硅烷偶联化壳聚糖负载CuBr高活性催化合成1,2,3-三唑化合物

Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Silane Coupled Chitosan-Cu Br Catalyst

以壳聚糖为原料,将其与N-(2-氨乙基)-3-氨丙基三乙氧基硅烷(AAPTS)反应制得胺基功能化的壳聚糖(CS-AAPTS),然后将CS-AAPTS与Cu Br进行络合制备得到负载型催化剂(CS-Cu Br).通过FT-IR,TGA,XRD以及EDX等分析方法对CS-Cu Br催化剂进行表征.结合微波辐射技术以及"一锅法"合成策略,以CS-Cu Br为催化剂催化有机炔、卤代烷以及Na N3之间的环加成反应制备1,2,3-三唑.结果表明,CS-Cu Br具有良好的催化性能,微波辐射功率为480W,温度为70℃条件下,可快速合成出1,2,3-三唑类化合物.CS-Cu Br易回收和重复使用,重复使用4次后仍可保持良好收率.初步放大实验表明,1,2,3-三唑类化合物能够以94%的收率以十数克规模制备.

N-（2-Aminoethyl）-3-aminopropyltriethoxysilane-modified chitosan （CS-AAPTS） was successfully prepared by simply refluxing the corresponding CS and AAPTS in toluene solution. Subsequently, CS-AAPTS bound CuBr （CS-CuBr） was synthesized by the reaction of CS-AAPTS with CuBr in DMF at room temperature under N2 atmosphere. The obtained catalyst was characterized by FT-IR, TGA, XRD and EDX. The catalytic performances were evaluated in one-pot multicom- ponent copper-catalyzed azide-alkyne cycloaddition （CuAAC） reaction under microwave-assisted condition. CS-CuBr was found to exhibit obvious catalytic activity to rapidly prepare 1,2,3-triazole compounds under the microwave irradiation power of 480 W and 70℃ operating conditions. Furthermore, the catalyst could be easily recovered by simple filtration and recycled at least 4 cycles without significant loss of activity, and the preparation of 1,2,3-triazoles could be scaled up to multiole-gram conveniently with a yield uo to 94%.