含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化

doi:10.1016/S1872-2067(15)61047-6

催化学报 ›› 2016, Vol. 37 ›› Issue (4): 533-538.DOI: 10.1016/S1872-2067(15)61047-6

含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化

朱英红, 张健青, 陈姿颖, 张安伦, 马淳安

浙江工业大学化工学院, 绿色化学合成技术培育基地, 浙江杭州 310032

收稿日期:2015-12-01 修回日期:2016-01-27 出版日期:2016-03-30 发布日期:2016-03-30
通讯作者: Chunan Ma
基金资助:
973计划前期研究专项(2012CB722604).

Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol

Yinghong Zhu, Jianqing Zhang, Ziying Chen, Anlun Zhang, Chunan Ma

State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China

Received:2015-12-01 Revised:2016-01-27 Online:2016-03-30 Published:2016-03-30
Contact: Chunan Ma
Supported by:
This work was supported by the Special Program for the National Basic Research Program of China(973 Program, 2012CB722604).

摘要/Abstract

摘要：

有机小分子的电催化氧化是催化领域的一个重要研究内容. 通过醇的选择性氧化合成相应醛或酮类化合物在精细化学品和有机化学中间体的合成领域均具有十分重要的意义. 有机电催化合成用电子代替强氧化还原剂, 可以使反应在比较温和的条件下进行. 但在直接电氧化合成反应中, 电极表面容易生成有机聚合物膜, 使电极钝化, 电流效率急剧下降. 而在电子转移媒质作用下的有机电催化反应不仅可以避免电极表面钝化, 还可以控制目标产物的过度氧化. 三芳胺类化合物是一类新型的电氧化还原媒质, 由于其具有较宽的电化学氧化还原电位已引起研究者的广泛关注. 咔唑类化合物相比于三芳胺类具有更好的平面性, 使得取代基效应更为显著. 咔唑类化合物被广泛作为荧光材料, 但用于电化学方面的研究很少. 本文通过在咔唑类化合物中引入具有强吸电子性的硝基以提高该类化合物的氧化电位, 并将其作为有机电催化媒质, 采用间接电化学氧化的方式, 在室温下研究醇的电化学催化氧化反应, 合成相应醛类化合物.
我们合成了三种含硝基咔唑类有机电催化剂, 通过¹H NMR对其结构进行了鉴定. 采用循环伏安法测试了该类有机电催化剂的电化学氧化还原性能. 发现取代基的电子效应对有机电催化剂的氧化还原电位及电化学氧化还原可逆性有很大的影响, 供电子基(-OCH₃)的引入使氧化电位负移(0.717 V), 吸电子基(-Br)的引入使氧化电位明显正移(1.282 V). 同时, 取代基的引入有效改善了有机电催化剂的电化学可逆性, 从而可以作为有效的电氧化还原媒质应用于电化学氧化反应中. 而当把化合物中的NO₂还原为NH₂后, 咔唑类化合物的电化学氧化还原可逆性完全消失, 表明硝基的引入对咔唑类有机电催化剂的电化学性能有很大的影响.
循环伏安结果发现, 在咔唑类硝基化合物的作用下, 对甲氧基苯甲醇(p-MBzOH)的电化学氧化峰电位从1.350 V降至1.286 V, 表明可以在较低电位下进行电解, 有效降低了电氧化反应的能耗, 同时氧化峰电流明显增加, 说明该类有机电催化剂对p-MBzOH具有良好的电催化性能. 随着p-MBzOH浓度的增加, 氧化峰电流也明显增大, 说明在咔唑类有机电催化剂的作用下, p-MBzOH可以在比较高的浓度下进行电化学氧化电解. 通过对不同对位取代基的苯甲醇类化合物进行循环伏安研究, 发现含硝基咔唑类化合物对具有较高氧化电位的反应底物均表现出良好的电催化氧化性能.
在含硝基咔唑类有机电催化剂的氧化电位(1.28 V)和室温下, 对不同浓度的p-MBzOH进行恒电位电解6 h, 发现当催化剂的用量为底物的2.5 mol%时, p-MBzOH可以完全转化为相应的醛类目标产物. 而且恒电位电解后分离回收的含硝基咔唑类有机电催化剂仍具有良好的电化学氧化还原可逆性.

关键词: 硝基咔唑类化合物, 有机电催化剂, 间接电氧化, 选择性电氧化, 氧化还原可逆性

Abstract:

Three compounds with nitrocarbazole frameworks were synthesized and their electrochemical reversibility as organic electrocatalysts was studied by cyclic voltammetry. The electrochemical reversibility and oxidation-reduction potential of the compounds were greatly affected by their substituents. The oxidation-reduction potential of the compound with an electron-donating group was negative, while that of the compound with an electron-withdrawing group on the carbazole framework was positive. The electrocatalytic oxidation activities of the nitrocarbazole compounds were investigated through cyclic voltammetry and controlled potential electrolysis at room temperature. The electrocatalysts showed excellent selectivity for p-methoxybenzyl alcohol, converting it to the corresponding aldehyde through electro-oxidation with just 2.5 mol% of the electrocatalysts presented. The electrocatalysts maintained their excellent electroredox activity following recycling.

