Xu Shurui, Wu Jie, Huang Peng, Lao Chunwen, Lai Hanchao, Wang Yuxiong, Wang Zhenyu, Zhong Guoyu, Fu Xiaobo, Peng Feng
Engineering Research Center of None-food Biomass Efficient Pyrolysis and Utilization Technology of Guangdong Higher Education Institutes, Dongguan University of Technology, Dongguan, China.
Key Laboratory of Distributed Energy Systems of Guangdong Province, School of Chemical Engineering and Energy Technology, Dongguan University of Technology, Dongguan, China.
Front Chem. 2020 Mar 20;8:151. doi: 10.3389/fchem.2020.00151. eCollection 2020.
In this paper, ferric nitrate was used to oxidize benzyl alcohol in a mild condition and demonstrated its better performance compared to HNO. In the reaction, the conversion rate and product selectivity could be both as high as 95% in N atmosphere, while the benzaldehyde yield also reached 85% in air. Similar to Fe(NO)·9HO, the other metallic nitrates such as Al(NO)·9HO and Cu(NO)·3HO could also oxidize the benzyl alcohol with high activity. The applicability of Fe(NO)·9HO for other benzylic alcohol was also investigated, and the reaction condition was optimized at the same time. The results showed the Fe(NO)·9HO would be more conducive in oxidizing benzyl alcohol under the anaerobic condition. The experiments in N or O atmospheres were conducted separately to study the catalytic mechanism of Fe(NO). The results showed the co-existence of Fe and will generate high activity, while either was with negligible oxidation property. The cyclic transformation of Fe and Fe provided the catalytic action to the benzyl alcohol oxidation. The role of was also an oxidant, by providing HNO in anaerobic condition, while would be regenerated from NO in aerobic condition. O did not oxidize the benzyl alcohol conversion directly, while it could still be beneficial to the procedure by eliminating the unwelcome NO and simultaneously reinforcing the circulation of Fe and Fe, which therefore forms a green cyclic oxidation. Hence, the benzyl alcohol oxidation was suggested in an air atmosphere for efficiency and the need of green synthesis.
本文中，硝酸铁用于在温和条件下氧化苯甲醇，并显示出比硝酸更好的性能。在该反应中，在氮气气氛下转化率和产物选择性均可高达95%，而在空气中苯甲醛产率也达到85%。与硝酸铁九水合物类似，其他金属硝酸盐如硝酸铝九水合物和硝酸铜三水合物也能以高活性氧化苯甲醇。还研究了硝酸铁九水合物对其他苄醇的适用性，同时优化了反应条件。结果表明，硝酸铁九水合物在厌氧条件下更有利于氧化苯甲醇。分别在氮气或氧气气氛中进行实验以研究硝酸铁的催化机理。结果表明，铁和（此处原文可能有误，推测是某个相关物质）共存会产生高活性，而单独任何一种的氧化性能都可忽略不计。铁和亚铁的循环转化为苯甲醇氧化提供了催化作用。（此处原文可能有误，推测是某个相关物质）的作用也是一种氧化剂，在厌氧条件下提供硝酸，而在有氧条件下会从一氧化氮再生。氧气不会直接氧化苯甲醇转化，但它通过消除有害的一氧化氮并同时加强铁和亚铁的循环，仍对该过程有益，从而形成绿色循环氧化。因此，建议在空气气氛中进行苯甲醇氧化以提高效率并满足绿色合成的需求。
