Sustainable route to methyl-9-hydroxononanoate (polymer precursor) by oxidative cleavage of fatty acid methyl ester from rapeseed oil

Abstract

International audienceFatty acid methyl esters from rapeseed oil can be converted to monomers for polymer industries (85% methyl-9-hydroxynonanoate) by an oxydoreductive cleavage step in solvent free medium at room temperature, followed by a reduction step. All by-products are valuable and the reactions are performed under mild conditions

Oxidative Cleavage of Methyl 9,10‐Epoxystearate over WO3/MCM‐41 for Methyl 9‐Oxononanoate Production

“…In previous reports, oxidative cleavage of UFAME mostly resulted in carboxylic acids rather than aldehydes. To obtain aldehydes from UFAME, the methods of reductive ozonolysis and Fe catalysis are the direct routes that provides fatty aldehydes. Yet, ozone used in the reductive ozonolysis is not environmentally friendly, and Fe‐catalyzed way has the long reaction time with complex reaction conditions.…”

“…Because the epoxy bond in EFAME is often not as stable as CC double bond and EFAME is an intermediate in the process of oxidative cleavage of UFAME with H 2 O 2 , it is worth considering that EFAME as the starting material undergo the cleavage reaction for the fatty aldehydes production under more gentle conditions . Fatty aldehydes obtained from EFAME are of great interest for various applications, for example, it can be transformed into a monomer for use in polymer industry (Scheme ) . However, few reports on the oxidative cleavage of EFAME were found.…”

One-pot ozonolytic synthesis of acyclic α,ω-bifunctional compounds from methyl 10-undecenoate and 10-undecen-1-ol

“…For example, ozonolysis of unsaturated ester 1 allows preparation of methyl 10-hydroxydecanoate (3) in 91% yield after treatment with NaBH 4 [4] or in 98% yield after treatment with BH 3 -Me 2 S [5], or of methyl 9-formylnonanoate in 93% yield after hydrogenation on Pd/C [6], in 80-85% yield after treatment with Me 2 S [7,8], in 60% yield after treatment with triethylamine [9], and in 83% yield after treatment with Zn/AcOH [10]. Ozonolytic transformations of unsaturated alcohol 2 were not studied.…”

“…On replacement of methanol by isopropanol, the reaction with hydroxylamine hydrochloride becomes less selective and yields a mixture of methyl isopropyl sebacate (5), methyl hydrogen sebacate (6), and methyl 9-cyanononanoate (7), separated chromatographically.…”

“…When the ozonolysis products were treated with semicarbazide hydrochloride, methyl hydrogen sebacate (6) was obtained in high yield as the only product (Scheme 3).…”