Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products.
The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1-24 h gives rise to 5-arylmethylfurfurals (yields of 17-91%) and 2-arylmethyl-5-(diarylmethyl)furans (yields of 10-37%). The formation of these two types of reaction products depends on the nucleophilicity of the arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation of only 5-arylmethylfurfurals (yields of 45-79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of AlBr3at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51-90%). The reactive protonated species of 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.
Department of Chemistry, Saint Petersburg State Forest Technical University, Institutsky per., 5, Saint Petersburg, 194021, Russia; Institute of Chemistry, Saint Petersburg State University, Saint Petersburg State University, Universitetskaya nab., 7/9, Saint Petersburg, 199034, Russia.
Dmitry S
DS
Ryabukhin
Department of Chemistry, Saint Petersburg State Forest Technical University, Institutsky per., 5, Saint Petersburg, 194021, Russia; The All-Russia Scientific Research Institute of Fats, ul. Chernyakhovskogo, 10, Saint Petersburg, 191119, Russia.
Dmitry N
DN
Zakusilo
L.M. Litvinenko Institute of Physico-Organic and Coal Chemistry of NASU, Kharkivs'ke Hgw, 50, Kiyv, 02160, Ukraine.
Mikhail O
MO
Kompanets
Department of Chemistry, Saint Petersburg State Forest Technical University, Institutsky per., 5, Saint Petersburg, 194021, Russia.
Anton
A
A Tarakanov
Institute of Chemistry, Saint Petersburg State University, Saint Petersburg State University, Universitetskaya nab., 7/9, Saint Petersburg, 199034, Russia.
Irina A
IA
Boyarskaya
Institute of Nanobiotechnologies, Peter the Great St. Petersburg Polytechnic University, Polytechnicheskaya ul., 29, Saint Petersburg, 195251, Russia.
Tatiana O
TO
Artamonova
Institute of Nanobiotechnologies, Peter the Great St. Petersburg Polytechnic University, Polytechnicheskaya ul., 29, Saint Petersburg, 195251, Russia.
Mikhail A
MA
Khohodorkovskiy
Department of Physical Chemistry of Combustible Minerals, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry of NASU, Naukova St., 3a, Lviv, 79053, Ukraine.
Iosyp O
IO
Opeida
Department of Chemistry, Saint Petersburg State Forest Technical University, Institutsky per., 5, Saint Petersburg, 194021, Russia; Institute of Chemistry, Saint Petersburg State University, Saint Petersburg State University, Universitetskaya nab., 7/9, Saint Petersburg, 199034, Russia.
Aleksander V
AV
Vasilyev
2,5-diformylfuran; 5-hydroxymethylfurfural; Friedel–Crafts reaction; superacids; zeolites