AlCl3@MNPs催化硫杂Michael加成串联反应研究

doi:10.6023/cjoc202205008

摘要/Abstract

利用化学共沉淀法制备了超顺磁性Fe₃O₄纳米颗粒, 然后在碱性环境中水解正硅酸四乙酯得到二氧化硅包覆的核壳结构(MNPs), 进一步负载AlCl₃得到非均相催化剂AlCl₃@MNPs. 采用X射线电子能谱、X射线衍射、透射电镜、扫描电镜及磁滞回线测试等手段对AlCl₃@MNPs的物化性能和结构进行表征, 表明氯化铝通过与载体表面弱配位键的形成成功负载到磁性纳米粒上. 将得到的超顺磁性纳米粒负载的氯化铝(AlCl₃@MNPs)应用到硫杂Michael加成串联反应中. 研究发现, 该催化剂能有效促进胺、二硫化碳和α,β-不饱和羰基化合物加成反应, 产品收率为59%~99%. 催化剂具备的超顺磁性纳米颗粒的大表面积、反应时的良好分散性和AlCl₃与载体表面羟基的配位作用保证了其高催化活性. 另外, 由于AlCl₃@MNPs的超顺磁性, 在外加磁场存在条件下可以简便回收, 并重复使用10次, 其催化效果未见大幅下降, 明显优于未负载AlCl₃母体, 这显示了其良好的工业化应用前景.

关键词: 超顺磁性纳米颗粒, 硫杂Michael加成, 重复使用性, 绿色化学

Magnetic nanoparticles (MNPs), prepared by co-precipitation method, were coated using hydrolysis of tetraethyl orthosilicate (TEOS) under basic conditions. The core-shell structured supporters were further grafted by AlCl₃ to obtain the finally catalyst AlCl₃@MNPs, which was fully characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM) and vibrating sample magnetometer (VSM), indicating the successful immobilization of AlCl₃ on the surface of the MNPs through coordination bond, and the magnetic nanoparticles supported aluminum chloride AlCl₃@MNPs was used in the thia-Michael addition tandem reactions. The as-prepared catalyst AlCl₃@MNPs promoted smoothly the reaction of amines, carbon disulfide and α,β-unsaturated carbonyl compounds to achieve good to excellent product yields of 59%~99%. Large surface area, excellent dispersion of catalyst in reaction solution and coordinative bond between AlCl₃ and hydroxyl cluster in MNPs ensure the highly catalytic efficiency. In addition, AlCl₃@MNPs can be readily recovered with external magnetic field and recycled for 10 times without significant loss of catalytic activity, demonstrating its advantage over the precursor AlCl₃ and excellent potential in industrial application.

Key words: magnetic nanoparticles, thia-Michael addition, recyclability, green chemistry

引用此文

应安国, 白林盛, 侯海亮, 许松林, 鲁小彤, 王丽敏. AlCl₃@MNPs催化硫杂Michael加成串联反应研究[J]. 有机化学, 2022, 42(11): 3843-3852.

Anguo Ying, Linsheng Bai, Hailiang Hou, Songlin Xu, Xiaotong Lu, Limin Wang. Research on Thia-Michael Addition Tandem Reactions Catalyzed by AlCl₃@MNPs[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3843-3852.

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图/表 13

图1. 二硫代氨基甲酸酯衍生物的结构

Figure 1. Structrures of dithiocarbamate derivatives

图2. 超顺磁性纳米颗粒负载AlCl3的制备过程

Figure 2. Synthesis process of AlCl3 grafted on MNPs

图3. 催化剂AlCl3@MNPs的XPS谱图

Figure 3. XPS spectrum of catalyst AlCl3@MNPs

图4. AlCl3@MNPs和MNPs的XRD谱图

Figure 4. XRD spectrum of AlCl3@MNPs and MNPs

图5. SiO2@Fe3O4 (a)和AlCl3@MNPs (b)的透射电镜图

Figure 5. TEM images of SiO2@Fe3O4 (a) and AlCl3@MNPs (b)

