3-Formylpyrazolo[1,5-a]pyrimidines as Key Intermediates for the Preparation of Functional Fluorophores

被引:70
作者
Castillo, Juan-Carlos [1 ,2 ]
Tigreros, Alexis [1 ]
Portilla, Jaime [1 ]
机构
[1] Univ Los Andes, Dept Chem, Bioorgan Cpds Res Grp, Carrera 1 18A-10, Bogota, Colombia
[2] UPTC, Fac Ciencias, Escuela Ciencias Quim, Ave Cent Norte, Tunja, Colombia
关键词
PHOTOLUMINESCENCE QUANTUM YIELD; REGIOSELECTIVE SYNTHESIS; SOLVATOCHROMIC PROPERTIES; FACILE SYNTHESIS; BOND-CLEAVAGE; DISAZO DYES; AMINES; POTENT; RECOGNITION; ALDEHYDES;
D O I
10.1021/acs.joc.8b01571
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A one-pot route for the regioselective synthesis of 3-formylpyrazolo[1,5-a]pyrimidines 4a-k in good yields through a microwave-assisted process is provided. The synthesis proceeds via a cyclocondensation reaction between beta-enaminones 1 with NH-3-aminopyrazoles 2, followed by formylation with an iminium salt moiety (Vilsmeyer-Haack reagent). These N-heteroaryl aldehydes 4 were successfully used as strategic intermediates for the preparation of novel functional fluorophores with yields up to 98%. The structures of the products obtained and regioselectivity of the reactions were determined on the basis of NMR measurements and X-ray diffraction analysis. Since pyrazolo[1,S-a]pyrimidines (PPs) 3 have shown an important fluorescence, photophysical properties of four 2-methylderivatives substituted at position 7 with different acceptor (A) or donor (D) groups were investigated. The compounds evaluated exhibited large Stokes shift in different solvents, but only the substituted p-methoxyphenyl (4-An) showed a strong fluorescence intensity with quantum yields up to 44% due to its greater ICT. Therefore, hybrid systems based on pyrazolo[1,5-a]pyrimidines could be used as fluorescent probes to detect biologically or environmentally relevant species.
引用
收藏
页码:10887 / 10897
页数:11
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