Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid

Abstract

Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid Beerthuis, R.; Granollers, M.; Brown, D.R.; Salavagione, H.J.; Rothenberg, G.; Shiju, N.R. Published in: RSC Advances DOI:10.1039/c4ra12695eLink to publication Citation for published version (APA):Beerthuis, R., Granollers, M., Brown, D. R., Salavagione, H. J., Rothenberg, G., & Shiju, N. R. (2015). Catalytic acetoxylation of lactic acid to 2-acetoxypropionic acid, en route to acrylic acid. RSC Advances, 5(6), 4103-4108. DOI: 10.1039/c4ra12695e General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present an alternative synthetic route to acrylic acid, starting from the platform chemical lactic acid and using heterogeneous catalysis. To improve selectivity, we designed an indirect dehydration reaction that proceeds via acetoxylation of lactic acid to 2-acetoxypropionic acid. This intermediate can then be pyrolized to acrylic acid. Acetic acid is used both as a reagent and a solvent in the first step, and may be recovered in the subsequent pyrolysis step. We tested a range of solid acid catalysts for the acetoxylation step (Y zeolites, sulfated zirconia, ion-exchange resins, sulfonated graphene, and various sulfonated silica gels and mixed oxides). Recycling studies were carried out for the most active catalysts. To enable quantitative analysis using gas chromatography we also developed a reliable silylation derivatization method, which is also reported. These results open opportunities for improving the biorenewable production of acrylic acid.

Bio‐Acrylates Production: Recent Catalytic Advances and Perspectives of the Use of Lactic Acid and Their Derivates

“…According to an extensive screening of the solid acid catalysts, Amberlyst 70, Nafion NR50, sulfonic acid‐functionalized activated carbon and sulfonated graphene were the most active solid replacements of sulfuric acid (with 83–90 % selectivity at 41–44 % LA conversion), while the activity of sulfated zirconia and zeolites was too low . The most promising procedure up to now is the use of a reactive distillation technology in presence of Amberlyst ion‐exchange resin as the solid catalyst, allowing to reach almost full LA conversion with up to 96 % APA selectivity…”

Dehydration of Lactic Acid: The State of The Art

“…The dehydration reaction of lactic acid to acrylic acid is thoroughly studied in the gas phase in one step, but also in water under supercritical and subcritical conditions even indirectly (acetoxylation of lactic acid to 2 ‐acetoxypropionic acid that is then pyrolysed to acrylic acid) (Scheme ).…”

Graphene oxide based solid acid as an efficient and reusable nano-catalyst for the green synthesis of diindolyl-oxindole derivatives in aqueous media

“…Recently, GO has been used as heterogeneous catalyst in reactions such as the oxidation of sulfides and thiols, oxidation of benzylic positions, and benzyl alcohol, ring opening of epoxides, aza-Michael addition reaction, synthesis of aldehydes or ketones and Friedel-Crafts addition of indoles to a,b-unsaturated ketones [8][9][10][11][12][13][14][15]. Moreover, sulfated GO was tested as a catalyst for the acetoxylation of lactic acid to 2-acetoxypropionic acid, the Beckmann condensation and hydration of propylene oxide [16,17]. In addition, some studies have demonstrated that the immobilization of transition metal nanoparticles on GO produce efficient catalysts [18][19][20][21].…”