微反应器内的有机合成前沿进展

doi:10.11949/0438-1157.20220403

摘要/Abstract

摘要：

微反应器一般是指特征尺寸为微米至百微米级的微型反应器，是微化工系统的核心设备之一。与传统的釜式反应器相比，微反应器在危险或易燃易爆产品的合成过程及快反应过程中体现出独特优势。凭借其优异的传热传质性能，微反应器技术使这些危险化工过程变得更精准、更高效、更安全，具有重要的工业应用价值，也是化工领域的重点发展方向之一。本文主要介绍了近年来微反应器技术在医药、农药、染颜料合成等精细化工领域的进展，重点综述了在霍夫曼重排、环加成、重氮化和偶合、烷基化、氮氧化等典型“强放热快反应”有机合成方向的研究进展，并展望了其发展前景。

关键词: 微反应器, 有机合成, 强放热, 危险反应, 本质安全

Abstract:

Microreactor generally refers to microreactor with characteristic size ranging from microns to hundreds of microns and is one of the core equipment of microchemical systems. Compared with the traditional tank reactor, microreactors show unique advantages in the synthesis process of dangerous or flammable and explosive products and in the rapid reaction process. Due to its excellent heat and mass transfer performance, the microreactor technology makes these hazardous chemical processes more accurate, efficient and safer. In this way, the microreactor has important industrial application value and is also one of the key development directions in the chemical industry. This paper mainly introduces the Hoffmann rearrangement, cycloaddition, diazotization and coupling, alkylation, nitrogen oxidation involved in the use of microreactor technology in the field of fine chemicals such as medicine, pesticide, dye and pigment in recent years. The research progress of typical “strong exothermic fast reaction” organic synthesis and its development prospects are prospected.

Key words: microreactor, organic synthesis, strong exothermic, hazardous reaction, intrinsic safety

中图分类号:

TQ 052.5

张经纬, 周弋惟, 陈卓, 徐建鸿. 微反应器内的有机合成前沿进展[J]. 化工学报, 2022, 73(8): 3472-3482.

Jingwei ZHANG, Yiwei ZHOU, Zhuo CHEN, Jianhong XU. Advances in frontiers of organic synthesis in microreactor[J]. CIESC Journal, 2022, 73(8): 3472-3482.

图/表 11

图1 制备环丙胺的微反应实验装置示意图[20]

Fig.1 Schematic diagram of a microreaction experimental apparatus for the preparation of cyclopropane[20]

图2 (a) 制备加巴喷丁的微反应实验装置示意图；(b) 合成反应方程；(c) 微通道的内部结构示意图[21]

Fig.2 (a) Schematic diagram of the microreaction reaction experimental setup for the preparation of Gapentin; (b) Synthesis equation; (c) Schematic diagram of the internal structure of the microchannel[21]

图3 制备碳酸丙烯酯的微反应实验装置示意图[32]

Fig.3 Schematic diagram of the microreaction experimental setup for preparation of propylene carbonate[32]

图4 由 [bmim]Br催化的CO2环加成的可能机理[34]

Fig.4 The possible mechanism for the cycloaddition of CO2 catalyzed by [bmim]Br[34]

图5 (a)合成颜料红146的偶合反应; (b) 合成颜料红146的微反应系统示意图[52]

Fig.5 (a) Coupling reaction of C.I. PR 146; (b)Experimental setup of the C.I. PR 146 synthesis microreactor system[52]

图6 颜料黄14合成的重氮化和偶合反应[54]

Fig.6 Diazotization and azo coupling reaction for Yellow 14[54]

图7 4-硝基苯胺重氮化/重氮偶合流程图[55]

Fig.7 Flow chart of diazotization/diazo coupling of 4-nitroaniline[55]

图8 红色基KD合成装置示意图[56]

Fig.8 Sketch for diazotization and azo coupling reaction for Red KD[56]

图9 连续流系统的示意图[66]

Fig.9 Schematic of the continuous-flow reactor system[66]

图10 循环微反应器示意图[72]

Fig.10 Sketch for circular microreaction[72]

图11 商业化微反应器示意图[74]

Fig.11 Sketch for commercial microreaction[74]

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