Preparation of chiral isobenzofurans from 3-carene in the presence of modified clays

Preparation of chiral isobenzofurans from 3-carene in the presence of modified clays Full article

Journal

Molecular Catalysis
ISSN: 2468-8231

Output data

Year: 2018, Volume: 459, Pages: 38-45 Pages count : 8 DOI: 10.1016/j.mcat.2018.07.025

Tags

3-Carene; Isomerization; 2-Carene; Isobenzofuran; Clays; K-10 montmorillonite

Authors

Sidorenko A.Yu. ¹ , Il'ina I.V. ^2,3 , Kravtsova A.V. ¹ , Aho A. ⁴ , Ardashov O.V. ^2,3 , Li-Zhulanov N.S. ^2,3 , Volcho K.P. ^2,3 , Salakhutdinov N.F. ^2,3 , Murzin D.Yu. ⁴ , Agabekov V.E. ¹

Affiliations

1	(Данные Web of science) Natl Acad Sci Belarus, Inst Chem New Mat, Skaryna Str 36, Minsk 220141, BELARUS
2	(Данные Web of science) Russian Acad Sci, Siberian Branch, Novosibirsk Inst Organ Chem, Lavrentjev Av 9, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, Pirogova Str 2, Novosibirsk 630090, Russia
4	(Данные Web of science) Abo Akad Univ, Biskopsgatan 8, Turku 20500, Finland

Isomerization of 3-carene to the reaction mixture, containing 2-carene and its further utilization in the synthesis of chiral isobenzofurans, was investigated in the presence of acid-modified clays at 140 degrees C. The catalysts were characterized by XRF, FTIR with pyridine and nitrogen adsorption. Quantification of the effect of the type and concentration of acid sites in different clays comprising commercial montmorillonite and natural illite on the yield of 2-carene as well as by-products was obtained for the first time. It was established that selectivity to 2-carene decreased with an increase of the Lewis to Bronsted acid sites ratio. The largest amount of 2-carene in the mixture (15.0 wt%) with the highest ratio of 2-carene to menthadienes (0.63) was observed at 50% 3-carene conversion over a commercial montmorillonite K-30 clay, which has a moderate (100 gmol/g) acidity. It was demonstrated for the first time that the mixture containing 2-carene can be effectively used as a starting material in the reaction with vanillin resulting in chiral isobenzofurans. The products obtained in this reaction exhibit neuroprotective activity in an animal Parkinson's disease model. It was established that isobenzofurans yield decreased with an increase in the Lewis to Bronsted acid sites ratio. The largest yield of these products was obtained in the presence of a commercial K-10 clay (59.8%), which is higher than using 2-carene per se. Catalytic synthesis of isobenzofurans based on a readily available monoterpene 3-carene instead of expensive 2-carene was thus developed.

Sidorenko A.Y. , Il'ina I.V. , Kravtsova A.V. , Aho A. , Ardashov O.V. , Li-Zhulanov N.S. , Volcho K.P. , Salakhutdinov N.F. , Murzin D.Y. , Agabekov V.E.
Preparation of chiral isobenzofurans from 3-carene in the presence of modified clays
Molecular Catalysis. 2018. V.459. P.38-45. DOI: 10.1016/j.mcat.2018.07.025 WOS Scopus РИНЦ

Published print:

Nov 1, 2018

Web of science	WOS:000447580300006
Scopus	2-s2.0-85052880420
Elibrary	35725790
OpenAlex	W2889041144