Oxidative cleavage of C–C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(V) oxide

Horvat, Monika (author), Iskra, Jernej (author)

We have developed a cheap, green, mild and environmentally friendly method for the selective cleavage of carbon–carbon double bonds with a 30% aqueous solution of hydrogen peroxide as the oxidant and vanadium(V) oxide as the catalyst. The selectivity of the oxidative cleavage of cinnamic acid derivatives 1 depends on the substituents and the solvent used (DME – MeOCH$_2$CH$_2$OMe, TFE – 2,2,2-trifluoroethanol or MeCN). In DME, p-hydroxy derivatives were selectively converted to benzaldehyde derivatives 2, in TFE, oxidative cleavage led to the formation of benzoquinone derivatives 4, while in MeCN, cinnamic acid derivatives were selectively converted to benzoic acid derivatives 3. Ferulic acid 1a was quantitatively and selectively converted to vanillin 2a in a 91% isolated yield on a gram scale. Dimeric difurandione 1a’ was isolated as an intermediate, which was confirmed by in situ ATR-IR spectroscopy, while the formation of diols or epoxides was not observed. The analogous styrene derivative, 4-vinylguaiacol 1e was also selectively converted to either vanillin 2a or 2-methoxyquinone 4a in a high yield. The green metric for the conversion of ferulic acid to vanillin by different methods was calculated and compared to our method, and showed that our method has better environmental parameters.

• Language: English
• Keywords: lignocellulosic biomass, oxidation, lignin, ferulic acid, vanillin, hydrogen peroxide
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2022
• Number of pages: Str. 2073-2081
• Numbering: Vol. 24, iss. 5
• PID: 20.500.12556/RUL-141871
• UDC: 547.5:542.943'7
• ISSN on article: 1463-9262
• DOI: 10.1039/D1GC04416H
• COBISS.SI-ID: 97890051
• Publication date in RUL: 10.10.2022

Record is a part of a journal

• Title: Green chemistry
• Shortened title: Green chem.
• Publisher: Royal Society of Chemistry
• ISSN: 1463-9262
• COBISS.SI-ID: 24129285

Licences

• License: CC BY-NC 3.0, Creative Commons Attribution-NonCommercial 3.0 Unported
• Link: http://creativecommons.org/licenses/by-nc/3.0/
• Description: You are free to reproduce and redistribute the material in any medium or format. You are free to remix, transform, and build upon the material. You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. You may not apply legal terms or technological measures that legally restrict others from doing anything the license permits.

Secondary language

• Language: Slovenian
• Keywords: lignocelulozna biomasa, oksidacija, lignin, ferulna kislina, vanilin, vodikov peroksid

Projects

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0134
• Name: Kemija za trajnostni razvoj

• Funder: EC - European Commission
• Funding programme: European Regional Development Fund, Urban Innovative Actions
• Acronym: APPLAUSE