SnCl2@MNPs催化Biginelli反应一锅法合成3,4-二氢嘧啶-2-酮衍生物

doi:10.6023/cjoc202101015

有机化学 ›› 2021, Vol. 41 ›› Issue (7): 2743-2749.DOI: 10.6023/cjoc202101015 上一篇下一篇

研究论文

SnCl₂@MNPs催化Biginelli反应一锅法合成3,4-二氢嘧啶-2-酮衍生物

赵雯辛^a, 黄孟君^b, 李胜男^a, 刘玉静^a, 刘中秋^a^,^*(), 应安国^a^,^b^,^*()

a 曲阜师范大学化学与化工学院山东曲阜 273100
b 台州学院医药化工学院浙江台州 318000

收稿日期:2021-01-08 修回日期:2021-02-04 发布日期:2021-04-16
通讯作者: 刘中秋, 应安国
基金资助:
国家自然科学基金(21978154); 山东省自然科学基金(ZR2020QB191); 曲阜师范大学国家级大学生创新创业训练计划(201910446018)

One-Pot Synthesis of 3,4-Dihydropyrimidine-2-one Derivatives via Biginelli Reactions Catalyzed by SnCl₂@MNPs

Wenxin Zhao^a, Mengjun Huang^b, Shengnan Li^a, Yujing Liu^a, Zhongqiu Liu^a(), An'guo Ying^a^,^b()

a College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, Shandong 273100
b College of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou, Zhejiang 318000

Received:2021-01-08 Revised:2021-02-04 Published:2021-04-16
Contact: Zhongqiu Liu, An'guo Ying
Supported by:
National Natural Science Foundation of China(21978154); Natural Science Foundation of Shandong Province(ZR2020QB191); National Students' Platform for Innovation and Entrepreneurship Training Programs(201910446018)

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摘要/Abstract

采用化学共沉淀法制备磁性Fe₃O₄纳米颗粒, 以磁性Fe₃O₄纳米颗粒为核, 通过碱催化正硅酸四乙酯水解法制备了具有核壳结构的磁性纳米颗粒(MNPs), 然后再利用化学共沉淀法制备了MNPs负载SnCl₂催化剂(SnCl₂@MNPs). 采用多种现代分析手段表征SnCl₂@MNPs的微观结构及其组成, 结果发现, SnCl₂均匀分散于MNPs表面, 且与MNPs之间形成较强的作用力. 通过SnCl₂@MNPs催化Biginelli反应来探究其催化性能, 结果发现, SnCl₂@MNPs能高效催化芳香醛或杂环醛、尿素或硫脲与α,β-二羰基化合物的三组分一锅法合成3,4-二氢嘧啶-2-酮衍生物, 且产率高达78%~96%. 由于SnCl₂@MNPs中活性组分SnCl₂在载体表面呈微粒形式存在, 从而增大了其与反应物的接触面积, 其高的催化活性归结于高度分散的SnCl₂与载体表面丰富的羟基簇的协同作用. 此外, SnCl₂@MNPs还具有强磁回收的特点, 该催化剂在磁力回收循环7次后, 仍然保持优异的催化性能.

关键词: 磁纳米颗粒, Biginelli反应, 芳香醛, α,β-二羰基化合物

The magnetic Fe₃O₄ nanoparticles were prepared by a co-precipitation method. The magnetic nanoparticles (MNPs) with core-shell structure were constructed by alkali-catalyzed hydrolysis of tetraethyl orthosilicate, and SnCl₂ grafted on MNPs (SnCl₂@MNPs) was successfully synthesized by a co-precipitation method. Then the catalyst of SnCl₂@MNPs was further analyzed by a series of modern characterization methods for exploring the microstructure and composition. The results showed that SnCl₂ was uniformly dispersed on the surfaces of MNPs and there were strong interaction forces between SnCl₂ and MNPs. Subsequently, the Biginelli reaction was performed to investigate the catalyst performance, the results showed that 3,4-dihydropyrimidin-2(1H)-ones were efficiently synthesized by a three component one-pot reactions of aromatic aldehydes or heterocyclic aldehydes, carbamide or thiourea, andα,β-dicarbonyl compounds with high yields of 78%~96%. The active fraction of SnCl₂ in SnCl₂@MNPs is uniformly distributed on the surface of MNPs and in the form of microcrystalline that increases the effective contact area with substrates. The highly activity of SnCl₂@MNPs is ascribed to the synergistic effect of SnCl₂ and the abundant hydroxyl cluster in MNPs. In addition, the catalyst can be recovered using an external magnetic field and reused at least 7 times without a considerable decrease in its catalytic activity.

