Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
권호 표지
DOI QR코드

DOI QR Code

Selective Conversion of Benzyl Alcohol to Benzaldehyde via Anodic Oxidation Using the Constant Current Method

정전류법 양극산화를 통한 벤질알코올로부터 벤즈알데하이드의 선택적 변환

  • Keunyoung Lee (Department of Chemistry and Research Institute for Green Energy Convergence Technology, Gyeongsang National University) ;
  • Ki-Young Kwon (Department of Chemistry and Research Institute for Green Energy Convergence Technology, Gyeongsang National University)
  • 이근영 (경상국립대학교 화학과) ;
  • 권기영 (경상국립대학교 화학과)
  • Received : 2024.11.12
  • Accepted : 2024.11.18
  • Published : 2024.12.10
Download PDF
⟨ Previous Next ⟩

Abstract

This study focuses on optimizing the reaction conditions for selectively oxidizing benzyl alcohol to benzaldehyde through a cost-effective and environmentally friendly electrochemical anodic oxidation process. To minimize the formation of cyanomethylation byproducts (3-phenyl-3-hydroxypropanenitrile), previously observed under constant voltage conditions (1.9 V), a constant current method (3 mA/㎠) was introduced. After a 16-hour reaction, a complete conversion (100%) of benzyl alcohol was achieved, yielding benzaldehyde as the main product, along with approximately 9% benzoic acid byproduct and a small amount of TBAP-related impurities. Additionally, experiments were conducted by replacing TBAP with TBAN as the electrolyte to reduce impurity formation; the advantages of the usage of TBAN are discussed.

본 연구는 친환경적이고 비용 효율적인 전기화학적 양극 산화 반응을 통하여 선택적으로 벤질알코올을 벤즈알데하이드로 산화하는 최적의 반응 조건을 모색하는 데 중점을 두었다. 기존 정전압 방식(1.9 V)에서 발생하는 cyanomethylation화된 부산물(3-phenyl-3-hydroxypropanenitrile)을 최소화하고자, 정전류 방식(3 mA/㎠)을 도입하였다. 반응 16 시간 후 100%의 벤질알코올 전환율을 달성했으며, 벤즈알데하이드를 주생산물로 생성하는 동시에 약 24.6%의 벤조산 부산물과 전해질인 tetrabutylammonium perchlorate (TBAP)와 연관된 불순물이 소량으로 존재함을 확인하였다. 추가적으로, 전해질로 TBAP를 사용할 때 발생하는 불순물의 감소를 위해 tetrabutylammonium nitrate (TBAN)로 교체하여 실험하였으며, 이에 대한 벤즈알데하이드로의 선택성 향상에 관하여 토의하였다.

Keywords

Acknowledgement

본 연구는 2022년 교육부의 재원으로 지역대학우수과학자지원사업(NRF-2022R1I1A3071407), 2020년도 교육부의 재원으로 한국기초과학지원연구원 국가연구시설 장비진흥센터 (2019R1A6C1010042) 지원과 2024년도 경상국립대학교 연구년제 연구교수 연구지원비에 의하여 수행되었음.

