Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

• Published in: Green chemistry : an international journal and green chemistry resource : GC Vol. 23; no. 18; pp. 71 - 7114
• Main Authors: van Slagmaat, Christian A. M. R, Noordijk, Jurrie, Monsegue, Luciano G, Mogensen, Siri, Hadavi, Darya, Han, Peiliang, Quaedflieg, Peter J. L. M, Verzijl, Gerard K. M, Alsters, Paul L, De Wildeman, Stefaan M. A
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 20.09.2021
• Subjects: Catalysts; Cyclopentane; Diamines; Diketones; Furfural; Furfuryl alcohol; Green chemistry; Hydroxymethylfurfural; Isomerization; Isomers; Lactones; Monomers; Polyurethane; Synthesis
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/d1gc02372a

A novel and green route for the synthesis of cyclopentane-1,3-diamine ( CPDA ) from hemicellulosic feedstock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone ( 4-HCP ), (2) a highly improved isomerization of 4-HCP into cyclopentane-1,3-dione ( CPDO ) using the Ru Shvo catalyst, (3) conversion of CPDO into cyclopentane-1,3-dioxime ( CPDX ), and (4) a mild oxime hydrogenation of CPDX over Rh/C to afford the desired CPDA . In addition, diastereomerically pure cis - and trans -isomers of CPDA were reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer 5 , derived using γ-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes. Synthesis of cyclopentane-1,3-diamine from hemi-cellulosic origin is established for the first time, with useful chemical insights and potential applications demonstrated.