CN112479989A - 同侧湾位双识别基团的苝系衍生物与制备方法及其应用 - Google Patents
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Abstract
本发明公开了同侧湾位双识别基团的苝系衍生物与制备方法及其应用，具有通式(I)或(II)所示的化学结构，
式中，其中R1为不多于8个碳原子的烃基；R2为不多于8个碳原子的烃基；R3为不多于12个碳原子的烃基；R4为不多于12个碳原子的烃基；R5为不多于12个碳原子的烃基；R6为不多于12个碳原子的烃基。本发明提供的化合物在湾位同侧同时连接羟基及希夫碱的类联吡啶结构，通过二者对铜(II)离子的分别识别作用及空间协同识别作用，成为荧光增强型比率荧光分子探针，用于铜(II)离子的荧光法检测。
Description
技术领域
本发明涉及同侧湾位双识别基团的苝系`衍生物与制备方法及其应用，属于有机合成技术领域。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
苝类稠环芳烃是有强烈荧光的芳香烃化合物，具有大的共轭π体系。苝系衍生物被认为是一个封闭的发色团，荧光量子产率几乎是定量的，且产率和寿命不受氧的影响；还对从可见区到红外区的光有很强的吸收。苝系衍生物是缺电子体系，非常容易被还原，而难以被氧化，其缺电子特征也是它具有高度光稳定性的一个先决条件。苝系衍生物具有优异的化学、热和光化学稳定性，是一类性能特异的分子电子学材料，在荧光探针分子领域有很好的应用前景。
铜(II)离子是人体内第三大含量的过渡金属，其含量水平直接关系着身体组织的功能和代谢的进程。在生物生命过程中扮演着十分重要的角色，是生命活动的必需微量元素，环境中铜(II)离子的含量的多少，是环境检测中的重要指标之一。因此，如何简单、快速、高效地对生命过程中铜(II)离子含量的检测也就成为铜(II)离子检测领域研究的热点。
发明内容
为了解决现有技术的不足，本发明的目的是提供同侧湾位双识别基团的苝系衍生物与制备方法及其应用，这类化合物在湾位同侧的双识别基团具有协同空间识别作用，能够作为一种比色法检测的荧光增强型的比率探针。
本发明采用的技术方案如下：
一方面，一种同侧湾位双识别基团的苝系衍生物，具有通式(I)或(II)所示的化学结构，
式中，其中R1为不多于8个碳原子的烃基；R2为不多于8个碳原子的烃基；R3为不多于12个碳原子的烃基；R4为不多于12个碳原子的烃基；R5为不多于12个碳原子的烃基；R6为不多于12个碳原子的烃基。
另一方面，一种上述同侧湾位双识别基团的苝系衍生物的制备方法，包括如下步骤：
对1-NO2-3,4,9,10-苝四羧酸类化合物的1位硝基进行还原及12位的氢进行羟基化反应获得1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物；
将1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物与2-吡啶酮类化合物进行席夫碱反应获得所述同侧湾位双识别基团的苝系衍生物；
1-NO2-3,4,9,10-苝四羧酸类化合物为1-NO2-3,4,9,10-苝四羧酸四酯或1-NO2-3,4,9,10-苝四羧酸二酰亚胺；
1-NO2-3,4,9,10-苝四羧酸四酯的化学结构式为
1-NO2-3,4,9,10-苝四羧酸二酰亚胺的化学结构式为
2-吡啶酮类化合物的化学结构式为
其中，R1～R6如上述所定义。
第三方面，一种上述同侧湾位双识别基团的苝系衍生物在二价铜离子检测中的应用。
第四方面，一种检测二价铜离子的方法，将上述同侧湾位双识别基团的苝系衍生物与待测含有二价铜离子的样品混合，对混合后的溶液进行荧光检测。
本发明的有益效果为：
(1)本发明提供同侧湾位双识别基团的苝系衍生物的湾位同侧同时连接羟基及希夫碱的类联吡啶结构，二者对铜(II)离子具有分别识别作用，还有空间协同识别作用。
(2)荧光探针法具有灵敏度高、快速便捷、可视化和原位无损检测等优点，但铜(II)离子的顺磁特性常使荧光母体分子发生荧光猝灭，本发明提供的同侧湾位双识别基团的苝系衍生物是一种荧光增强型的比率探针。
(3)本发明提供的同侧湾位双识别基团的苝系衍生物，由于分子平面性提高使得其可见光吸收发生了较大红移，便于降低生物组织检测的背景干扰，实验研究表明所述化合物还可用于铜(II)的比色法检测，提高了检测效果。
其空间协同识别作用表现为，相对于对比结构，1、呈现出荧光比率探针的特征；2、结合比由对比结构多数情况下的2：1降为1：1。见下图：
