Synthesis of isobenzofuran derivatives from renewable 2-carene over halloysite nanotubes

Synthesis of isobenzofuran derivatives from renewable 2-carene over halloysite nanotubes Full article

Journal

Molecular Catalysis
ISSN: 2468-8231

Output data

Year: 2020, Volume: 490, Article number : 110974, Pages count : 8 DOI: 10.1016/j.mcat.2020.110974

Tags

Terpene; carenes; Isobenzofuran; halloysite; reaction mechanism; acidity; DFT

Authors

Sidorenko A.Yu ^1,2 , Kravtsova A.V. ¹ , Mäki-Arvela P. ² , Aho A. ² , Il'ina I.V. ³ , Li-Zhulanov N.S. ^3,4 , Korchagina D. ³ , Volcho K.P. ^3,4 , Salakhutdinov N.F. ^3,4 , Murzin D.Yu ² , Sandberg T. ²

Affiliations

1	Institute of Chemistry of New Materials of National Academy of Sciences of Belarus, 220141, Skaryna str, 36, Minsk, Belarus
2	Åbo Akademi University, Biskopsgatan 8, 20500 Turku/Åbo, Finland
3	Novosibirsk Institute of Organic Chemistry, Lavrentjev av. 9, 630090, Novosibirsk, Russian Federation
4	Novosibirsk State University, Pirogova st. 1, 630090, Novosibirsk, Russian Federation

Condensation of a terpene 2-carene with 4-methoxybenzaldehyde over a range of acid aluminosilicates including halloysite nanotubes (HNT) was studied for as a model for preparation of isobenzofuran derivatives with a pharmaceutical potential. The catalysts were characterized by FTIR with pyridine, UV by adsorption of 2-phenylethylamine from the aqueous phase, SEM, TEM and N-2 physisorption. The largest selectivity to the desired product (ca. 70%) over halloysite nanotubes is associated with weak acidity of these catalysts (45 mu mol/g), allowing avoiding side isomerization and condensation reactions. Moreover, the highest yield on air-dry HNT clearly indicates that weak Bronsted sites favored the reaction. On the contrary, over strong Bronsted and Lewis acids (Amberlyst-15, scandium triflate), the yield of isobenzofurans did not exceed 16% with formation of mainly 2-carene isomerization products. DFT calculations showed that interactions of the aldehyde with cyclopropane moiety of 2-carene giving isobenzofurans are more beneficial than an alternative direct attack of a proton, leading to side reactions. A possibility to reuse of HNT catalyst was confirmed. Overall, halloysite is a highly effective catalyst for production of isobenzofuran compounds based on 2-carene.

Sidorenko A.Y. , Kravtsova A.V. , Mäki-Arvela P. , Aho A. , Il'ina I.V. , Li-Zhulanov N.S. , Korchagina D. , Volcho K.P. , Salakhutdinov N.F. , Murzin D.Y. , Sandberg T.
Synthesis of isobenzofuran derivatives from renewable 2-carene over halloysite nanotubes
Molecular Catalysis. 2020. V.490. 110974 :1-8. DOI: 10.1016/j.mcat.2020.110974 WOS Scopus РИНЦ

Submitted:	Mar 21, 2020
Accepted:	Apr 19, 2020
Published print:	Jul 1, 2020

Web of science	WOS:000541664600017
Scopus	2-s2.0-85084216503
Elibrary	43282509
OpenAlex	W3022303782