Citation: Cao Zhicheng, Liu Jianchao, Chu Youqun, Zhao Fengming, Zhu Yinghong, She Yuanbin. Paired Electro-synthesis of Aryl Nitriles[J]. Chinese Journal of Organic Chemistry, ;2019, 39(9): 2499-2506. doi: 10.6023/cjoc201903052 shu

Paired Electro-synthesis of Aryl Nitriles

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032

Corresponding author: Zhu Yinghong, yhzhuchem@zjut.edu.cn She Yuanbin, sheyb@zjut.edu.cn
Received Date: 24 March 2019
Revised Date: 30 April 2019
Available Online: 15 September 2019
Fund Project: the National Program on Key Basic Research Project 973 Program, No. 2012CB722604Project supported by the National Key Research and Development Program of China (No. 2017YFB0307503) and the National Program on Key Basic Research Project (973 Program, No. 2012CB722604)the National Key Research and Development Program of China 2017YFB0307503

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The electro-oxidation cyanation of p-methoxybenzyl alcohol (p-MeOC₆H₄CH₂OH) to prepare aryl nitriles was studied by using cyclic voltammetry (CV) and constant current electrolysis (CCE). The effects of the volume ratio of H₂O, concentration of H₂SO₄, temperature, electrode materials, current density and solvents on the electro-chemical reaction were studied. The results showed that the yield of p-methoxylbenzonitrile (p-MeOBN) was 90% in 0.15 mol·L^-1 H₂SO₄ and 30% H₂O-DMSO solution at 60℃ and 10 mA/cm² of current density when tetrabutylammonium perchlorate (Bu₄NClO₄) was used as electrolyte. The CCE of aromatic benzyl alcohols with different p-and o-substituted analogs was investigated under the optimized reaction conditions, and the yields toward formation of the corresponding aryl nitriles were 61%~92%. A plausible mechanism for the electro-oxidation cyanation procedure was proposed. A novel paired electrochemical method for the synthesis of aryl nitriles from aromatic benzyl alcohols with hydroxylamine (HAM) as "N" source and aldehyde in situ in undivided electrochemical cell was successfully developed.
- aromatic benzyl alcohols,
- aryl nitriles,
- direct electro-oxidation,
- paired electro-synthesis
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