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为本发明的实施例1中化合物1的核磁氢谱；
图2为本发明实施例1中的化合物1的碳谱；
图3为本发明的实施例1中的化合物1的质谱；
图4为本发明的实施例1中的化合物1的荧光表征图，A为滴定图，B为比率曲线；
图5为本发明的实施例2中化合物2的核磁氢谱；
图6为本发明的实施例2中化合物2的碳谱；
图7为本发明的实施例2中的产品2的质谱；
图8为本发明的实施例2中的产品2的荧光滴定图，A为滴定图，B为比率曲线；
图9为对比结构1的荧光表征图，插图为波长606nm处的荧光曲线；
图10为对比结构2的荧光表征图，插图为波长521nm处的荧光曲线；
图11为对比结构3的荧光表征图，插图为波长571nm处的荧光曲线；
图12为对比结构4的荧光表征图，插图为波长582nm处的荧光曲线。
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、器件、组件和/或它们的组合。
本发明提出了同侧湾位双识别基团的苝系衍生物与制备方法及其应用。
本发明的一种典型实施方式，提供了一种同侧湾位双识别基团的苝系衍生物，具有通式(I)或(II)所示的化学结构，
式中，其中R1为不多于8个碳原子的烃基；R2为不多于8个碳原子的烃基；R3为不多于12个碳原子的烃基；R4为不多于12个碳原子的烃基；R5为不多于12个碳原子的烃基；R6为不多于12个碳原子的烃基。
本发明的另一种实施方式，提供了一种上述同侧湾位双识别基团的苝系衍生物的制备方法，包括如下步骤：
对1-NO2-3,4,9,10-苝四羧酸类化合物的1位硝基进行还原及12位的氢进行羟基化反应获得1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物；
将1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物与2-吡啶酮类化合物进行席夫碱反应获得所述同侧湾位双识别基团的苝系衍生物；
1-NO2-3,4,9,10-苝四羧酸类化合物为1-NO2-3,4,9,10-苝四羧酸四酯或1-NO2-3,4,9,10-苝四羧酸二酰亚胺；
1-NO2-3,4,9,10-苝四羧酸四酯的化学结构式为
1-NO2-3,4,9,10-苝四羧酸二酰亚胺的化学结构式为
2-吡啶酮类化合物的化学结构式为
其中，R1～R6如上述所定义。
其反应过程为：
1-NO2-3,4,9,10-苝四羧酸类化合物参考专利(ZL2015100460461)报道方法合成。
该实施方式的一些实施例中，1-NO2-3,4,9,10-苝四羧酸类化合物制备1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物的过程为：向1-NO2-3,4,9,10-苝四羧酸类化合物的溶液中添加锌粉和氯化铵进行反应获得。
该实施方式的一些实施例中，1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物的纯化过程为柱色谱层析。采用二氯甲烷与乙酸乙酯的体积比为9～11:1的混合液作为淋洗液。
该实施方式的一些实施例中，席夫碱反应的溶剂为甲醇或乙醇。
该实施方式的一些实施例中，席夫碱反应的催化剂为甲酸或乙酸。
该实施方式的一些实施例中，席夫碱反应的条件为加热回流。回流时间为24～48h。
该实施方式的一些实施例中，1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物与2-吡啶酮类化合物的摩尔比为1:1～20。
该实施方式的一些实施例中，同侧湾位双识别基团的苝系衍生物的纯化过程为柱色谱层析。采用二氯甲烷与乙酸乙酯的体积比为19～21:1的混合液作为淋洗液。
本发明的第三种实施方式，提供了一种上述同侧湾位双识别基团的苝系衍生物在二价铜离子检测中的应用。
本发明的第四种实施方式，提供了一种检测二价铜离子的方法，将上述同侧湾位双识别基团的苝系衍生物与待测含有二价铜离子的样品混合，对混合后的溶液进行荧光检测。
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。
以下实施例中所述1-硝基-苝四羧酸四酯及1-硝基-苝四羧酸二酰亚胺参考专利(ZL2015100460461)报道方法合成。
以下实施例中同侧湾位双识别基团的苝系衍生物的分子式：
对比结构1～4的分子式如下：
实施例1
