Obtaining (5-formylfuran-2-yl)methyl 4-chlorobenzoate through an esterification of 5-hydroxymethylfurfural: Interesting achiral molecule crystallizing in a Sohncke P 2 1 2 1 2 1 space group

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 degrees 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 P 2 1 2 1 2 1 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. (c) 2022 Elsevier B.V. All rights reserved.

Automated summary

In this study, the catalyst-free synthesis of (5-formylfuran-2-yl)methyl 4-chlorobenzoate was achieved by an O-acylation reaction of 5-hydroxymethylfurfural with 4-chlorobenzoyl chloride using a slight excess of triethylamine in dichloromethane. The structure of the compound was characterized by various spectroscopic techniques and it was found to crystallize in a Sohncke P212121 space group, indicating its potential nonlinear optic property.