25571-14-6Relevant articles and documents
Fe(III)-catalyzed α-terpinyl derivatives synthesis from β-pinene via reactions with hydrogen peroxide in alcoholic solutions
Da Silva,Carari,Manoel Da Silva, Adalberto
, p. 10529 - 10536 (2015)
In this study, a novel and environmentally benign Fe(iii)-catalyzed terpinyl derivatives synthesis using hydrogen peroxide in alcohol solutions (i.e. methyl, ethyl, propyl, isopropyl and butyl alcohols) was investigated. The use of Bronsted acid catalysts was avoided and β-pinene was used as the starting reactant. High conversions (ca. 90%) and combined selectivities for the α-terpineol and terpinyl alkyl ethers (ca. 70-73%) were obtained when Fe(NO3)3 was used as the catalyst. The role of each component catalyst system was studied with special focus on the solvent. The use of a biodegradable and renewable origin solvent (ethyl alcohol), which was added to an inexpensive and mildly toxic catalyst and a green oxidant are the main positive features of this process.
Exploring the Keggin-Type Heteropolyacid-Catalyzed Reaction Pathways of the Β-Pinene with Alkyl Alcohols
Polo, Henrique Priori,Lopes, Neide Paloma Goncalves,da Silva, Márcio José
, p. 2844 - 2853 (2019/05/28)
Abstract: In this work, we investigated the activity of Keggin heteropolyacid catalysts (i.e., H3PW12O40, H3PMo12O40 and H4SiW12O40) in β-pinene reactions with alkyl alcohols (i.e. methyl, ethyl, propyl, sec-propyl, butyl and sec-butyl alcohols), and exploring the different aspects that drive the selectivity of this process. We have found that carbon skeletal rearrangements and isomerization providing intermediate carbocations that controlling the reaction selectivity. β-pinene was preferentially converted to α-terpinyl ion which undergoes a nucleophilic attack of alcohol providing alkyl alcohol. Bornyl ion was converted to bornyl and fenchyl ethers. The other secondary products were β-pinene isomers obtained from bornyl and α-terpinyl carbocations. Phosphotungstic acid (i.e., H3PW12O40) was the most active catalyst and selective toward the main product (α-terpinyl alkyl ether); the highest conversion (ca. 96%) and ether selectivity (ca. 61%) was achieved in the reactions with β-pinene. Although having also been alkoxylate, α-pinene was less reactive (ca. 40%), while camphene and limonene remained unreactive under reaction conditions studied. An increase of temperature resulted in an improvement on conversion of β-pinene and selectivity toward α-terpinyl methyl ether. Similarly, the H3PW12O40 concentration played a crucial role on reaction selectivity. This work presents positive features such as a short reaction time, high atom economy, mild reaction conditions (i.e., low temperature and room pressure). Even though soluble the catalyst was easily recovered by liquid -liquid extraction and efficiently reused. Graphical Abstract: [Figure not available: see fulltext.].
