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

doi:10.7503/cjcu20160252

Abstract

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

CLC Number:

O643.3
O631

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1863.

Figures/Tables 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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