新型取代10H-吡啶并“1，2-α”吲哚高氯酸盐的合成及光谱性质
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摘要
取代10H-吡啶并[1,2-a]吲哚盐是一类良好的光敏染料、荧光增白剂、有机光导体增感剂。研究发现,取代10H-吡啶并[1,2-a]吲哚高氯酸盐的光谱性质与其分子中8-位取代基性质密切相关,在8-位引入具有给电子能力的共轭基团是获得具有较大吸收和发射波长的取代10H-吡啶并[1,2-a]吲哚盐的有效方法。本研究从提高分子的共轭程度入手,在取代吡啶并[1,2-a]吲哚高氯酸盐的8-位引入具有给电子能力更强的杂环:呋喃、噻吩、吲哚、N-乙基咔唑,设计合成了10种取代10H-吡啶并[1,2-a]吲哚高氯酸盐,并讨论了它们的光谱性质。主要研究内容和结果如下:
1.以苯肼和甲基异丙基酮为原料制备2,3,3-三甲基-3H-吲哚,再与高氯酸作用制得其高氯酸盐,然后与巴豆醛经过迈克尔加成、环化、芳构化得到8,10,10-三甲基-10H-吡啶并吲哚高氯酸盐,最后8,10,10-三甲基-10H-吡啶并吲哚高氯酸盐与杂环醛在六氢吡啶的催化下缩合得到10种8-杂环乙烯基-10,10-二甲基-10H-吡啶并[1,2-a]吲哚高氯酸盐(1a~1c、2a~2e、3a~3b),并通过1H NMR、IR和元素分析确证了目标化合物的结构。
2.利用X-射线衍射技术对目标化合物2a~2c的晶体结构进行了表征和解析,结果显示,2a~2c的分子都有较好的平面性,均能形成较大的共轭体系。同时,由于2b、2c中苯基和甲苯基的引入,形成了比2a更大的共轭体系。
3.研究了10个目标化合物在乙腈中的紫外光谱。结果表明,1a~1c、2a~2e、3a~3b的最大吸收波长(1a~1c、2b~2e中λ_(max)~2;2a、3a中λ_(max)~3;3b中λ_(max)~4)随着各个系列中8-位取代基给电子共轭能力的增强发生红移,而且与8-苯乙烯基类似物相比都产生了非常显著的红移,分别红移了94.5 nm、108.5 nm、100.5 nm。另外,对每个目标化合物各个紫外吸收峰的归属也进行了讨论。
4.研究了10个目标化合物在乙腈中的荧光光谱。结果表明,1a~1c、2a~2d、3a~3b的最大发射波长随着各个系列中取代基给电子共轭能力的增强发生红移,荧光强度增大;2e的最大发射波长介于2b和2c之间,荧光强度却在2a~2e中是最大的;10个目标化合物的最大发射波长与8-苯乙烯基类似物相比都产生了非常显著的红移,分别最大红移了111.0 nm、145.0 nm、152.0 nm;1a~1c、2a~2e的荧光量子产率都较小,在0.044~0.069之间,3a、3b的荧光量子产率较大,分别为0.106、0.228,表明二者是较强的荧光化合物。
5.探讨了10个目标化合物在溶剂乙醇、甲醇、乙腈、DMF中的光谱性质变化情况。结果表明:(1)溶剂对1a~1c、2a~2e、3b的紫外光谱性质影响不大。但是3a的最大吸收波长λ_(max)~3随着溶剂的不同却发生了明显变化,3a在乙醇、甲醇、DMF中的λ_(max)~3比在乙腈中的λ_(max)~3分别红移了21.0、12.5、10.5 nm;(2)溶剂对10个目标化合物荧光光谱性质影响不大。
Substituted 10H-pyrido[1,2-a]indolium perchlorates can be used as photosensitive dyes, fluorescent whiteners and organic light-guide sensitizers. On the basis of the study of synthesis and spectral property about many compounds of this series, it is found that the conjugated substituents introduced at 8-position make the maximum absorption(λ_(max)) and maxium emission(λ_(em)) red shift significantly. To obtain the compound with a largerλ_(max) andλ_(em), herein, we introduced furan, thiophene, indole, N-ethylcarbazole with stronger electron-donating conjugation capability into 8-position and synthesized the target compounds. In view of this, ten of novel substituted 10H-pyrido[1,2-a]indolium perchlorates were designed and synthesized, and their spectral properties were investigated. Main work and results were listed as follows:
1. Ten novel 8-heterocyclic vinyl-10,10-dimethyl-10H-pyrido[1,2-a]indolium perchlorates (1a~1c, 2a~2e, 3a~3b) were synthesized by phenylhydrazine and 3-methylbutanone (starting materials) in multi-steps. Structures of target compounds were confirmed by ~1H NMR, IR and elemental analysis.
