The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

Svetlana A Kuznetsova; Alexander S Gak; Yulia V Nelyubina; Vladimir A Larionov; Han Li; Michael North; Vladimir P Zhereb; Alexander F Smol'yakov; Artem O Dmitrienko; Michael G Medvedev; Igor S Gerasimov; Ashot S Saghyan; Yuri N Belokon

doi:10.3762/bjoc.16.99

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

Beilstein J Org Chem. 2020 May 26:16:1124-1134. doi: 10.3762/bjoc.16.99. eCollection 2020.

Authors

Affiliations

¹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, 119991 Moscow, Russian Federation.
² Moscow State University, Faculty of Material Science, Leninskie Gory 1/73, 119991 Moscow, Russian Federation.
³ Department of Inorganic Chemistry, People's Friendship University of Russia (RUDN University), Miklukho-Maklaya Street 6, 117198 Moscow, Russian Federation.
⁴ Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, YO10 5DD, United Kingdom.
⁵ Siberian Federal University, School of Non-Ferrous Metals and Material Science, 95 Krasnoyarskiy Rabochiy pr., 660025 Krasnoyarsk, Russian Federation.
⁶ N. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prospect, 47, 119991 Moscow, Russian Federation.
⁷ Institute of Pharmacy, Yerevan State University, 1 Alex Manoogian Str, Yerevan 0025, Armenia.

Abstract

The acid-base neutralization reaction of commercially available disodium 2,6-naphthalenedisulfonate (NDS, 2 equivalents) and the tetrahydrochloride salt of tetrakis(4-aminophenyl)methane (TAPM, 1 equivalent) in water gave a novel three-dimensional charge-assisted hydrogen-bonded framework (CAHOF, F-1). The framework F-1 was characterized by X-ray diffraction, TGA, elemental analysis, and ¹H NMR spectroscopy. The framework was supported by hydrogen bonds between the sulfonate anions and the ammonium cations of NDS and protonated TAPM moieties, respectively. The CAHOF material functioned as a new type of catalytically active Brønsted acid in a series of reactions, including the ring opening of epoxides by water and alcohols. A Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone was also catalyzed by F-1 in heptane. Depending on the polarity of the solvent mixture, the CAHOF F-1 could function as a purely heterogeneous catalyst or partly dissociate, providing some dissolved F-1 as the real catalyst. In all cases, the catalyst could easily be recovered and recycled.

Keywords: Brønsted acid catalyst; Diels–Alder; charge-assisted hydrogen-bonded framework; epoxide ring opening; heterogeneous catalyst.

Grants and funding

The X-ray diffraction data were collected with financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of the Center for Molecular Composition Studies of INEOS RAS. Quantum chemical calculations were performed with financial support from RFBR (#17-03-00907). The publication has been prepared with the support of the “RUDN University Program 5-100” (V.A.L., PXRD investigation). The authors gratefully acknowledge financial support from a RFBR research grant No 18–53-05004 Arm-a.