羰基化合物直接还原胺化合成伯胺催化剂研究进展

doi:10.16085/j.issn.1000-6613.2021-1551

摘要/Abstract

摘要：

胺类化合物是一类重要的化工原料和中间体，在农药、医药、染料、高分子聚合物等领域有着广泛的应用。通过羰基化合物（醛或酮类）的还原胺化来制备胺类化合物是当前的研究热点。研究表明，贵金属基和非贵金属基的多相和均相催化剂均能够高效催化醛或酮类的还原胺化反应。本文对近年来羰基化合物直接还原胺化（或一锅法）合成伯胺的研究现状进行了综述，包括还原胺化反应、催化剂、反应条件、底物适用范围和催化作用机制等，其中重点阐述了直接还原胺化催化剂的研究进展。文章指出：通常多相催化剂具有活性高以及可重复使用等优点，而均相催化剂的优势在于催化效率高，伯胺选择性高；另一方面，以Pd、Rh、Ru等为代表的贵金属催化剂催化性能优异，但价格昂贵，因此可采用Co、Ni等性能同样优异但价格相对低廉的非贵金属催化剂以降低成本。文中提出，催化效率高、反应条件温和、普适性高的羰基化合物还原胺化催化剂应成为未来重点研究方向。

关键词: 直接还原胺化, 羰基化合物, 伯胺, 均相催化, 多相催化, 催化剂

Abstract:

Amines, especially primary amines, have been extensively employed in pesticide, medicine, dye and high molecular polymer as raw materials or intermediates. Recently, direct reductive amination of carbonyl compounds (aldehydes or ketones) has been a research focus for synthesizing primary amines. Heterogeneous and homogeneous catalysts based on noble and non-noble metals have been proven to be efficient for direct reductive amination of carbonyl compounds. In this paper, we carefully review the state of art of direct reductive amination of carbonyl compounds (one-pot method) to synthesize primary amines, including reaction profile, recent progress in catalysts, reaction conditions, the substrate scope and catalytic mechanism, especially the catalysts. Generally, heterogeneous catalysts are highly active and could be reused, while homogeneous catalysts have the advantages of high efficiency and high primary amines selectivity. On the other hand, noble catalysts like Pd, Rh and Ru are more active and expensive, so non-noble metal based catalysts like Co and Ni catalysts could be alternative for the sake of economic. Thus, the catalysts for direct reductive amination to synthesize primary amines with high efficiency, mild reaction condition and high universality should be developed.

Key words: direct reductive amination, carbonyl compounds, primary amine, homogeneous catalysis, heterogeneous catalysis, catalysts

中图分类号:

O622.6

吴静航, 陈臣举, 梁杰, 张春雷. 羰基化合物直接还原胺化合成伯胺催化剂研究进展[J]. 化工进展, 2022, 41(6): 2981-2992.

WU Jinghang, CHEN Chenju, LIANG Jie, ZHANG Chunlei. Recent progress in the synthesis of primary amine via direct reductive amination of aldehydes and ketones[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2981-2992.

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催化剂	反应条件	反应底物	反应结果
Rh/Al₂O₃^［26］	80℃，氨水，2MPa H₂，2h	糠醛	X_糠醛=100%，S_糠胺=91.5%
Rh/CeO₂^［27］	50℃，0.1MPa H₂，14h	苯甲醛	X_苯甲醛=100%，S_苄胺=88%
Ru/γ-Al₂O₃^［28］	80℃，0.4MPa NH₃，3MPa H₂，2h	庚醛	X_庚醛=100%，S_庚胺=94%
Ru/Nb₂O₅^［29］	90℃，0.1MPa NH₃，4MPa H₂，4h	糠醛	X_糠醛=100%，S_糠胺=99%
Ru/HZSM-5^［31］	80℃，NH₃（7mol/L MeOH 溶液），3MPa H₂，15min	糠醛	X_糠醛=100%，S_糠胺=76%
Ru/ZrO₂^［32］	85℃，氨水，2MPa H₂，12h	乙醇醛	X_乙醇醛=100%，S_乙醇胺=93%
Pt-MoO _x /TiO₂^［34］	100℃，0.4MPa NH₃，0.2MPa H₂，20h	2-金刚烷酮	X_{2-金刚烷酮}=100%，S_{2-金刚烷胺}=93%
Pd/NPs^［35］	室温，NH₃，0.1MPa H₂，3h	苯甲醛	X_苯甲醛=100%，S_苄胺=98%

催化剂	反应条件	反应底物	反应结果
Co-DABCO-TPA@C-800^［36］	120℃，0.5MPa NH₃，4MPa H₂，15h	3,4-二甲氧基苯甲醛	Y_{3,4-二甲氧基苄胺}=88%
Co/GS@C^［37］	120℃，0.5MPa NH₃，4MPa H₂，15h	苯甲醛	Y_卞胺=88%
Co@NC-800^［38］	130℃，氨水，1MPa H₂，12h	苯甲醛	Y_卞胺=96.9%
Co@NC^［39］	110℃，氨水，2MPa H₂，5h	对甲氧基苯甲醛	Y_{对甲氧基卞胺}=94.5%
Ni/MC^［40］	80℃，氨水，0.1MPa H₂，2h	苯甲醛	Y_苄胺=99.1%
Fe/(N)SiC^［41］	140℃，氨水，6.5MPa H₂，20h	苯乙酮	Y_1-苯乙胺=99%
Ni/γ-Al₂O₃^［42］	80℃，氨水，0.1MPa H₂，20h	苯甲醛	Y_苄胺=99%
Ni-TA@SiO₂-800^［43］	120℃，0.5MPa NH₃，2MPa H₂，15h	邻溴苯甲醛	Y_邻溴卞胺=96%

催化剂	反应条件	反应底物	反应结果
[Rh(COD)Cl]₂/TPPTS^[45]	135℃，氨水，6.5MPa H₂，2h	苯甲醛	Y_苄胺=86%
[Ru(CO)ClH(PPh₃)₃]^[46]	120℃，0.9MPa NH₃，4MPa H₂，16h	苯乙酮	Y_α-苯乙胺=95%
[Ru(PPh₃)₃H(CO)Cl]^[47]	80℃，NH₄I，3MPa H₂，24h	甲基酮环己酯	Y₍_S_{)-(+)-1-环己基乙胺}=78%
RuCl₂(PPh₃)₃^[48]	120℃，0.5~0.7MPa NH₃，4MPa H₂，24h	苯甲醛	Y_卞胺=95%
Ru-1^［49］	130℃，0.5MPa NH₃，5MPa H₂，12h	苯甲醛	Y_苄胺=94%
Cp*Ir^［50］	80℃，甲酸铵，4h	苯乙酮	Y_1-苯乙胺=97%

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