2. Compounds 2a~2c were characterized and analyzed by X-ray diffraction. Crystal Structure analysis indicated that the moleculars of 2a~2c were coplanar, respectively, meanwhile, there was a larger conjugated system in 2b and 2c owing to the introduction of phenyl and tolyl group.
3. The UV-vis spectrum of ten target compounds were investigated. The results indicated that, with the electron-donating conjugation capability of the substituting group in 8-position being enhanced in each series, the maximum absorption(λ_(max)~2 in 1a~1c, 2b~2e;λ_(max)~3 in 2a, 3a;λ_(max)~4 in 3b) of 1a~1c, 2a~2e, 3a~3b had a red-shift, while they red shifted 94.5 nm, 108.5 nm, 100.5 nm in maximum, respectively, in comparison with 8-styryl analog. The absorption bands in UV-Vis spectrum of the ten title compounds were also allocated.
4. The fluorencence spectrum of ten target compounds were investigated. The results indicated that, with the electron-donating conjugation capability of the substituting group in 8-position being enhanced in each series, the maxium emission(λ_(em)) of 1a~1c, 2a~2d, 3a~3b had a red-shift, and the fluorescence intensity was also increasing;λ_(em) of 2e was between 2b and 2c, while the fluorescence intensity was strongest in 2a~2e.λ_(em) of 1a~1c, 2a~2d, 3a~3b red shifted 111.0 nm, 145.0 nm, 152.0 nm in maximum, respectively, in comparison with 8-styryl analog. The fluorencence quantum yield of 1a~1c、2a~2e was small, which was between 0.044 and 0.069, however, the fluorencence quantum yield 3a and 3b were 0.106 and 0.228, respectively. It indicated that 3a and 3b can be used as fluorescent acridine compounds, and have a certain application value in analysis.
5. The absorbtion and emission spectrum in methanol, ethanol, acetonitrile, DMF were studied. The solvent had no obvious effects on the absorbtion spectrum of 1a~1c, 2a~2e and 3b. However, the maximum absorption (λ_(max)~3) of 3a in methanol, ethanol and DMF red shifted 21.0 nm, 12.5 nm and 10.5 nm in comparison with 3a in acetonitrile, respectively. The solvent had no obvious effects on the emission spectrum of ten target compounds.
1.以苯肼和甲基异丙基酮为原料制备2,3,3-三甲基-3H-吲哚,再与高氯酸作用制得其高氯酸盐,然后与巴豆醛经过迈克尔加成、环化、芳构化得到8,10,10-三甲基-10H-吡啶并吲哚高氯酸盐,最后8,10,10-三甲基-10H-吡啶并吲哚高氯酸盐与杂环醛在六氢吡啶的催化下缩合得到10种8-杂环乙烯基-10,10-二甲基-10H-吡啶并[1,2-a]吲哚高氯酸盐(1a~1c、2a~2e、3a~3b),并通过1H NMR、IR和元素分析确证了目标化合物的结构。
2.利用X-射线衍射技术对目标化合物2a~2c的晶体结构进行了表征和解析,结果显示,2a~2c的分子都有较好的平面性,均能形成较大的共轭体系。同时,由于2b、2c中苯基和甲苯基的引入,形成了比2a更大的共轭体系。
3.研究了10个目标化合物在乙腈中的紫外光谱。结果表明,1a~1c、2a~2e、3a~3b的最大吸收波长(1a~1c、2b~2e中λ_(max)~2;2a、3a中λ_(max)~3;3b中λ_(max)~4)随着各个系列中8-位取代基给电子共轭能力的增强发生红移,而且与8-苯乙烯基类似物相比都产生了非常显著的红移,分别红移了94.5 nm、108.5 nm、100.5 nm。另外,对每个目标化合物各个紫外吸收峰的归属也进行了讨论。
4.研究了10个目标化合物在乙腈中的荧光光谱。结果表明,1a~1c、2a~2d、3a~3b的最大发射波长随着各个系列中取代基给电子共轭能力的增强发生红移,荧光强度增大;2e的最大发射波长介于2b和2c之间,荧光强度却在2a~2e中是最大的;10个目标化合物的最大发射波长与8-苯乙烯基类似物相比都产生了非常显著的红移,分别最大红移了111.0 nm、145.0 nm、152.0 nm;1a~1c、2a~2e的荧光量子产率都较小,在0.044~0.069之间,3a、3b的荧光量子产率较大,分别为0.106、0.228,表明二者是较强的荧光化合物。
5.探讨了10个目标化合物在溶剂乙醇、甲醇、乙腈、DMF中的光谱性质变化情况。结果表明:(1)溶剂对1a~1c、2a~2e、3b的紫外光谱性质影响不大。但是3a的最大吸收波长λ_(max)~3随着溶剂的不同却发生了明显变化,3a在乙醇、甲醇、DMF中的λ_(max)~3比在乙腈中的λ_(max)~3分别红移了21.0、12.5、10.5 nm;(2)溶剂对10个目标化合物荧光光谱性质影响不大。
