Obtaining (5-formylfuran-2-yl)methyl 4-chlorobenzoate through an esterification of 5-hydroxymethylfurfural: Interesting achiral molecule crystallizing in a Sohncke P212121 space group

Abstract

We report the catalyst-free synthesis of (5-formylfuran-2-yl)methyl 4-chlorobenzoate in 71% yield by an O-acylation reaction of 5-hydroxymethylfurfural with 4-chlorobenzoyl chloride using a slight excess of triethylamine in dichloromethane at 20 °C for 24 h. The structure of the 5-HMF aryl ester was characterized by FT–IR, UV–Vis, 1D and 2D NMR spectroscopy, mass spectrometry, and differential scanning calorimetry (DSC). This compound was recrystallized from methanol at ambient temperature under normal pressure conditions. X-Ray diffraction analyses show that achiral 5-HMF aryl ester crystallizes in a Sohncke P212121 space group, which could be related to a potential nonlinear optic property from inexpensive and readily abundant biomass sources. In the supramolecular structure, short hydrogen bonds were detected. However, computed CE-B3LYP (kJ/mol) intermolecular interaction energies indicate that the growth of the crystal is preferentially driven by dispersion forces.