Fe-MIL-101催化Paal-Knorr反应合成吡咯衍生物

doi:10.7503/cjcu20150462

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (1): 108.doi: 10.7503/cjcu20150462

Fe-MIL-101催化Paal-Knorr反应合成吡咯衍生物

杨明¹, 汤甲¹, 王静静¹, 范爽¹, 张欢¹, 陶柳实¹, 谭丽²()

1. 北京科技大学材料科学与工程学院,
2. 新材料技术研究院, 北京 100083

收稿日期:2015-06-12 出版日期:2016-01-10 发布日期:2015-12-20
作者简介:联系人简介: 谭丽, 女, 博士, 工程师, 主要从事催化材料研究. E-mail: tljw060606@163.com
基金资助:
中央高校基本科研业务费专项资金(批准号: FTF-TP-14-061A1)资助

Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles^†

YANG Ming¹, TANG Jia¹, WANG Jingjing¹, FAN Shuang¹, ZHANG Huan¹, TAO Liushi¹, TAN Li^2,^*()

1. Dalian National Laboratory for Clean Energy,
2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Received:2015-06-12 Online:2016-01-10 Published:2015-12-20
Contact: TAN Li E-mail:tljw060606@163.com

摘要/Abstract

摘要：

以Fe-MIL-101为非均相催化剂, 通过多种伯胺与2,5-二甲氧基四氢呋喃进行Paal-Knorr反应, 高效合成相应的吡咯衍生物. 在Fe-MIL-101结构中, 裸露的Fe(Ⅲ)配位点作为催化活性中心参与吡咯衍生物的催化合成反应. 同时Fe-MIL-101的高比表面积和大的孔尺寸确保了底物分子与催化活性中心的充分接触以及产物的自由脱离, 从而促进了催化反应的快速进行. Fe-MIL-101在催化反应过程中具有很好的稳定性, 多次循环使用后仍能表现出良好的催化性能. 此外, 该催化剂在伯胺(包括脂肪胺、芳香胺)与2,5-己二酮的Paal-Knorr缩合反应中也具有优异的催化性能.

关键词: Fe-MIL-101非均相催化剂, Paal-Knorr反应, 吡咯衍生物

Abstract:

A highly porous metal-organic frameworks(Fe-MIL-101) was synthesized as a heterogeneous catalyst for the Paal-Knorr reaction. The free coordination position of Fe(Ⅲ) in Fe-MIL-101 can be used as catalytic active sites for the Paal-Knorr reaction. The large surface area and pore size of Fe-MIL-101 contribute to offer an access for organic substrates to the active sites sufficiently, which ensure a high catalytic performance of Fe-MIL-101 for pyrroles. The catalyst could be reused five times without loss of its catalytic activity. In addition, the catalyst also exhibits high catalytic activity in other amines system with 2,5-hexane-dione for Paal-Knorr condensation reaction.

Key words: Fe-MIL-101 heterogeneous catalyst, Paal-Knorr reaction, Pyrrole derivative

中图分类号:

O643

TrendMD:

杨明, 汤甲, 王静静, 范爽, 张欢, 陶柳实, 谭丽. Fe-MIL-101催化Paal-Knorr反应合成吡咯衍生物. 高等学校化学学报, 2016, 37(1): 108.

YANG Ming, TANG Jia, WANG Jingjing, FAN Shuang, ZHANG Huan, TAO Liushi, TAN Li. Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles^†. Chem. J. Chinese Universities, 2016, 37(1): 108.

图/表 8

参考文献 35

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Entry	Catalyst	Time/min	Conversion(%)	Selectivity(%)
1		60	20.4	99.9
2	FeCl₃·6H₂O	50	99.9	99.9
3	Fe(NO₃)₃·9H₂O	50	99.9	99.9
4	Fe₂(SO₄)₃	50	98.8	99.9
5	Fe(C₅H₅)₂	50	13.3	99.9
6	Fe-MIL-101	50	98.9	99.9

Entry	Catalyst	Time/min	Conversion(%)	Selectivity(%)
1		60	20.4	99.9
2	FeCl₃·6H₂O	50	99.9	99.9
3	Fe(NO₃)₃·9H₂O	50	99.9	99.9
4	Fe₂(SO₄)₃	50	98.8	99.9
5	Fe(C₅H₅)₂	50	13.3	99.9
6	Fe-MIL-101	50	98.9	99.9

Entry	Solvent	Time/min	Conversion(%)	Selectivity(%)
1		50	2.4	99.9
2	C₂H₅OH^b	50	9.1	99.9
3	CH₃CN^b	50	12.5	99.9
4	CHC	50	17.7	99.9
5	C₄H₈O^b	50	31.0	99.9
6	C₂H₄C	50	8.7	99.9
7	H₂O^b	50	98.9	99.9
8	C₂H₄C	50	64.1	99.9
9	C₂H₄C	180	99.9	99.9

Entry	Solvent	Time/min	Conversion(%)	Selectivity(%)
1		50	2.4	99.9
2	C₂H₅OH^b	50	9.1	99.9
3	CH₃CN^b	50	12.5	99.9
4	CHC	50	17.7	99.9
5	C₄H₈O^b	50	31.0	99.9
6	C₂H₄C	50	8.7	99.9
7	H₂O^b	50	98.9	99.9
8	C₂H₄C	50	64.1	99.9
9	C₂H₄C	180	99.9	99.9

Entry	Temperature/℃	Time	Conversion(%)	Selectivity(%)
1	60	1 h	1.91	99.9
2	60	24 h	46.8	99.9
3	80	1 h	37.1	99.9
4	80	3 h	89.9	99.9
5	80	6 h	99.5	99.9
6	100	50 min	98.9	99.9
7	100	1 h	99.6	99.9

Fe-MIL-101催化Paal-Knorr反应合成吡咯衍生物

Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles^†

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Entry	Conversion(%)	Selectivity(%)	Entry	Conversion(%)	Selectivity(%)
1	98.9	99.9	5	99.4	99.9
2	99.9	99.9	6	99.7	99.9
3	99.7	99.9	7	98.2	99.9
4	99.0	99.9	8	99.4	99.9

Entry	Conversion(%)	Selectivity(%)	Entry	Conversion(%)	Selectivity(%)
1	93.6	99.9	6	91.8	99.9
2	53.2	99.9	7	67.8	99.9
3	93.4	99.9	8	99.0	99.9
4	99.0	99.9	9	99.0	99.9
5	96.7	99.9

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[2]	王建华, 范风格. 4-羰基-2-戊烯醛与硫代乙酸加成的研究[J]. 高等学校化学学报, 1991, 12(9): 1200.

Fe-MIL-101催化Paal-Knorr反应合成吡咯衍生物

Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles†

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Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles^†