Oxidative cleavage of C–C double bond in cinnamic acids with hydrogen peroxide catalysed by vanadium(v) oxide. Issue 5 (14th February 2022)

• Record Type: Journal Article
• Authors: Horvat, Monika; Iskra, Jernej
• Is Part Of: Green chemistry. Volume 24:Issue 5(2022)
• Page Start: 2073
• Page End: 2081
• Publication Date: 2022-02-14
• Subjects: Environmental chemistry -- Industrial applications -- Periodicals; Environmental management -- Periodicals; 660
• DOI: 10.1039/d1gc04416h
• Languages: English
• ISSNs: 1463-9262

Abstract

Abstract : A simple process to cleave C=C bonds with H2 O2 converts cinnamic acids to benzaldehydes, benzoic acids or quinones, with selectivity depending on the solvent. A comparison of green metrics was performed for the conversion of ferulic acid to vanillin. Abstract : 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 – MeOCH2 CH2 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.