Substituted 10H-pyrido[1,2-a]indolium perchlorates can be used as photosensitive dyes, fluorescent whiteners and organic light-guide sensitizers. On the basis of the study of synthesis and spectral property about many compounds of this series, it is found that the conjugated substituents introduced at 8-position make the maximum absorption(λ_(max)) and maxium emission(λ_(em)) red shift significantly. To obtain the compound with a largerλ_(max) andλ_(em), herein, we introduced furan, thiophene, indole, N-ethylcarbazole with stronger electron-donating conjugation capability into 8-position and synthesized the target compounds. In view of this, ten of novel substituted 10H-pyrido[1,2-a]indolium perchlorates were designed and synthesized, and their spectral properties were investigated. Main work and results were listed as follows:
1. Ten novel 8-heterocyclic vinyl-10,10-dimethyl-10H-pyrido[1,2-a]indolium perchlorates (1a~1c, 2a~2e, 3a~3b) were synthesized by phenylhydrazine and 3-methylbutanone (starting materials) in multi-steps. Structures of target compounds were confirmed by ~1H NMR, IR and elemental analysis.
2. Compounds 2a~2c were characterized and analyzed by X-ray diffraction. Crystal Structure analysis indicated that the moleculars of 2a~2c were coplanar, respectively, meanwhile, there was a larger conjugated system in 2b and 2c owing to the introduction of phenyl and tolyl group.
3. The UV-vis spectrum of ten target compounds were investigated. The results indicated that, with the electron-donating conjugation capability of the substituting group in 8-position being enhanced in each series, the maximum absorption(λ_(max)~2 in 1a~1c, 2b~2e;λ_(max)~3 in 2a, 3a;λ_(max)~4 in 3b) of 1a~1c, 2a~2e, 3a~3b had a red-shift, while they red shifted 94.5 nm, 108.5 nm, 100.5 nm in maximum, respectively, in comparison with 8-styryl analog. The absorption bands in UV-Vis spectrum of the ten title compounds were also allocated.
4. The fluorencence spectrum of ten target compounds were investigated. The results indicated that, with the electron-donating conjugation capability of the substituting group in 8-position being enhanced in each series, the maxium emission(λ_(em)) of 1a~1c, 2a~2d, 3a~3b had a red-shift, and the fluorescence intensity was also increasing;λ_(em) of 2e was between 2b and 2c, while the fluorescence intensity was strongest in 2a~2e.λ_(em) of 1a~1c, 2a~2d, 3a~3b red shifted 111.0 nm, 145.0 nm, 152.0 nm in maximum, respectively, in comparison with 8-styryl analog. The fluorencence quantum yield of 1a~1c、2a~2e was small, which was between 0.044 and 0.069, however, the fluorencence quantum yield 3a and 3b were 0.106 and 0.228, respectively. It indicated that 3a and 3b can be used as fluorescent acridine compounds, and have a certain application value in analysis.
5. The absorbtion and emission spectrum in methanol, ethanol, acetonitrile, DMF were studied. The solvent had no obvious effects on the absorbtion spectrum of 1a~1c, 2a~2e and 3b. However, the maximum absorption (λ_(max)~3) of 3a in methanol, ethanol and DMF red shifted 21.0 nm, 12.5 nm and 10.5 nm in comparison with 3a in acetonitrile, respectively. The solvent had no obvious effects on the emission spectrum of ten target compounds.
引文
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