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

doi:10.6023/cjoc202101015

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (7): 2743-2749.DOI: 10.6023/cjoc202101015 Previous Articles Next Articles

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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

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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Abstract

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

Cite this article

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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Fig. & Tab. 12

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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

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

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

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

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

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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