Isomerization of α-Pinene Oxide: Solvent Effects, Kinetics and Thermodynamics

Mäki‐Arvela, Päivi; Shcherban, Nataliya D.; Lozachmeur, Chloé; Russo, Vincenzo; Wärnå, Johan; Murzin, Dmitry Yu.

doi:10.1007/s10562-018-2617-8

Cited by 16 publications

(21 citation statements)

References 13 publications

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“…On the other hand, the highest initial reaction rate was observed using 1,4-dioxane. In the case of nonpolar solvents, campholenic aldehyde was the major product, which is in accordance with the results already published in the literature [19,23,41]. As basicity cannot be the main reason (the difference between donor number of toluene and cyclohexane is negligible), other factors have to play an important role.…”

Section: Catalytic Testingsupporting

confidence: 90%

“…It is known that used solvent can significantly influence the reaction course; in our case of APO rearrangement, the selectivity to specific products would be the most important parameter. So far, to the best of our knowledge, widely studied solvent influence was performed using iron-based catalysts (Fe-zeolite, Fe-MCM-41) in APO rearrangement [15,21,41]. A wide number of solvents-nonpolar, polar protic, and polar aprotic-were used and further described using donor number to compare their Lewis basicity and dielectric constant to compare their polarity.…”

Section: Catalytic Testingmentioning

confidence: 99%

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Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified Zeolite BETA

et al. 2020

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Natural source turpentine is an available source of α-pinene oxide. This compound’s value is especially given by the possibility of producing important compounds campholenic aldehyde and trans-carveol. In this work, we would like to present the usage of MoO3-modified zeolite BETA in α-pinene oxide isomerization concerning campholenic aldehyde and trans-carveol formation using a wide range of solvents. Catalyst calcination temperature also influenced the reaction course (selectivity to desired compounds and reaction rate). MoO3-zeolite BETA was prepared by the wet impregnation method and characterized by different techniques. The use of polar aprotic solvents had the most positive effect on the reaction course. Solvent basicity and polarity considerably influenced the reaction rate and selectivity to particular products. The combination of high basicity and the high polarity was the most suitable for the studied reaction from the reaction rate point of view. Selectivity to campholenic aldehyde and trans-carveol was the most influenced by solvent basicity. Higher solvent basicity caused the preferential formation of trans–carveol, influence on selectivity to campholenic aldehyde formation was the opposite. The described catalyst may be used for α-pinene oxide rearrangement to both desired products dependently on the used solvent. Molybdenum offers an exciting alternative for previously described modifications of zeolites for this reaction.

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Section: Catalytic Testingsupporting

confidence: 90%

Section: Catalytic Testingmentioning

confidence: 99%

Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified Zeolite BETA

et al. 2020

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“…Turpentine is a valuable and renewable natural resource widely used in the medical industry, for the synthesis of new important chemicals foruse as cosmetic, flavours, fragrances, and pharmaceuticals sectors as well as in the synthesis of chemical intermediates [3]. Thus, α-Pinene is considered a versatile building block for the synthesis of high-value added chemicals, mainly through catalytic processes, such as hydration [4,5,6,7,8,9], isomerization [10,11], epoxidation and pinene oxide isomerization [12,13,14], esterification [15,16], and etherification [17,18,19,20,21,22], among others can be applied to obtain a wide variety of added value products.…”

mentioning

confidence: 99%

Potassium Alum [KAl(SO4)2∙12H2O] solid catalyst for effective and selective methoxylation production of alpha-pinene ether products

