67136-05-4

Upstream product

• 112-62-9 Methyl oleate 
• 2566-91-8 epoxidized methyl oleate 
• 7297-29-2 methyl 9⁽¹⁰⁾-hydroxy 10⁽⁹⁾-oxo octadecanoate 
• 1931-63-1 methyl ester of azelaic acid aldehyde 
• 94-41-7 benzalacetophenone 
• 13481-97-5 dimethyl (Z)-octadec-9-ene-1,18-dioate 
• 20701-68-2 (9Z)-octadec-9-enedioic acid 

Downstream Products

• 1931-63-1 methyl ester of azelaic acid aldehyde 

Relevant academic research and scientific papers

Valorization of Methyl Azelaaldehydate – A Vegetable Oil Based Platform Molecule for the Synthesis of Monomers through Stetter Reaction

The valorization of vegetable oil-derived methyl azelaaldehydate (methyl 9-oxo-nonanoate) to monomers was studied through NHC-catalysed Stetter reaction. Among the Michael acceptors tested, dimethyl fumarate gave the highest selectivity (97 %) for the corresponding Stetter adduct, thus limiting the competing benzoin condensation.

Homogeneous and heterogeneous catalytic (dehydrogenative) oxidation of oleochemical 1,2-diols to α-hydroxyketones

Herein, the preparation of methyl oleate α-hydroxyketone from the corresponding 1,2-diol was investigated using both homogeneous and heterogeneous systems. Homogeneous conditions using a Pd(OAc)2/neocuproine complex were first developed using oxygen as a sole oxidant under mild conditions (MeOH, 50 °C). Under these conditions, the conversion of diol reached 95%, and α-hydroxyketone was obtained with 97% selectivity. The access to α-hydroxyketone has also been studied by dehydrogenation using a range of heterogeneous catalysts under solvent-free conditions at high temperatures (160-180 °C). Dehydrogenation using activated Ru/C under vacuum provided α-hydroxyketone with 93% conversion and 82% GC yield. The optimized conditions were applied to a range of oleochemical diols, including a vegetable oil derivative, to obtain the corresponding α-hydroxyketones with up to 74% isolated yields.

Thiazolylidene-Catalyzed Cleavage of Methyl Oleate-Derived α-Hydroxy Ketone to the Corresponding Free Aldehydes

The thiazolylidene-catalyzed cleavage of the α-hydroxy ketone derived from methyl oleate gave the corresponding aldehydes under nonoxidative conditions through a retro-benzoin process. The aldehydes produced are in equilibrium with their corresponding acyloins. To illustrate the synthetic utility of this protocol, the aldehydes were recovered by distillation.