UCST型玫瑰红催化剂的制备与催化合成四氢异喹啉类化合物  

UCST type Rose Bengal catalyst preparation and its catalytic synthesis of tetrahydroisoquinoline derivatives

作　　者：黄宝强 蔡亭伟 王照朋 赵强强[1,2] HUANG Baoqiang;CAI Tingwei;WANG Zhaopeng;ZHAO Qiangqiang(College of Chemical and Bioengineering,Donghua University,Shanghai 201620,China;Shandong Zhongkang Guochuang Advanced Printing and Dyeing Technology Research Institute Co.,Ltd.,National Advanced Printing and Dyeing TechnologyInnovationCenter,Taian271000,Shandong,China)

机构地区：[1]东华大学化学化工与生物工程学院,上海201620 [2]山东中康国创先进印染技术研究院有限公司国家先进印染技术创新中心,山东泰安271000

出　　处：《精细化工》2022年第10期2086-2091,共6页Fine Chemicals

基　　金：中国博士后科学基金资助项目(2021M690599);山东省自然科学基金资助项目(ZR2021ME251)。

摘　　要：以甲基丙烯酸甲酯(MMA)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)为原料,合成了聚合物P(MMA-x DMC)(x为DMC的含量,以MMA物质的量为基准,下同)。通过P(MMA-x DMC)对玫瑰红(RB)的吸附作用,制得高临界溶解温度(UCST)型RB催化剂[P(MMA-x DMC)-RB]。对聚合物的相对分子质量、UCST以及P(MMA-x DMC)-RB在溶液中溶解再析出的稳定性进行了测试,考察了P(MMA-x DMC)-RB催化N-苯基四氢异喹啉衍生物与硝基甲烷反应的活性与稳定性。结果表明,x为0.5%~2.0%时,产物的UCST在37~42℃,P(MMA-1%DMC)-RB经过4次溶解-沉淀实验后,溶解再析出百分率达第一次的93%以上;在N-苯基四氢异喹啉衍生物和硝基甲烷的交叉脱氢偶联反应中,P(MMA-1%DMC)-RB具有较高的催化活性,与常规RB相当。在反应温度为45℃、白色1 W LED光源下反应8 h,产物四氢异喹啉衍生物的收率在80%以上。该UCST型RB催化剂具有良好循环稳定性,循环使用8次后,四氢异喹啉衍生物的收率降为77.9%。UCST(high critical dissolution temperature) type Red Bengal(RB) catalyst P(MMA-x DMC)-RB(x refers to the content of DMC, based on the molar amount of MMA, the same below) was prepared via adsorption of P(MMA-x DMC) on RB, of which P(MMA-x DMC) was synthesized from methyl methacrylate(MMA) and methyl acryloxyethyl trimethyl ammonium chloride(DMC). The relative molecular mass of the polymer obtained, UCST and stability of P(MMA-x DMC)-RB dissolved and reprecipitated in solution were analyzed, followed by investigation on its catalytic activity and stability in the reaction of N-phenyltetrahydroisoquinoline derivatives with nitromethane. The results showed that the UCST of products prepared was 37~42 ℃ when x = 0.5%~2.0%, and the recovery of P(MMA-1%DMC)-RB still reached >93% after four cycles of dissolution-precipitation. In the cross dehydrogenation coupling reaction between N-phenyltetrahydroisoquinoline derivatives and nitromethane, P(MMA-1%DMC)-RB exhibited high catalytic activity comparable to that of conventional RB. The yield of tetrahydroisoquinoline was higher than 80% with white 1 W LED light source irradiation for 8 h at 45 ℃.Moreover, the UCST type RB catalyst displayed good cycle stability with the yield of tetrahydroisoquinoline derivatives decreased 77.9% after catalyst being cycled for 8 times.

关 键 词：交叉脱氢偶联反应 UCST聚合物 玫瑰红 光催化反应 催化技术 

分 类 号：O643.3[理学—物理化学]