Wijayati

Lestari

Wulandari

et al. 2021

Heliyon

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Methoxylation is a relevant technological process applied in the production of high-value α-pinene derivatives.This report investigates the use of potassium alum [KAl(SO 4 ) 2 ⋅ 12H 2 O] as a catalyst in the methoxylation of α-pinene. In this study, the methoxylation reaction was optimized for the highest conversion of α-pinene and selectivity, assessed for the factors, catalyst loading (0.5; 1.0; and 1.5 g), volume ratio of α-pinene: methanol (1:4, 1:7, 1:10), reaction temperature (50, 55, 60 and 65 C), and reaction time (72, 144, 216, 288, 360 min). The highest selectivity of KAl(SO 4 ) 2 •12H 2 O in the methoxylation of α-pinene was achieved under an optimal condition of 1 g of catalyst loading, volume ratio of 1:10, as well as the reaction temperature and incubation time of 65 C and 6 h, respectively. GC-MS results revealed the yields of the methoxylated products from the 98.2% conversion of α-pinene, to be 59.6%, 8.9%, and 7.1% for α-terpinyl methyl ether (TME), fenchyl methyl ether (FME), bornyl methyl ether (BME), respectively. It was apparent that a lower KAl(SO 4 ) 2 •12H 2 O loading (0.5-1.5 g) was more economical for the methoxylation reaction. The findings seen here indicated the suitability of the KAl(SO 4 ) 2 ⋅ 12H 2 O to catalyze the methoxylation of α-pinene to produce an commercially important ethers.

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“…88 The size of micropore was generally smaller than the size of reactant, consequently restricted the diffusion into the internal pore cavities, resulting in the deactivation of catalysts. 89 Restriction in molecular diffusion during isomerization and acetalization was mitigated via the introduction of secondary pores (meso or macro). Secondary pores reduced the steric hindrance of bulky molecules and also increased the intracrystalline diffusion rate.…”

Section: The Effect Of Zeolite Porositymentioning

confidence: 99%

“…In the isomerization of large bulky molecules, the reaction was often restricted by intracrystalline diffusion particularly when using microporous zeolites 88 . The size of micropore was generally smaller than the size of reactant, consequently restricted the diffusion into the internal pore cavities, resulting in the deactivation of catalysts 89 . Restriction in molecular diffusion during isomerization and acetalization was mitigated via the introduction of secondary pores (meso or macro).…”

Section: Zeolite and Hierarchical Aluminosilicate Catalystsmentioning

confidence: 99%

Review on heterogeneous catalysts for the synthesis of perfumery chemicals via isomerization, acetalization and hydrogenation

Hartati

Firda

Bahruji

et al. 2021

Flavour & Fragrance J

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Synthetic fragrance has dominated the perfumery industry in recent decades due to the ability to produce perfumery ingredients on a large scale at a low cost. Extensive research in the field of synthetic perfumery chemical involved the utilization of catalysts to improve the productivity. This review will discuss recent advances of heterogeneous catalysts for the synthesis of perfumery chemicals as fragrance ingredients. Transition from homogeneous to heterogeneous catalysts will be included in order to provide insight into the benefits of heterogeneous catalysts to overcome the limitation of homogeneous reaction. Isomerization, acetalization and hydrogenation were identified as three main reactions for the synthesis of perfumery chemicals based on the number of reported work since 2000. This review will focus on α‐pinene and α‐pinene oxide as the main molecular substrates, however, different molecules, for example, linalool, citronellal and cinnamaldehyde will also be included. The synthesis, modification and possible mechanisms for the reactions involving zeolite, aluminosilicate, metal oxides, metal organic framework, monometallic and bimetallic nanoparticles as heterogeneous catalysts will be discussed. Discussion on isomerization and acetalization reactions will focus on the acidity and the porosity of the catalysts as the two main factors that determine the conversion and selectivity. For perfumery chemicals produced via hydrogenation reaction, the role of monometallic and bimetallic nanoparticles catalysts will be discussed in the chemoselective reduction of cinnamaldehyde and citronellal.

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Isomerization of α-Pinene Oxide: Solvent Effects, Kinetics and Thermodynamics

Cited by 16 publications

References 13 publications

Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified Zeolite BETA

Solvent Influence on Selectivity in α-Pinene Oxide Isomerization Using MoO3-Modified Zeolite BETA

Potassium Alum [KAl(SO4)2∙12H2O] solid catalyst for effective and selective methoxylation production of alpha-pinene ether products

Review on heterogeneous catalysts for the synthesis of perfumery chemicals via isomerization, acetalization and hydrogenation

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