的一种;
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.根据权利要求2所述的苯并二吡咯酮氟硼荧光染料,其中,R1、R2和R3各自独立为H、C1-C12的直链或支链烷基、C1-C12的直链或者支链环烷基团、Cl、噻吩基团、呋喃基团、苯环基团、OR6、NR6R7、或SR6中的一种;
R6、R7各自独立为H、CH2COOEt、萘基、噻吩基、C1-C12的直链或者支链烷基、C1-C12的直链或者支链环烷基团中的一种。
4.根据权利要求3所述的苯并二吡咯酮氟硼荧光染料,其中,所述R1、R3各自独立为H或甲基,所述R2各自独立为H或乙基,所述R5各自独立为H或C1-C12的直链或支链烷基。
6.根据权利要求5所述的制备方法,其中,相对于1mmol所述的异吲哚啉酮,所述吡咯或其衍生物的用量为0.5-1.2mmol。
7.根据权利要求5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℃,反应时间为2-100h;
和/或,第二接触反应的条件包括:温度为0-30℃,反应时间为1-100h。
和/或,第三接触反应的条件包括:温度为0-120℃,反应时间为30min-100h。
8.根据权利要求5所述的制备方法,其中,所述路易斯酸选自四氯化钛、三氯氧磷和三溴氧磷中的一种或多种;
9.根据权利要求8所述的制备方法,其中,第一接触反应开始时,体系的pH为2.0-6.0。
10.根据权利要求5所述的制备方法,其中,所述溶剂为三氯甲烷、1,2-二氯甲烷、二氯甲烷、甲苯、氯苯、邻二氯苯、对二氯苯、间二氯苯和乙酸乙酯中的一种或多种。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4122087A (en) * | 1976-03-10 | 1978-10-24 | Imperial Chemical Industries Limited | Benzodipyrrole dyestuffs |
JPH02233684A (ja) * | 1989-03-06 | 1990-09-17 | Nippon Soda Co Ltd | ピリドイミダゾキノキサリン類及びその製造方法 |
CN102702774A (zh) * | 2012-04-11 | 2012-10-03 | 安徽师范大学 | 一类近红外氟硼二吡咯荧光染料及其合成方法 |
CN106479216A (zh) * | 2015-08-27 | 2017-03-08 | 中国科学院武汉物理与数学研究所 | 一种近红外氮杂氟硼二吡咯染料及其微波法合成方法 |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4122087A (en) * | 1976-03-10 | 1978-10-24 | Imperial Chemical Industries Limited | Benzodipyrrole dyestuffs |
JPH02233684A (ja) * | 1989-03-06 | 1990-09-17 | Nippon Soda Co Ltd | ピリドイミダゾキノキサリン類及びその製造方法 |
CN102702774A (zh) * | 2012-04-11 | 2012-10-03 | 安徽师范大学 | 一类近红外氟硼二吡咯荧光染料及其合成方法 |
CN106479216A (zh) * | 2015-08-27 | 2017-03-08 | 中国科学院武汉物理与数学研究所 | 一种近红外氮杂氟硼二吡咯染料及其微波法合成方法 |
Non-Patent Citations (1)
Title |
---|
于长江: "氟硼吡咯类功能染料分子的设计合成及性能研究", 《工程科技I辑》 * |
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