以丹皮酚为前体催化合成一氯查尔酮及黄酮  

Catalytic synthesis of monochlorchalone and flavone with paeonol as precursor

作　　者：安超娜 王乙颖 刘萌 邹肖 刘存芳[1] 田光辉[1] AN Chaona;WANG Yiying;LIU Meng;ZOU Xiao;LIU Cunfang;TIAN Guanghui(Shaanxi Key Laboratory for Catalysis,Shaanxi University of Technology,Hanzhong 723000,Shaanxi,China)

机构地区：[1]陕西理工大学陕西省催化基础与应用重点实验室,陕西汉中723000

出　　处：《精细化工》2023年第7期1618-1624,共7页Fine Chemicals

基　　金：国家级大学生创新创业训练计划项目(202210720017);陕西省科技厅社会发展科技攻关项目(2021SF-382);2022年研究生创新基金项目(SLGYCX2227)。

摘　　要：以丹皮酚为起始原料,与不同取代位次的一氯苯甲醛在碱催化下通过Claisen-Schmidt反应合成一氯查尔酮(Ⅲa~Ⅲc),再将其进行碘催化关环反应合成一氯黄酮(Ⅳa~Ⅳc),产率分别为88.6%、87.7%、86.1%。以合成(E)-3-(2-氯苯基)-1-(2-羟基-4-甲氧基苯基)丙-2-烯-1-酮(Ⅲa)为例,通过单因素实验和响应面法考察碱、温度、溶剂量对Ⅲa产率的影响,得到最佳合成条件为:一氯苯甲醛3.6 mmol、丹皮酚3 mmol、无水乙醇15 mL、NaOH 0.239 g(6 mmol)、70℃下回流10 h,在该条件下Ⅲa、Ⅲb、Ⅲc平均产率分别为93.7%、92.3%和92.1%。通过1HNMR、13CNMR、135°DEPT(无畸变极化转移技术)、FTIR确定产物的结构,并测试其紫外和荧光性能。Ⅳa~Ⅳc在波长375.8、377.6和376.8 nm处荧光强度分别为421.0、555.0、611.4 a.u.。将原料量放大5、10倍的实验中,Ⅲa~Ⅲc的产率为90.1%~93.7%,Ⅳa~Ⅳc的产率为84.7%~88.9%。Chlorinated chalconesⅢa~Ⅲc were synthesized via Claisen-Schmidt condensation reaction of paeonol and chlorinated benzaldehydes with different substituent sites in presence of alkali catalyst,and then further iodine-catalyzed for synthesis of flavonoidsⅣa~Ⅳc with a yield of 88.6%,87.7%and 86.1%,respectively.The influence of alkali,temperature,solvent dosage on the yield of(E)-3-(2-chlorophenyl)-1-(2-hydroxyl-4-methoxyphenyl)prop-2-en-1-one(Ⅲa)was investigated,with the response surface method employed for synthesis condition optimization.Under the optimum conditions of 3.6 mmol chlorinated benzaldehyde,3 mmol paeonol,15 mL ethanol,0.239 g(6.0 mmol)NaOH,reaction temperature 70℃and reaction time 10 h,the average yield of chalconeⅢa was up to 93.7%with those of chalconeⅢb andⅢc 92.3%and 92.1%respectively.The products obtained were characterized by 1HNMR,13CNMR,135°DEPT and FTIR,and further evaluated for their UV and fluorescence properties.The fluorescence intensity ofⅣa~Ⅳc at 375.8,377.6 and 376.8 nm was 421.0,555.0 and 611.4 a.u.,respectively.When the synthesis scaled up 5 or 10 times,the yields ofⅢa~Ⅲc were 90.1%~93.7%,and those ofⅣa~Ⅳc were 84.7%~88.9%.

关 键 词：丹皮酚 催化合成 查尔酮 黄酮 氯代 精细化工中间体 

分 类 号：O626.41[理学—有机化学] O629[理学—化学]