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化学进展 2020, Vol. 32 Issue (1): 72-83 DOI: 10.7536/PC190501 前一篇   后一篇

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硝基芳烃与醇还原胺化:催化剂和催化机制

杨萍, 刘敏节, 张昊, 郭雯婷, 吕朝阳, 刘迪**()   

  1. 1. 山东科技大学化学与生物工程学院 青岛 266590
  • 收稿日期:2019-05-08 出版日期:2020-01-15 发布日期:2019-12-11
  • 通讯作者: 刘迪
  • 基金资助:
    国家自然科学基金项目资助(21878178)
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Reductive Amination of Nitroarenes and Alcohols: Catalyst and Catalytic Mechanism

Ping Yang, Minjie Liu, Hao Zhang, Wenting Guo, Chaoyang Lv, Di Liu**()   

  1. 1. College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China
  • Received:2019-05-08 Online:2020-01-15 Published:2019-12-11
  • Contact: Di Liu
  • About author:
    ** E-mail:
  • Supported by:
    National Natural Science Foundation of China(21878178)

胺类化合物由于其化学结构和性质上的特点,在合成药物、染料和精细化学品等方面有着重要的应用。胺类化合物的合成方法很多,其中硝基芳烃与醇还原胺化反应由于可以“一锅”法将性质稳定、来源广泛的硝基芳烃、醇转化为各类胺类化合物,且无需提供额外的氢源,从而成为研究的热点。本文即以硝基芳烃与醇还原胺化反应路径为主线,从催化剂及其催化机制两方面对硝基芳烃与醇还原胺化反应的研究进展进行综述,分别对已开发的贵金属催化剂、光催化剂及一些其他类型催化剂作了介绍,重点阐述了催化剂的催化性能、底物适用范围和催化机制。尽管目前各类催化体系都已取得较大的进展,但在一定程度上依然存在着催化剂成本高,底物适应性窄,需要大量使用碱性助剂、溶剂、供氢试剂等问题。基于以上问题,本文指出硝基芳烃与醇还原胺化应重点发展绿色高效、廉价、普适性好、通用性强的催化体系;同时,还要系统地对各种催化剂的催化机制进行深入的研究,为催化体系的开发提供指导。

关键词： 硝基芳烃, 醇, 还原胺化, 胺类化合物, 贵金属, 光催化剂, 催化机制

Amine compounds have been widely applied in the field of pharmaceuticals, dyes and fine chemicals due to its characteristics of chemical structure and property. Many methods for the synthesis of amine compounds are available, in which the reductive amination of nitroarenes and alcohols has attracted extensive attention because nitroarenes and alcohols with the advantages of good accessibility and stable chemical properties can directly be converted to amines by one-pot method without additional hydrogen sources. The recent progress is summarized from two aspects: catalyst and catalytic mechanism based on reaction pathways of the reductive amination of nitroarenes in this article. We introduce all kinds of catalytic systems in detail such as noble metal, photocatalyst, and so on, the catalytic performance, applicability and catalytic mechanism of which are highlighted. It needs to be pointed out that these catalytic systems show varying degrees of success as well as limitations like high cost of catalyst, narrow applicable range of substrates, excessive exogenous base, additional hydrogen source and/or toxic organic solvents. Based on the above problems, it would be desirable to develop a green, efficient, inexpensive and universal catalytic system, the catalytic mechanism of various catalysts should be systematically studied to provide guidance for the development of catalytic system on the other hand.

