三丁基锡/SBA-15功能配合物的合成、表征及对Friedel-Crafts反应的选择性催化

doi:10.3724/SP.J.1095.2013.20580

摘要/Abstract

摘要： 将三丁基氯化锡与SBA-15介孔分子筛在N2气气氛中进行回流反应，得到有机锡无机配合物(C4H9)3Sn-O-SBA-15[Bu3SnS]。利用X射线衍射(XRD)、透射电子显微镜(TEM)、氮气吸附脱附、固体核磁（NMR）和吡啶吸附脱附红外光谱分析(Py-IR)等方法对产物的组成、结构和性质进行了表征。结果表明，产物Bu3SnS具有高度有序的六方介孔结构，与SBA-15相比，Bu3SnS比表面积、孔容和孔径变小，酸性增强。 Bu3SnS对苯甲醚Friedel-Crafts酰基化反应具有优异的催化性能，当反应温度为130 ℃，n（苯甲醚）∶n（苯甲酰氯）=1.0∶2.0，w（cat）=6%（相对于苯甲醚用量），反应时间为5 h，苯甲醚的转化率达到76.0%，对甲氧基二苯酮（p-MBP）选择性达到97.8%。

关键词: 三丁基锡, SBA-15, 功能配合物, Friedel-Crafts反应, 选择性催化

Abstract: The organotin inorganic complexes (C4H9)3Sn-O-SBA-15[Bu3SnS] were successfully synthesized by grafting tributyltin on SBA-15 mesoporous molecular sieves in a nitrogen atmosphere. The composition, structure and properties of the samples were characterized by X-ray diffraction(XRD), transmittance electron microscopy(TEM), Hammett indicator method, N2 adsorption-desorption, solid nuclear magnetic resonance(NMR) , in-situ pyridine infrared spectroscopy(Py-IR) and so on. The results show that the hexagonal P6mm mesostructure of parent siliceous SBA-15 is maintained in Bu3SnS. The surface areas, proe size and volume of Bu3SnS are all deceased with the increase of acidity, compared to those of SBA-15. Friedel-Crafts acylation of anisole and benzoyl chloride can be efficiently catalyzed in the presence of Bu3SnS. The reaction conversion of anisole and the selectivity of p-benzoylanisole are 76.0% and 97.8%, respectively, when the molar ratio of anisole to benzoyl chloride is 0.5∶1.0, the amount of catalyst is 6%, the reaction temperature is 130 ℃ and the reaction time is 5 h.

Key words: tributyltin, SBA-15, functional complex, Friedel-Crafts reaction, selective catalytsis

中图分类号:

O643

荆, 涛, 覃志乐, 宋伟明, 赵云鹏, 邓启刚. 三丁基锡/SBA-15功能配合物的合成、表征及对Friedel-Crafts反应的选择性催化[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20580.

JING Tao, QIN Zhile, SONG Weiming*, ZHAO Yunpeng, DENG Qigang. Synthesis, Characterization and Catalytic Performance Toward the Friedel-Crafts Acylation of Tributyltin Functionalized SBA-15[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20580.

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