Research output: Contribution to journal › Article › peer-review
Synthesis of isobenzofuran derivatives from renewable 2-carene over halloysite nanotubes. / Sidorenko, A. Yu; Kravtsova, A. V.; Mäki-Arvela, P. et al.
In: Molecular Catalysis, Vol. 490, 110974, 07.2020.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Synthesis of isobenzofuran derivatives from renewable 2-carene over halloysite nanotubes
AU - Sidorenko, A. Yu
AU - Kravtsova, A. V.
AU - Mäki-Arvela, P.
AU - Aho, A.
AU - Sandberg, T.
AU - Il'ina, I. V.
AU - Li-Zhulanov, N. S.
AU - Korchagina, D. V.
AU - Volcho, K. P.
AU - Salakhutdinov, N. F.
AU - Murzin, D. Yu
AU - Agabekov, V. E.
N1 - Publisher Copyright: © 2020 Elsevier B.V. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/7
Y1 - 2020/7
N2 - 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 N2 physisorption. The largest selectivity to the desired product (ca. 70%) over halloysite nanotubes is associated with weak acidity of these catalysts (45 μmol/g), allowing avoiding side isomerization and condensation reactions. Moreover, the highest yield on air-dry HNT clearly indicates that weak Brønsted sites favored the reaction. On the contrary, over strong Brønsted 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.
AB - 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 N2 physisorption. The largest selectivity to the desired product (ca. 70%) over halloysite nanotubes is associated with weak acidity of these catalysts (45 μmol/g), allowing avoiding side isomerization and condensation reactions. Moreover, the highest yield on air-dry HNT clearly indicates that weak Brønsted sites favored the reaction. On the contrary, over strong Brønsted 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.
KW - acidity
KW - carenes
KW - DFT
KW - halloysite
KW - Isobenzofuran
KW - reaction mechanism
KW - Terpene
KW - 3-CARENE
KW - CATALYTIC ISOMERIZATION
KW - ACID CATALYSTS
KW - CLAY NANOTUBES
KW - ALDEHYDES
KW - GREEN
KW - ALPHA-PINENE
KW - BIOMASS
KW - ZEOLITES
UR - http://www.scopus.com/inward/record.url?scp=85084216503&partnerID=8YFLogxK
U2 - 10.1016/j.mcat.2020.110974
DO - 10.1016/j.mcat.2020.110974
M3 - Article
AN - SCOPUS:85084216503
VL - 490
JO - Molecular Catalysis
JF - Molecular Catalysis
SN - 2468-8231
M1 - 110974
ER -
ID: 24163339