Key words: nitrobenzenes, alcohols, reductive amination, amines, noble-metal, photocatalyst, catalytic mechanism
()
图1 目前常用合成胺类化合物的方法
Fig. 1 Current methods for synthesizing amine compounds
表1 伯醇和硝基芳烃的催化缩合反应a [12]
Table 1 Catalytic condensation of primary alcohols and nitroarenesa [12]
Entry R1 R2 t(h) Product Yield (%)b
1 4-Me C6H5 3 83
2 4-MeO C6H5 3 55
3 H 4-Me-C6H5 5 90
4 H 4-MeO-C6H5 20 50(43)
5 H C6H5CH=CHCH2 20 17
6 H C6H5CH2 12 92
7 H C6H5 3 82
8 4-Me 4-Me-C6H5 12 89
9 4-Me 4-MeO-C6H5 12 83
10 4-MeO C6H5 3 75
11 4-MeO 4-Me-C6H5 12 84
12 4-MeO 4-MeO-C6H5 12 70(65)
图2 硝基苯与苯甲醇之间的催化串联反应:(a)硝基芳烃还原的两种途径; (b)醇氧化;(c)胺/醛缩合[13]
Fig. 2 Catalyzed tandem reaction between nitrobenzene and benzyl alcohol: (a) two pathways in the reduction of nitroarene; (b) alcohol oxidation, and (c) amine/aldehyde condensation products[13]
图3 反应机制的推测[18]
Fig. 3 Proposed reaction mechanism[18]
图4 以甘油为还原剂合成N-烷基苯胺的可能机制[21]
Fig. 4 The plausible mechanism of the synthesis of N-alkyl aniline using glycerol as the reducing agent[21]
图5 亚胺合成中Cu-Au的协同效应[22]
Fig. 5 Cu-Au cooperation effect in imine production[22]
图6 P25 TiO2催化合成亚胺的反应路径[24]
Fig. 6 Proposed pathways for the imine formation on P25 TiO2 [24]
图7 在CdS-TiO2光催化剂上从苯甲醇和硝基苯一锅法合成亚胺[25]
Fig. 7 The one-pot synthesis of imine from benzyl alcohol and nitrobenzene on the CdS-TiO2 photocatalyst[25]
表2 CdS-TiO2光催化带有不同取代基的苯甲醇和硝基苯一锅法合成亚胺[26]
Table 2 One-pot synthesis of imines from several benzylic alcohols and nitrobenzene on the CdS-TiO2 photocatalyst[26]
X Time(h) Yields of imines(%)
acetonitrile cyclohexane
H 12 44 99
CF3 24 55 81
Cl 24 59 87
CH3 24 49 81
OCH3 12 70 90
表3 Co-N-C/CNT@AC催化硝基苯与醇的还原偶联合成亚胺a [33]
Table 3 Co-N-C/CNT@AC-catalyzed reductive coupling of nitrobenzenes and alcohols to imina [33]
Entry Substrate 1 Substrate 2 Time (h) Conversion
(%)b 		Selectivity
(%)c
1 18 98 99
2 24 98 94
3 28 100 97
4 20 100 90
5 30 98 98
6 36 97 98
7 42 91 97
8 40 95 96
9 36 96 98
10 22 100 99
11 28 75 22
12 24 21 44
13 24 12 10
图8 硝基芳烃直接烷基化的机理[34]
Fig. 8 A mechanism path for the direct alkylation of nitroarenes[34]
表4 硝基芳烃与醇还原烷基化结果a [7]
Table 4 Results of the reductive alkylation of nitrobenzenes with alcoholsa [7]
Entry Products t (h) Yield(%)b Entry Products t (h) Yield(%)b
1 12 94 10 24 83
2 12 95
11 24 85
3 12 83 12 18 82
13 24 75
4 12 84
14 24 73
5 12 87
15 12 93
6 12 93
16 12 83
7 12 89
17 24 83
8 16 92
18 12 70
9 24 86
19 24 81
图9 硝基芳烃的还原性N-烷基化反应机理[35]
Fig. 9 Proposed mechanism for the reductive N-alkylation of nitro aromatics[35]
图10 硝基芳烃直接烷基化的反应途径[38]
Fig. 10 A tentative pathway for the direct alkylation of nitroarenes[38]
图11 Pd/TiO2光催化剂催化硝基苯和苯甲醇合成仲胺的反应途径[39]
Fig. 11 Proposed pathway for secondary amine formation from alcohols and nitroarenes on the photoactivated Pd/TiO2 catalyst[39]
图12 Co-N-C/CNT@AC催化硝基苯与苯甲醇还原胺化反应机理研究[33]
Fig. 12 The reaction mechanism for the reductive amination of nitrobenzene with benzyl alcohol over Co-N-C/CNT@AC[33]
表5 催化硝基芳烃与醇合成叔胺a[37]
Table 5 Catalytic formation of tertiary amines from nitroarenes and alcohols a[37]
Entry R1 R2 Product Yield(%)c
1 H C6H5 98 (96)
2 p-Me C6H5 94
3 p-MeO C6H5 87
4 p-Cl C6H5 85 (83)
5 m-Me C6H5 88
6 H C6H5CH2 80
7 H p-MeC6H4 92 (90)
8 H p-Cl C6H4 81
9 H o-Cl C6H4 56
10 b H C7H15 70 (67)
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