三联噻吩-异噁唑、吡唑啉类化合物的合成与光活化性能研究
收稿日期: 2013-08-06
修回日期: 2013-09-29
网络出版日期: 2013-10-11
基金资助
国家自然科学基金（No.21105030）和华南农业大学211三期建设（No.2009B010100001）资助项目.
Synthesis and Phototoxic Activity of Isoxazole and Pyrazoline Derivatives Containing α-Terthiophene
Received date: 2013-08-06
Revised date: 2013-09-29
Online published: 2013-10-11
Supported by
Project supported by the National Natural Science Foundation of China (No. 21105030) and the Key Academic Program of 211 Project of South China Agricultural University (No. 2009B010100001).
α-三联噻吩（a-T）是一类具有优异性能的光活化农药. 以三联噻吩为先导化合物，经a醛基化制得关键中间体2-醛基三联噻吩，然后与取代苯乙酮反应，得到三联噻吩取代的α，β-不饱和酮，再与盐酸羟胺、水合肼关环，最终合成两类含3，5-二芳基异噁唑和3，5-二芳基吡唑啉的α-三联噻吩衍生物. 其结构经1H NMR，IR和元素分析确证. 初步生物活性测定试验表明，绝大多数目标化合物具有良好的光活化活性，异噁唑类衍生物的光活化活性普遍要好于吡唑啉类衍生物，其中化合物3b光照前后的细胞毒杀活性差异为64.06倍. 但部分吡唑啉类衍生物整体显示出较高的细胞毒杀活性，其中化合物4d光照细胞毒杀活性为83.9%.
罗志刚 , 刘正勇 , 张广龙 , 叶杰欣 , 杨卓鸿 . 三联噻吩-异噁唑、吡唑啉类化合物的合成与光活化性能研究[J]. 有机化学, 2014 , 34(2) : 392 -397 . DOI: 10.6023/cjoc201308008
α-Terthiophene is a class of pesticides with predominant photoactivity. In this work, using terthiophene as the lead compound, the important mediator, 2-carbonyl terthiophene, was synthesized by the carbonylation. After reaction with substituted phenylethanone, terthiophene-substituted α,β-unsaturated ketones were synthesized. Followed by the ring closure reaction with hydroxylamine hydrochloride and hydrazine, a series of 3,5-diaryl isoxazole and 3,5-diaryl pyrazoline drivatives containing α-terthiophene were synthesized, respectively. Their structures were confirmed by 1H NMR, IR and elemental analysis. The biological activity assay indicated that most of the synthesized compounds exhibit strong photoactivities. In addition, the photoactivities of isoxazole derivatives were much better than those of pyrazoline derivatives, where the photoactivity difference of compound 3b was 64.06 before and after illumination, especially. However, some of the pyrazoline derivatives showed higher activities of killing cells, where the activity of the compound 4d was as high as 83.9%.
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