将320mg 1-硝基-3,4:9,10-苝四羧酸正丁酯溶于THF中，加入300mg处理过的锌粉、200mg氯化铵，常温下反应，TLC跟踪反应进程。反应结束后，过滤得滤液，除去溶剂，得到粗产品。粗产品进行柱色谱层析，淋洗液为二氯甲烷：乙酸乙酯＝10:1，除去溶剂，真空干燥，得到1-氨基-12-羟基-3,4:9,10-苝四羧酸正丁酯。将200mg1-氨基-12-羟基-3,4:9,10-苝四羧酸正丁酯溶于甲醇中，加入催化量甲酸，0.5ml 2-乙酰吡啶,回流反应48小时。去除溶剂，粗产品进行柱色谱层析，淋洗液为二氯甲烷：乙酸乙酯＝25:1，得到最终产物1,产率约为55％。
1H-NMR(400MHz,CDCl3:D-dmso＝50:1,δppm)δ:8.65(1H,d,J＝7.0Hz),8.00(1H,m),7.92(1H,d,J＝8.0Hz),7.85(1H,d,J＝8.0Hz),7.79(1H,m),7.74(1H,s),7.62(1H,s),7.50(1H,d,J＝8.1Hz),7.47-7.39(1H,m),7.31(2H,d,J＝8.1Hz),4.43-4.31(4H,m),4.18(4H,m),2.72(3H,s),1.88-1.72(8H,m),1.59-1.44(8H,m),1.08-0.96(12H,m).如图1所示。
13C-NMR(400MHz,CDCl3:D-dmso＝50:1,δppm)δ:200.23,169.28,168.99,168.30,168.21,153.43,152.35,148.94,136.82,135.74,131.51,129.50,127.77,127.18,126.72,123.69,121.61,120.57,116.03,77.45,77.33,77.13,76.81,65.64,65.31,53.46,37.06,30.52,29.32,25.72,20.52,19.30,14.38,13.79.如图2所示。
MS:calcd.for C47H49N2O9(M-1):785.3456,found:785.3430.如图3所示。
产物1对铜(II)离子的识别采用荧光滴定的方法测试。所使用为物质量浓度为1×10-5mol·L-1的二氯甲烷溶液测试，铜(II)离子的来源采用的是硝酸铜。加入的量如图4所示，其中每一个Equiv表示加入硝酸铜的浓度为10-5mol·L-1。由图4可以看出产物1的荧光谱图有两个发射峰，分别在525nm和595nm，在加入铜离子后，595nm处的发射峰逐渐降低，在522nm处的发射峰逐渐升高，在1equiv时即达到饱和。
实施例2
将300mg 1-硝基-3,4:9,10-苝四羧酸二酰亚胺溶于THF中，加入280mg处理过的锌粉、210mg氯化铵，常温下反应，TLC跟踪反应进程。反应结束后，过滤得滤液，除去溶剂，得到粗产品。粗产品进行柱色谱层析，淋洗液为二氯甲烷：乙酸乙酯＝10:1，除去溶剂，真空干燥，得到1-氨基-12-羟基-3,4:9,10-苝四羧酸二酰亚胺。将220mg1-氨基-12-羟基-3,4:9,10-苝四羧酸二酰亚胺溶于甲醇中，加入催化量甲酸，0.5ml 2-乙酰吡啶,回流反应48小时。去除溶剂，粗产品进行柱色谱层析，淋洗液为二氯甲烷：乙酸乙酯＝20:1，得到最终产物2,产率约为57％。
1H-NMR(400MHz,CDCl3,δppm)δ：10.91(1H,s),9.41(1H,s),8.97(1H,d,J＝8Hz),8.70(2H,m),8.57(4H,m),8.44(1H,d,J＝7Hz),8.03(1H,m),7.62(1H,m),5.12-4.98(2H,m),2.64-2.50(3H,m),1.97-1.87(4H,m),1.82-1.70(6H,m),1.65-1.54(3H,m),1.53-1.40(4H,m),1.33(3H,s).如图5所示。
13C-NMR(400MHz,CDCl3,δppm)δ:164.00,163.93,163.79,163.26,162.19,149.13,148.47,138.21,134.49,134.12,131.25,129.96,129.31,129.20,127.91,127.21,127.15,126.77,126.26,125.23,124.22,123.75,123.43,123.24,122.60,54.03,29.71,29.05,26.56,25.56.如图6所示。
MS:calcd.for C43H35N4O5(M-1):687.2626found:687.2606.如图7所示。
产物2对铜(II)离子的识别采用荧光滴定的方法测试。所使用为物质量浓度为1×10-5mol·L-1的二氯甲烷溶液测试，铜(II)离子的来源采用的是硝酸铜。加入的量如图8所示，其中每一个Equiv表示加入硝酸铜的浓度为10-5mol·L-1。由图8可以看出产物2的荧光谱图有两个发射峰，分别在514nm和608nm，在加入铜离子后，608nm处的发射峰逐渐降低，在514nm处的发射峰逐渐升高，在1equiv时即达到饱和。