References

  1. C. Della Pina, E. Falletta, and M. Rossi, Highly selective oxidation of benzyl alcohol to benzaldehyde catalyzed by bimetallic gold–copper catalyst, J. Catal., 260, 384-386 (2008). https://doi.org/10.1016/j.jcat.2008.10.003
  2. X. Fu, J. Feng, H. Wang, and K. M. Ng, Room temperature synthesis of a novel γ-MnO2 hollow structure for aerobic oxidation of benzyl alcohol, Nanotechnology, 20, 375601 (2009). https://doi.org/10.1088/0957-4484/20/37/375601
  3. N. Jose, S. Sengupta, and J. K. Basu, Selective production of benzaldehyde by permanganate oxidation of benzyl alcohol using 18-crown-6 as phase transfer catalyst, J. Mol. Catal. A: Chem., 309, 153-158 (2009). https://doi.org/10.1016/j.molcata.2009.05.009
  4. M. Yang, Q. Ling, H. Yang, C. Li, and A. Zhang, Enhanced catalytic activity of K-birnessite MnO2 confined in carbon nanotubes for selective oxidation of benzyl alcohol, Catal. Commun., 46, 238-241 (2014). https://doi.org/10.1016/j.catcom.2013.12.031
  5. M. M. Heravi, N. Ghalavand, and E. Hashemi, Hydrogen Peroxide as a Green Oxidant for the Selective Catalytic Oxidation of Benzylic and Heterocyclic Alcohols in Different Media: An Overview, Chemistry, 2, 101-178 (2020). https://doi.org/10.3390/chemistry2010010
  6. A. Tashiro, A. Mitsuishi, R. Irie, and T. Katsuki, (NO)Ru(salen) catalyzed aerobic oxidation of o-hydroxybenzyl alcohol derivatives, Synlett, 12, 1868-1870 (2003).
  7. M. Kitano, M. Matsuoka, M. Ueshima, and M. Anpo, Recent developments in titanium oxide-based photocatalysts, Appl. Catal. A: Gen., 325, 1-14 (2007). https://doi.org/10.1016/j.apcata.2007.03.013
  8. J. Luo, H. Yu, H. Wang, H. Wang, and F. Peng, Aerobic oxidation of benzyl alcohol to benzaldehyde catalyzed by carbon nanotubes without any promoter, Chem. Eng. J., 240, 434-442 (2014). https://doi.org/10.1016/j.cej.2013.11.093
  9. C. M. Crombie, R. J. Lewis, R. L. Taylor, D. J. Morgan, T. E. Davies, A. Folli, D. M. Murphy, J. K. Edwards, J. Qi, H. Jiang, C. J. Kiely, X. Liu, M. S. Skjøth-Rasmussen, and G. J. Hutchings, Enhanced selective oxidation of benzyl alcohol via in situ H2O2 production over supported Pd-based catalysts, ACS Catal., 11, 2701-2714 (2021). https://doi.org/10.1021/acscatal.0c04586
  10. S. G. Savari and S. J. Selvaraj, The highly effective electrochemical oxidation of substituted benzyl alcohols in a biphasic medium is mediated by bromate on a platinum electrode, Anal. Bioanal. Electrochem., 15, 587-602 (2023).
  11. G. Qiu, H. Huang, S. Dharmarathna, E. Benbow, L. Stafford, and S. L. Suib, Hydrothermal synthesis of manganese oxide nanomaterials and their catalytic and electrochemical properties, Chem. Mater., 23, 3892-3901 (2011). https://doi.org/10.1021/cm2011692
  12. G. S. Shanker, A. Ghatak, S. Binyamin, R. Balilty, R. Shimoni, I. Liberman, and I. Hod, Regulation of catalyst immediate environment enables acidic electrochemical benzyl alcohol oxidation to benzaldehyde, ACS Catal., 14, 5654-5661 (2024). https://doi.org/10.1021/acscatal.4c00476
  13. J. Bai, L. Chen, C. Lv, H. Ruo, Y. Pan, S. Xu, J. Chen, B. Yang, D. Zhang, and H. Yang, Synergistic effects of vanadium incorporation in cobalt-based LDH on electron and proton transfer during electrocatalytic benzyl alcohol oxidation, New J. Chem., 48, 8436-8444 (2024). https://doi.org/10.1039/D4NJ00728J
  14. R. Li, P. Kuang, L. Wang, H. Tang, and J. Yu, Engineering 2D NiO/Ni3S2 heterointerface electrocatalyst for highly efficient hydrogen production coupled with benzyl alcohol oxidation, Chem. Eng. J., 431, 134137 (2022). https://doi.org/10.1016/j.cej.2021.134137
  15. H. Choi, J. An, and K.-Y. Kwon, Electrochemical synthesis of β-hydroxynitrile by addition of acetonitrile into benzyl alcohol, Appl. Chem. Eng., 33, 436-439 (2022).
  16. J. Nikl, K. Hofman, S. Mossazghi, I. C. Möller, D. Mondeshki, F. Weinelt, F.-E. Baumann, and S. R. Waldvogel, Electrochemical oxo-functionalization of cyclic alkanes and alkenes using nitrate and oxygen, Nat. Commun., 14, 4565 (2023) https://doi.org/10.1038/s41467-023-40259-0