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Citation
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HERO ID
6837431
Reference Type
Journal Article
Title
An innovative synthesis pathway to benzodioxanes: the peculiar reactivity of glycerol carbonate and catechol
Author(s)
Tabanelli, T; Giliberti, C; Mazzoni, R; Cucciniello, R; Cavani, F
Year
2019
Is Peer Reviewed?
Yes
Journal
Green Chemistry
ISSN:
1463-9262
EISSN:
1463-9270
Volume
v. 21
Issue
no. 2
Page Numbers
329-338
DOI
10.1039/c8gc02811g
Abstract
A peculiar reactivity of glycerol carbonate (GlyC) as an innovative and highly reactive alkylating agent for phenolic compounds is investigated in this article. In particular, 2-hydroxymethyl-1,4-benzodioxane (HMB), a key intermediate for the pharmaceutical industry, has been selectively synthesized by the reaction of a slight excess of GlyC with catechol in the presence of a basic catalyst (NaOCH3, Na-mordenite, MgO), without requiring a reaction solvent. Both reagents have been quantitatively converted in just one hour at 170 °C with a HMB yield, up to 88%, in the presence of a homogeneous basic catalyst (NaOCH3). Notably, the main side product, the HMB isomer, may be an interesting intermediate for the synthesis of calone analogues, which are important scaffolds used in fragrances. A detailed mechanistic study, supported by kinetics, GC-MS, and HMBC NMR characterization, is also reported. Accordingly, this paper describes a completely innovative and greener synthesis pathway to benzodioxanes.
Keywords
alkylation agents; carbonates; catalysts; catechol; dioxane; gas chromatography-mass spectrometry; glycerol; green chemistry; isomers; magnesium oxide; nuclear magnetic resonance spectroscopy; pharmaceutical industry; solvents
Tags
OPPT REs
•
OPPT_1,4-Dioxane_D. Exposure
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