UCST型玫瑰红催化剂的制备与催化合成N-苯基四氢异喹啉类化合物

Preparation of dye supported UCST polymer and its application in the reaction of N-phenyl tetrahydroisoquinoline and its derivatives

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-DMC)，通过P(MMA-DMC)对玫瑰红（RB）的吸附作用，制得UCST（高临界溶解温度）型RB催化剂〔P(MMA-DMC)-RB〕。测定了聚合物的相对分子质量、UCST温度以及P(MMA-DMC)-RB在溶液中溶解再析出的稳定性，研究了P(MMA-DMC)-RB在催化N-苯基四氢异喹啉衍生物与硝基甲烷反应的催化活性与稳定性。结果表明，DMC含量为0.5%~2%时(DMC含量以MMA物质的量为基准计算)，UCST温度在35~42℃，P(MMA-1%DMC)-RB经过四次溶解-沉淀实验后，回收量仍可达到首次的93%以上；在N-苯基四氢异喹啉衍生物和硝基甲烷的CDC（交叉脱氢偶联反应）反应中，P(MMA-1%DMC)-RB具有较高的催化活性，催化性能与常规玫瑰红RB相当，在反应温度为45℃，白色1W LED光源下反应8h，产物四氢异喹啉衍生物的收率在80%以上，并且该UCST型RB催化剂具有良好的套用性和稳定性，循环套用8次后，四氢异喹啉衍生物的收率从90.2%降为77.9%。

Abstract:

The polymer P(MMA-DMC) was synthesized from methyl methacrylate (MMA) and methyl acryloxyethyl trimethyl ammonium chloride (DMC) as raw materials. By the adsorption of P(MMA-DMC) on Rose red (RB), UCST(High critical dissolution temperature) type RB catalyst P(MMA-DMC)-RB was prepared. The UCST temperature and the stability of P(MMA-DMC)-RB dissolved in solution were determined. The catalytic activity and stability of P(MMA-DMC)-RB catalyzed the reaction of N-phenyltetrahydroisoquinoline derivatives with nitromethane were studied. The results show that when DMC content is 0.5%~2% (DMC content is calculated based on MMA content),UCST temperature is 35~42℃,After four dissolution-precipitation experiments of P(MMA-1%DMC)-RB, the recovery can still reach more than 93% of the first time. In the CDC(cross dehydrogenation coupling reaction) between N-phenyltetrahydroisoquinoline derivatives and nitromethane,P(MMA-1%DMC) -RB has a high catalytic activity, and its catalytic performance is comparable to that of conventional rose Red RB. The yield of N-phenyltetrahydroisoquinoline was more than 80% when the reaction temperature was 45 and the white 1W LED light source was used for 8h. Moreover, the UCST RB catalyst has good adaptability and stability. After 8 times of application, the yield of N-phenyltetrahydroisoquinoline compounds decreases from 90.2% to 77.9%.