中氮茚衍生物合成及表征的综合化学实验
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摘要
以氯乙酸乙酯和喹啉为原料,一锅法合成了一种水溶性中氮茚衍生物,用高分辨质谱、~1HNMR、~(13)CNMR和二维~1H-~(13)C HSQC等技术表征了衍生物的结构,推测了衍生物的形成机理。结果表明,此化合物为氯乙酸乙酯喹啉季铵盐的二聚体衍生物,是喹啉叶立德与喹啉季铵盐通过1,3-偶极加成形成的中氮茚类衍生物。该实验项目可作为化学类专业大二或大三年级学生的综合化学实验项目。
By using the ethyl chloroacetate and quinoline as raw materials,a water-soluble nitrogen and indolizine derivative is synthesized by the one-pot method.The structure of the derivative is characterized by the technologies such as the high-resolution mass spectrometry,~1 HNMR,~(13) CNMR,two-dimensional ~1 H-~(13)C HSQC,etc.,and the formation mechanism of the derivative is deduced.The results show that this compound is a two-polymer derivative of the quaternary ammonium salt of the ethyl chloroacetate and quinolone,and it is the indolizine derivative formed by the quinolinium ylide and quinoline quaternary ammonium salt through 1,3-dipolar cycloaddition.This experiment can be used as a comprehensive chemical experiment project for the second-year or third-year students majoring in chemistry.
By using the ethyl chloroacetate and quinoline as raw materials,a water-soluble nitrogen and indolizine derivative is synthesized by the one-pot method.The structure of the derivative is characterized by the technologies such as the high-resolution mass spectrometry,~1 HNMR,~(13) CNMR,two-dimensional ~1 H-~(13)C HSQC,etc.,and the formation mechanism of the derivative is deduced.The results show that this compound is a two-polymer derivative of the quaternary ammonium salt of the ethyl chloroacetate and quinolone,and it is the indolizine derivative formed by the quinolinium ylide and quinoline quaternary ammonium salt through 1,3-dipolar cycloaddition.This experiment can be used as a comprehensive chemical experiment project for the second-year or third-year students majoring in chemistry.
引文
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[2]周璐珊,张文雄.化学类本科综合化学实验教学的实践与思考[J].化学通报,2012,75(3):279-283.
[3]罗娅君,胡晓黎,李松,等.探索综合化学实验,培养学生综合创新能力[J].实验室研究与探索,2011,30(11):100-102.
[4]吕梅香,汪朝阳,何广平,等.综合化学实验教学改革与实践[J].实验室研究与探索,2010,29(4):112-114.
[5]陈伟,柏正武.纤维素型手性固定相制备及手性分离综合实验设计[J].实验技术与管理,2017,34(5):44-47.
[6]孙二军,刘阳,宋哲,等.“卟啉化合物的合成、表征及性质研究”综合化学实验设计[J].长春师范学院学报(自然科学版),2013,32(2):118-121.
[7]刘士荣,杨兆昆,陈明清.基于科教融合的综合化学实验设计[J].实验技术与管理,2017,34(1):168-171.
[8]牛焕双,李宇,杜林,等.科研实验转化成综合化学教学实验的探索[J].实验室研究与探索,2014,33(2):150-154.
[9]郑云香,王向鹏,燕玉峰,等.喹啉型双季铵盐酸化缓蚀剂的合成与性能评价[J].腐蚀与防护,2015,36(1):14-18.
[10]战风涛,杨震,吕志凤,等.高效缓蚀剂氯化苄基喹啉衍生物制备与表征[J].石油学报,2015,36(9):1116-1121.
[11]Singh G S,Mmatli E E.Recent progress in synthesis and bioactivity studies of indolizines[J].Eur J Med Chem,2011,46(11):5237-5257.
[12]Beghyn T,Deprez-Poulain R,Willand N,et al.Natural compounds:leads or ideas?Bioinspired molecules for drug discovery[J].Chem Biol Drug Des,2008,72(1):3-15.
[13]孔伟伟,江玉亮,韩巧荣,等.新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为[J].高等学校化学学报,2015,36(2):287-292.
[14]Katritzky A R,Qiu Guofang,Yang Baozhen,et al.Novel syntheses of indolizines and pyrrolo[2,1-a]isoquinolines via benzotriazole methodology[J].J Org Chem,1999,64(20):7618-7621.
[15]Allgauer D S,Mayr H.One-pot two-step synthesis of 1-(ethoxycarbonyl)indolizines via pyridinium ylides[J].Eur J Org Chem,2013(28):6379-6388.
[16]Allgauer D S,Mayer P,Mayr H.Nucleophilicity parameters of pyridinium ylides and their use in mechanistic analyses[J].J Am Chem Soc,2013,135(40):15216-15224.