Key words: Nitro-carbazole compounds, Organic electro-catalyst, Indirect electro-oxidation, Selective electro-oxidation, Redox reversibility

朱英红, 张健青, 陈姿颖, 张安伦, 马淳安. 含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化[J]. 催化学报, 2016, 37(4): 533-538.

Yinghong Zhu, Jianqing Zhang, Ziying Chen, Anlun Zhang, Chunan Ma. Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol[J]. Chinese Journal of Catalysis, 2016, 37(4): 533-538.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(15)61047-6

https://www.cjcatal.com/CN/Y2016/V37/I4/533

参考文献

[1] R. A. Sheldon, J. K. Kochi, Metal Catalyzed Oxidations of Organic Compounds: Mechanistic Principles and Synthetic Methodology Including Biochemical Processes, Academic Press, New York, NY, 1981, 326-328.
[2] M. Hudlicky, Oxidations in Organic Chemistry (ACS Monograph, No. 186), American Chemical Society, Washington, DC, 1990, 114-127.
[3] C. D. Pina, E. Falletta, M. Rossi, J. Catal, 2008, 260, 384-386.
[4] Y. Hao, S. Wang, Q. Sun, L. Shi, A. H. Lu, Chin. J. Catal., 2015, 36, 612-619.
[5] A. Z. Jia, L. L. Lou, C. Zhang, Y. Q. Zhang, S. X. Liu, J. Mol. Catal. A, 2009, 306, 123-129.
[6] Y. Y. Yu, B. Lu, X. G. Wang, J. X. Zhao, X. Z. Wang, Q. H. Cai, Chem. Eng. J., 2010, 162, 738-742.
[7] Y. L. Yu, B. J. Gao, Y. F. Li, Chin. J. Catal., 2013, 34, 1776-1786.
[8] T. A. D Nguyen, A. M. Wright, J. S. Page, G. Wu, T. W. Hayton, Inorg. Chem., 2014, 53, 11377-11387.
[9] B. A. Frontana-Uribe, R. D. Little, J. G. Ibanez, A. Palma, R. Vasquez-Medrano, Green Chem., 2010, 12, 2099-2119.
[10] H. J. Schäfer, M. Harenbrock, E. Klocke, M. Plate, A. Weiper- Idelmann, Pure Appl. Chem., 2007, 79, 2047-2057.
[11] E. Steckhan, Angew Chem., 1986, 98, 681-699.
[12] M. Platen, E. Steckhan, Chem. Ber., 1984, 117, 1679-1694.
[13] N. T. Zhang, C. C. Zeng, C. M. Lam, R. K. Gbur, R. D. Little, J. Org. Chem., 2013, 78, 2014-2110.
[14] R. Francke, R. D. Little, J. Am. Chem. Soc., 2014, 136, 427-435.
[15] Y. S. Park, S. C. Wang, D. J. Tantillo, R. D. Little, J. Org. Chem., 2007, 72, 4351-4357.
[16] K. Takahashi, T. Furusawa, T. Sawamura, S. Kuribayashi, S. Inagi, T. Fuchigami, Electrochim. Acta, 2012, 77, 47-53.
[17] S. M. Halas, K. Okyne, A. Fry, Electrochim. Acta, 2003, 48, 1837-1844.
[18] R. Wend, E. Steckhan, Electrochim. Acta, 1997, 42, 2027-2039.
[19] G. S. Liou, S. H. Hsiao, N. K. Huang, Y. L. Yang, Macromolecules, 2006, 39, 5337-5346.
[20] S. C. Dong, Z. Li, J. G. Qin, J. Phys. Chem. B, 2008, 113, 434-441.
[21] H. M. Wang, S. H. Hsiao, J. Polym. Sci. Part A, 2014, 52, 272-286.
[22] M. L. Keshtov, Y. A. Udum, L. Toppare, V. S. Kochurov, A. R. Khokhlov, Mater. Chem. Phys., 2013, 139, 936-943.
[23] K. B. Zheng, W. Y. Lin, L. Tan, Org. Biomol. Chem., 2012, 10, 9683-9688.
[24] A. N. Bakiev, E. V. Shklyaeva, I. V. Lunegov, I. G. Mokrushin, G. G. Abashev, Russ. J. Gen. Chem., 2014, 84, 1313-1319.
[25] S. F. Wu, Y. Liu, G. P. Yu, J. G. Guan, C. Y. Pan, Y. Du, X. Xiong, Z. G. Wang, Macromolecules, 2014, 47, 2875-2882.

含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化

Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 0

编辑推荐

Metrics