title: Gas-phase basicity of 2-furaldehyde.
abstract: 2-Furaldehyde (2-FA), also known as furfural or 2-furancarboxaldehyde, is an heterocyclic aldehyde that can be obtained from the thermal dehydration of pentose monosaccharides. This molecule can be considered as an important sustainable intermediate for the preparation of a great variety of chemicals, pharmaceuticals and furan-based polymers. Despite the great importance of this molecule, its gas-phase basicity (GB) has never been measured. In this work, the GB of 2-FA was determined by the extended Cooks's kinetic method from electrospray ionization triple quadrupole tandem mass spectrometric experiments along with theoretical calculations. As expected, computational results identify the aldehydic oxygen atom of 2-FA as the preferred protonation site. The geometries of O-O-cis and O-O-trans 2-FA and of their six different protomers were calculated at the B3LYP/aug-TZV(d,p) level of theory; proton affinity (PA) values were also calculated at the G3(MP2, CCSD(T)) level of theory. The experimental PA was estimated to be 847.9 ± 3.8 kJ mol(-1), the protonation entropy 115.1 ± 5.03 J mol(-1) K(-1) and the GB 813.6 ± 4.08 kJ mol(-1) at 298 K. From the PA value, a ΔH°(f) of 533.0 ± 12.4 kJ mol(-1) for protonated 2-FA was derived.
authors.affiliation: Department of Scienze della Vita, Second University of Naples, Caserta, Italy. andreina.ricci@unina2.it
authors.forename: Andreina
authors.initials: A
authors.lastname: Ricci
authors.forename: Simona
authors.initials: S
authors.lastname: Piccolella
authors.forename: Federico
authors.initials: F
authors.lastname: Pepi
authors.forename: Alexandros
authors.initials: A
authors.lastname: Patsilinakos
authors.forename: Rino
authors.initials: R
authors.lastname: Ragno
authors.forename: Stefania
authors.initials: S
authors.lastname: Garzoli
authors.forename: Pierluigi
authors.initials: P
authors.lastname: Giacomello
mesh_terms: D005662:Furaldehyde / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D007700:Kinetics; D008958:Models, Molecular; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry
chemical_list: D005740:Gases; D011522:Protons; D005662:Furaldehyde