Schiff碱功能化壳聚糖负载CuBr高效催化合成1,2,3-三唑化合物

doi:10.7503/cjcu20160252

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (10): 1863.doi: 10.7503/cjcu20160252

Schiff碱功能化壳聚糖负载CuBr高效催化合成1,2,3-三唑化合物

熊兴泉(), 江云兵, 肖上运, 石霖, 宋思达

福建省高校功能材料重点实验室, 华侨大学材料科学与工程学院, 厦门361021

收稿日期:2016-04-18 出版日期:2016-10-10 发布日期:2016-08-31
作者简介:联系人简介: 熊兴泉, 男, 博士, 副教授, 主要从事绿色有机合成方面的研究. E-mail:xxqluli@hqu.edu.cn
基金资助:
国家自然科学基金(批准号: 21004024)、福建省自然科学基金(批准号: 2016J01063)、福建省“高校新世纪优秀人才支持计划”(批准号: 2012FJ-NCET-ZR03)和“华侨大学中青年教师科研提升资助计划”(批准号: ZQN-YX103)资助

Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst^†

XIONG Xingquan^*(), JIANG Yunbing, XIAO Shangyun, SHI Lin, SONG Sida

College of Materials Science and Engineering, Huaqiao University, the Key Laboratory for Functional Materials of Fujian Higher Education, Xiamen 361021, China

Received:2016-04-18 Online:2016-10-10 Published:2016-08-31
Contact: XIONG Xingquan E-mail:xxqluli@hqu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21004024), the Natural Science Foundation of Fujian Province, China(No.2016J01063), the Program for New Century Excellent Talents in Fujian Province, China(No.2012FJ-NCET-ZR03) and the Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University, China(No.ZQN-YX103)

摘要/Abstract

摘要：

以壳聚糖为原料, 在乙醇溶液中通过将其与2-吡啶甲醛反应制得Schiff碱功能化的壳聚糖(PYCS), 然后将PYCS与CuBr进行络合反应制得负载型催化剂(PYCS-CuBr). 采用红外光谱、热重分析和X射线衍射分析等方法对PYCS-CuBr催化剂进行表征. 热重分析结果表明, 该催化剂在200 ℃以内具有较好的热稳定性, 能够满足其使用温度. 结合微波辐射技术以及“一锅法”合成策略, 以PYCS-CuBr为催化剂催化有机炔、卤代烷以及NaN₃之间的环加成反应. 结果表明, PYCS-CuBr催化剂具有良好的催化性能, 在微波辐射功率为480 W, 温度为70 ℃条件下, 15 min可快速制得1,2,3-三唑类化合物, 该催化剂易回收, 且可重复使用至少4次, 活性未见明显降低. 放大反应结果表明, 1,2,3-三唑类化合物能够以较高收率并以数十克规模制备.

关键词: 壳聚糖, Schiff 碱, 异相催化剂, 1, 2, 3-三唑

Abstract:

Pyridine-2-carboxaldehyde-modified chitosan(PYCS) was prepared through a simple procedure using chitosan(CS) and pyridine-2-carboxaldehyde in ethanol solution. Subsequently, PYCS supported CuBr(PYCS-CuBr) was synthesized by the reaction of PYCS with CuBr in acetone at room temperature under N₂ atmosphere. The obtained catalyst was characterized by FTIR, TGA and XRD. TGA result showed that the catalyst had a good stability up to 200 ℃ and could meet the normal use. The catalytic performances were evaluated in one-pot multi-component copper(Ⅰ)-catalyzed azide-alkyne cycloaddition(CuAAC) reaction under microwave-assisted condition. PYCS-CuBr was found to exhibit obvious catalytic activity to rapidly produce 1,2,3-triazole compounds under the microwave irradiation(480 W) at 70 ℃. Furthermore, the catalyst could be easily recovered by simple filtration and recycled at least 4 cycles without obvious loss of catalytic activity. 1,2,3-triazoles can be exclusively generated on multi-gram scale.

Key words: Chitosan, Schiff base, Heterogeneous catalyst, 1, 2, 3-Triazole

中图分类号:

O643.3
O631

TrendMD:

熊兴泉, 江云兵, 肖上运, 石霖, 宋思达. Schiff碱功能化壳聚糖负载CuBr高效催化合成1,2,3-三唑化合物. 高等学校化学学报, 2016, 37(10): 1863.

XIONG Xingquan, JIANG Yunbing, XIAO Shangyun, SHI Lin, SONG Sida. Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst^†. Chem. J. Chinese Universities, 2016, 37(10): 1863.

图/表 12

Fig.1 Pharmaceutical molecules based on five-membered heterocycle

Scheme 1 Preparation of PYCS-CuBr catalyst

Scheme 2 Synthesis of 1,2,3-triazoles via one-pot strategy

Fig.2 FTIR spectra of CS(a), PYCS(b), PYCS-CuBr(c) and 2-pyridinecarboxaldehyde(d)

Fig.3 TGA curves of CS(a), PYCS(b) and PYCS-CuBr(c)

Fig.4 XRD patterns of CS(a), PYCS(b) and PYCS-CuBr(c)

Fig.5 EDX images of fresh PYCS-CuBr(A) and reused PYCS-CuBr(B) catalysts

Table 1 Effect of the phase transfer catalyst on the CuAAC reactiona

Entry	PTC^b	t/min	Yield^c(%)
1		15	39
2	TMAI	15	81
3	TBAC	15	97
4	PEG-400	15	68
5	PEG-1000	15	57

Table 2 Effect of catalyst on the CuAAC reaction in water

Entry	Catalyst	t^a/min	Isolated yield^a(%)	t^b/min	Isolated yield^b(%)
1		15	11	240	<5
2	CS	15	20	240	<5
3	PYCS	15	10	240	<5
4	CuBr	15	86	240	82
5	CuCl	15	78	240	70
6	Cu(Ⅱ)^c	15	80	240	75
7	PYCS-CuBr	15/15^b	97/57^b	240	93

Table 3 One-pot synthesis of 1,2,3-trazoles under microwave in aqueous phase conditions

Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

Fig.6 Reusability of catalyst PYCS-CuBr

Table 4 Scale-up synthesis on the CuAAC reaction of the catalysta

Entry	n/mmol	m/g	Yield^b(%)	Entry	n/mmol	m/g	Yield^b(%)
1	1.97	0.5	96	5	118.5	22.8	82
2	19.7	4.4	95	6^c	19.7	4.4	94
3	39.5	8.6	93	7^d	19.7	4.3	93
4	59.2	12.0	86	8^e	19.7	4.1	87

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Schiff碱功能化壳聚糖负载CuBr高效催化合成1,2,3-三唑化合物

Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst^†

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Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

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Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

Schiff碱功能化壳聚糖负载CuBr高效催化合成1,2,3-三唑化合物

Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst†

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参考文献 27

相关文章 15

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Metrics

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Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst^†

Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85

Entry	t/min	Yield^*(%)
1	15	96
2	15	90
3	15	97
4	15	96
5	15	86
6	15	91
7	15	96
8	15	87
9	15	95
10	15	87
11	15	92
12	15	89
13	15	89
14	15	84
15	15	85