Page 157 - 《精细化工》2022年第10期

第 10 期 黄宝强，等: 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 ·2091·

收率降低。 应的产物收率仍可达 77.9%。为进一步提升 UCST
综上可知，P(MMA-1% DMC)-RB 能够高效催 型 RB 的实用性产物，拓展催化反应种类与优化聚
化四氢异喹啉衍生物的合成，催化活性与常规 RB 合物结构是后续研究的重点。
相当。P(MMA-1% DMC)-RB 具有良好的稳定性，
参考文献：
经过 8 次循环套用实验，产物仍具有良好的收率，
[1] LIN W L, CAO T, FAN W, et al. Enantioselective double manipulation of
并且催化剂的结构没有明显变化。
tetrahydroisoquinolines with terminal alkynes and aldehydes under
copper (Ⅰ) catalysis[J]. Angewandte Chemie International Edition,
2014, 53(1): 277-281.
[2] RITLENGI V, SIRLIN C, PFEFFER M. Ru-, Rh-, and Pd-catalyzed
C—C bond formation involving C—H activation and addition on
unsaturated substrates: Reactions and mechanistic aspects[J]. Chemical
Reviews, 2002, 102(5): 1731-1770.
[3] ZUO C S (左长生), ZHANG H Y (张红英), YAN X M (颜雪明).
Cross dehydrogenative coupling reaction: A review[J]. Journal of
Capital Normal University: Natural Science Edition (首都师范大学
学报: 自然科学版), 2015, 36(1): 44-53.
[4] SHARMA S, SHARMA A. Recent advances in photocatalytic
manipulations of Rose Bengal in organic synthesis[J]. Organic &
Biomolecular Chemistry, 2019, 17(18): 4384-4405.
[5] XIAO L Q, HUANG Y X, LUO Y, et al. Organic cotton
图 3 P(MMA-DMC)-RB 的循环稳定性 photocatalysis[J]. ACS Sustainable Chemistry & Engineering, 2018,
Fig. 3 Cycle stability of P(MMA-DMC)-RB 6(11): 14759-14766.

[6] LI X R, LI Y Y, HUANG Y X, et al. Organic sponge photocatalysis[J].
Green Chemistry, 2017, 19(13): 2925-2930.
[7] ZHANG T, LIANG W W, HUANG Y X, et al. Bifunctional organic
sponge photocatalyst for efficient cross-dehydrogenative coupling of
tertiary amines to ketones[J]. Chemical Communications, 2018, 54(72):
12536-12539.
[8] HUANG Y X, XIN Z, YAO W L, et al. A recyclable self- assembled
composite catalyst consisting of Fe 3O 4-rose bengal-layered double
hydroxides for highly efficient visible light photocatalysis in water[J].
Chemical Communications, 2018, 54(96): 13587-13590.
[9] JIANG J X, LI Y Y, WU X F, et al. Conjugated microporous
polymers with Rose Bengal dye for highly efficient heterogeneous

organo-photocatalysis[J]. Macromolecules, 2013, 46(22): 8779-8783.
图 4 P(MMA-1% DMC)-RB 的 FTIR 谱图 [10] YANG W H (杨卫海), DOU H J (窦红静), SUN K (孙康). Heat
Fig. 4 FTIR spectra of P(MMA-1% DMC)-RB sensitive polymer materials with high critical phase transition
temperature[J]. Journal of East China University of Technology:
Natural Science Edition (华东理工大学学报：自然科学版), 2006,
3 结论 32(6): 731-735.
[11] HO D L, HAMMOUDA B, KLINEL S R, et al. Unusual phase
（1）基于 MMA 与 DMC 溶液聚合，制备了一 behavior in mixtures of poly (ethylene oxide) and ethyl alcohol[J].
Journal of Polymer Science Part B-Polymer Physics, 2006, 44(3):
系列可以负载 RB 的 UCST 聚合物 P(MMA-xDMC)， 557-564.
聚合物的 UCST 温度在 37~42 ℃，相对分子质量在 [12] PIETSCH C, HOOGENBOOM R, SCHUBERT U S. PMMA based
10500~12000 之间，PDI 分布在 1.56~1.80 之间。通 soluble polymeric temperature sensors based on UCST transition and
solvatochromic dyes[J]. Polymer Chemistry, 2010, 1(7): 1005-1008.
过聚合物对 RB 的吸附制备了 UCST 型 RB 催化剂。 [13] DONG Y Y, WANG Q F, WANG J T, et al. Temperature responsive
其中，P(MMA-1% DMC)-RB 在乙醇水溶液中溶解 copolymer as support for metal nanoparticle catalyst: A recyclable
再析出性能最佳，经 4 次溶解-析出实验后，玫瑰红 catalytic system[J]. Reactive & Functional Polymers, 2017, 112(35):
60-67.
RB 的溶解再析出百分率仍大于 90%。 [14] ZHANG Q L, HOOGENBOOM R. Polymers with upper critical
（2）P(MMA-1% DMC)-RB 在催化 N-苯基四氢 solution temperature behavior in alcohol/water solvent mixtures[J].
异喹啉及其衍生物与硝基烷烃的 CDC 反应中具有 Progress in Polymer Science, 2015, 48(24): 122-142.
[15] MENG Q Y, ZHONG J J, LIU Q, et al. A cascade cross-coupling
较高的催化活性，不同反应底物对应的产物收率均 hydrogen evolution reaction by visible light catalysis[J]. Journal of
大于 80%，且催化性能与常规 RB 相当。反应体系 the American Chemical Society, 2013, 135(51): 19052-19055.
中的 P(MMA-1% DMC)-RB 通过降温析出实现套 [16] LOSTE J, LOPEZ-CUESTA J M, BILLON L, et al. Transparent
polymer nanocomposites: An overview on their synthesis and advanced
用，套用 8 次后，N-苯基四氢异喹啉与硝基甲烷反 properties[J]. Progress in Polymer Science, 2019, 89(32): 133-158.