Trialkylamine-Catalyzed Aldolization of Unprotected 1,3-Dihydroxyacetone (DHA) toward C–C Bond-Linked Tetraol Surfactants

Biwen Zhu (1) , Dorine Belmessieri (1) , Jesús Fermin Ontiveros (2) , Jean-Marie Aubry (2) , Guo-Rong Chen (3) , Nicolas Duguet (1) , Marc Lemaire (1)

1 CASYEN - Catalyse Synthèse et Environnement
2 UCCS - Unité de Catalyse et Chimie du Solide - UMR 8181
3 East China University of Science and Technology

The aldolization of unprotected 1,3-dihydroxyacetone (DHA) was studied under mild conditions (20 °C) in a mixture of water/EtOH using hydrocinnamaldehyde as a model substrate. It was shown that trimethylamine is the most effective base for this transformation, giving the corresponding aldol with up to 98% selectivity and 82% yield. The method was extended to a range of (biobased) aldehydes to give α-hydroxyketones with 29–70% isolated yields. These α-hydroxyketones were reduced under hydrogen using 5%-Ru/Al2O3 in EtOH at 100 °C to give tetraols with 79–97% isolated yields. The physicochemical properties of these tetraols were studied (CMC, Krafft point, PIT-slope method), and these studies revealed that this new class of C–C bond-linked nonionic surfactants exhibits high effectiveness, reducing the surface tension of water.

Keywords: Aldolisation; 1; 3-Dihydroxyacetone; Surfactants; Tetraols; Trialkylamines

Domains: Organic chemistry; Catalysis

Biwen Zhu, Dorine Belmessieri, Jesús Fermin Ontiveros, Jean-Marie Aubry, Guo-Rong Chen, et al.. Trialkylamine-Catalyzed Aldolization of Unprotected 1,3-Dihydroxyacetone (DHA) toward C–C Bond-Linked Tetraol Surfactants. ACS Sustainable Chemistry & Engineering, 2018, 6 (2), pp.2630-2640. ⟨10.1021/acssuschemeng.7b04135⟩. ⟨hal-02128577⟩