Key words: magnetic nanoparticle, Biginelli reaction, aromatic aldehyde, α,β-dicarbonyl compound

引用此文

赵雯辛, 黄孟君, 李胜男, 刘玉静, 刘中秋, 应安国. SnCl₂@MNPs催化Biginelli反应一锅法合成3,4-二氢嘧啶-2-酮衍生物[J]. 有机化学, 2021, 41(7): 2743-2749.

Wenxin Zhao, Mengjun Huang, Shengnan Li, Yujing Liu, Zhongqiu Liu, An'guo Ying. One-Pot Synthesis of 3,4-Dihydropyrimidine-2-one Derivatives via Biginelli Reactions Catalyzed by SnCl₂@MNPs[J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2743-2749.

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图/表 12

图式1. Biginelli反应

Scheme 1. Biginelli reaction

图1. MNPs和SnCl2@MNPs的XRD谱图

Figure 1. XRD specta of MNPs and SnCl2@MNPs

图2. SnCl2@MNPs的XPS谱图

Figure 2. XPS spectrum of SnCl2@MNPs

图3. SnCl2@MNPs的SEM图像

Figure 3. SEM images of SnCl2@MNPs

Element	Weight/%	Atom/%
O K	14.64	36.85
Si K	4.41	6.31
Cl K	1.03	1.16
Fe K	74.84	53.95
Sn K	5.08	1.73

表1. SnCl2@MNPs的EDX分析

Table 1. EDX analysis of SnCl2@MNPs

图4. SnCl2@MNPs的TEM图像

Figure 4. TEM images of SnCl2@MNPs

Catalyst	Time/h	Yield/%
AlCl₃	5	50
FeCl₃	5	75
SnCl₂	5	78
SnCl₂@MNs	5	96

表2. 不同催化剂对Biginelli反应的影响a

Table 2. Effect of different catalysts on Biginelli reaction

图5. 温度对Biginelli反应的影响

Figure 5. Effect of temperature for the Biginelli reaction

图6. 催化剂用量对Biginelli反应的影响

Figure 6. Effect of catalyst amount on the Biginelli reaction

Entry	4	R¹	X	R²	Yield/%
1	4a	EtO	O	C₆H₅	96
2	4b	EtO	O	3-NO₂-C₆H₄	87
3	4c	EtO	O	2-Cl-C₆H₄	87
4	4d	EtO	O	2-CH₃O-C₆H₄	95
5	4e	EtO	O	4-CH₃O-C₆H₄	88
6	4f	EtO	O	4-CH₃-C₆H₄	87
7	4g	EtO	O	4-(CH₃)₂N-C₆H₄	92
8	4h	EtO	O	3,4-(CH₃O)₂-C₆H₃	89
9	4i	EtO	O	3-CH₃O-4-HO-C₆H₃	90
10	4j	EtO	O	C₄H₃S	93
11	4k	EtO	O	C₁₀H₇	88
12	4l	MeO	S	C₆H₅	78
13	4m	MeO	O	C₆H₅	94
14	4n	Me	O	C₆H₅	95
15	4o	Ph	O	C₆H₅	82

表3. SnCl2@MNPs催化多种芳香醛参与的Biginelli反应a

Table 3. Biginelli reactions concerning various aromatic aldehydes catalyzed by SnCl2@MNPs

图式2. SnCl2@MNPs催化合成3,4-二氢嘧啶-2-酮衍生物的反应机理

Scheme 2. Reaction mechanism of 3,4-dihydropyrimidin-2(1H)-ones catalyzed by SnCl2@MNPs

图7. (a) SnCl2@MNPs磁回收特性、(b) SnCl2@MNPs的回收利用和(c)七次循环后SnCl2@MNPs的TEM图像

Figure 7. (a) Magnetic recovery of SnCl2@MNPs, (b) reusability of SnCl2@MNPs and (c) TEM image of SnCl2@MNPs after 7 times

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SnCl₂@MNPs催化Biginelli反应一锅法合成3,4-二氢嘧啶-2-酮衍生物

One-Pot Synthesis of 3,4-Dihydropyrimidine-2-one Derivatives via Biginelli Reactions Catalyzed by SnCl₂@MNPs

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