对比结构1的铜离子荧光滴定曲线，如图9所示，对比结构1最大发射波长为608nm随着铜离子的加入，荧光发生了猝灭，当铜离子加到约2当量时，达到饱和状态，并且荧光强度下降到1/3。
对比结构2的铜离子荧光滴定曲线，如图10所示，对比结构2最大发射波长为521nm随着铜离子的加入，荧光发生了猝灭，当铜离子加到约1当量时，达到饱和状态，并且荧光强度下降到原来的1/4。
通过图4、9、10的对比可以表明本发明制备的产物1具有荧光比率探针的特征，同时结合比降为1:1，证明产物1同侧湾位双识别基团能够产生空间协同识别。
对比结构3的铜离子荧光滴定曲线，如图11所示，对比结构3最大发射波长为571nm,此外还有一个肩峰，随着铜离子的加入，荧光强度逐渐增加，当铜离子加到2当量时，达到饱和状态，最大峰增加了约2.6倍。
对比结构4的铜离子荧光滴定曲线，如图12所示，对比结构4最大发射波长为582nm，随着铜离子的加入，荧光逐渐猝灭；当铜离子加到约2当量时，达到饱和状态，荧光强度是原来的1/3。
通过图8、11、12的对比可以表明本发明制备的产物2具有荧光比率探针的特征，同时结合比变为1:1，证明产物2同侧湾位双识别基团能够产生空间协同识别。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种同侧湾位双识别基团的苝系衍生物，其特征是，具有通式(I)或(II)所示的化学结构，
式中，其中R1为不多于8个碳原子的烃基；R2为不多于8个碳原子的烃基；R3为不多于12个碳原子的烃基；R4为不多于12个碳原子的烃基；R5为不多于12个碳原子的烃基；R6为不多于12个碳原子的烃基。
2.一种权利要求1所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，包括如下步骤：
对1-NO2-3,4,9,10-苝四羧酸类化合物的1位硝基进行还原及12位的氢进行羟基化反应获得1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物；
将1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物与2-吡啶酮类化合物进行席夫碱反应获得所述同侧湾位双识别基团的苝系衍生物；
1-NO2-3,4,9,10-苝四羧酸类化合物为1-NO2-3,4,9,10-苝四羧酸四酯或1-NO2-3,4,9,10-苝四羧酸二酰亚胺；
1-NO2-3,4,9,10-苝四羧酸四酯的化学结构式为
1-NO2-3,4,9,10-苝四羧酸二酰亚胺的化学结构式为
2-吡啶酮类化合物的化学结构式为
其中，R1～R6如权利要求1所定义。
3.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，1-NO2-3,4,9,10-苝四羧酸类化合物制备1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物的过程为：向1-NO2-3,4,9,10-苝四羧酸类化合物的溶液中添加锌粉和氯化铵进行反应获得。
4.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，席夫碱反应的溶剂为甲醇或乙醇。
5.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，席夫碱反应的催化剂为乙酸。
6.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，席夫碱反应的条件为加热回流。
7.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，1-NH2-12-OH-3,4,9,10-苝四羧酸类化合物与2-吡啶酮类化合物的摩尔比为1:1～20。
8.如权利要求2所述的同侧湾位双识别基团的苝系衍生物的制备方法，其特征是，同侧湾位双识别基团的苝系衍生物的纯化过程为柱色谱层析。
9.一种权利要求1所述的同侧湾位双识别基团的苝系衍生物在二价铜离子检测中的应用。
10.一种检测二价铜离子的方法，其特征是，将权利要求1所述的同侧湾位双识别基团的苝系衍生物与待测含有二价铜离子的样品混合，对混合后的溶液进行荧光检测。
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