图6. MNPs和AlCl3@MNPs的磁力曲线

Figure 6. Magnetic curves of MNPs and AlCl3@MNPs

图7. 催化剂AlCl3@MNPs的扫描电镜图

Figure 7. SEM images of catalyst AlCl3@MNPs

图8. 催化剂AlCl3@MNPs的能量色散X射线光谱分析(图中表格为具体的元素含量)

Figure 8. EDX analysis of catalyst AlCl3@MNPs (specific element content depicted in inert table)

Entry	Catalyst (g)	Solvent	Time/h	Yield^b/%
1	AlCl₃@MNPs (0.20)	Ethanol	5	97
2	AlCl₃ (0.04)	Ethanol	5	95
3	FeCl₃ (0.04)	Ethanol	5	53
4	ZnCl₂ (0.04)	Ethanol	5	38
3	MNPs (0.16)	Ethanol	10	Trace
4	—	Ethanol	14	Trace
5	AlCl₃@MNPs (0.20)	Methanol	5	93
6	AlCl₃@MNPs (0.2)	CH₂Cl₂	6	82
7	AlCl₃@MNPs (0.2)	Toluene	6	84
8	AlCl₃@MNPs (0.01)	Ethanol	8	30
9	AlCl₃@MNPs (0.05)	Ethanol	6	58
10	AlCl₃@MNPs (0.10)	Ethanol	5	76
11	AlCl₃@MNPs (0.25)	Ethanol	5	96

表1. 4-甲基哌啶、二硫化碳及丙烯酰胺间的Michael加成反应的条件优化a

Table 1. Optimization reaction conditions for Michael addition of 4-methyl piperidine, CS2 and acrylamide

Entry	R¹	R²	Time/h	8	Yield^b/%
1	4-Me-piperidyl	NH₂	5	8a	97
2	4-Me-piperidyl	N(CH₃)₂	6	8b	90
3	4-Me-piperidyl	NHCH(CH₃)₂	6	8c	92
4	4-Me-piperidyl	Morpholinyl	6	8d	93
5	4-Me-piperidyl	NHCH₂OH	6	8e	95
6	4-Me-piperidyl	NHC(CH₃)₃	7	8f	68
7	4-Me-piperidyl	NHC(CH₃)₂- CH₂COCH₃	8	8g	59
8	4-Me-piperidyl	OCH₃	5	8h	99
9	Piperidyl	NH₂	5	8i	86
10	Piperidyl	NHCH₂OH	6	8j	90
11	Piperidyl	Morpholinyl	6	8k	86
12	Piperidyl	NHCH(CH₃)₂	6	8l	87
13	Piperidyl	N(CH₃)₂	5	8m	87
14	Morpholinyl	Morpholinyl	6	8n	80
15	Morpholinyl	N(CH₃)₂	6	8o	90
16	Morpholinyl	OCH₃	5	8p	86
17	Pyrrolidyl	NHCH(CH₃)₂	6	8q	95
18	Pyrrolidyl	NHCH₂OH	6	8r	95
19	Pyrrolidyl	Morpholinyl	6	8s	85
20	Pyrrolidyl	N(CH₃)₂	6	8t	84

表2. AlCl3@MNPs催化的硫杂Michael加成反应a

Table 2. Thio-Michael addition reactions catalyzed by AlCl3@- MNPs

图9. AlCl3@MNPs催化硫杂Michael加成的可能反应机理

Figure 9. Proposed mechanism for AlCl3@MNPs catalyzed thio-Michael addition reaction

图10. AlCl3@MNPs在反应过程中的分散图(a)、外加磁场分离图(b)和回收后催化剂的电镜图(c)

Figure 10. Photographs of the dispersion of catalyst AlCl3@- MNPs in reaction procedure (a), separation with external magnetie (b), and TEM image of reused catalyst (c)

图11. 磁性纳米粒负载的催化剂AlCl3@MNPs催化4-甲基哌啶、CS2及丙烯酰胺间的硫杂Michael加成反应中重复使用性研究

Figure 11. Recyclability investigation of AlCl3@MNPs used as a catalyst for the thio-Michael addition reaction of 4-methyl piperidine, CS2 and acrylamide

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AlCl₃@MNPs催化硫杂Michael加成串联反应研究

Research on Thia-Michael Addition Tandem Reactions Catalyzed by AlCl₃@MNPs

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