Isomerization of α-pinene oxide over ZSM-5 based micro-mesoporous materials

Shcherban, Nataliya D.; Barakov, Roman; Mäki‐Arvela, Päivi; Sergiienko, Sergii A.; Bezverkhyy, Igor; Eränen, Kari; Murzin, Dmitry Yu.

doi:10.1016/j.apcata.2018.05.007

Cited by 33 publications

(43 citation statements)

References 48 publications

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“…Qualitative kinetics of -pinene oxide isomerization was investigated previously by our group over different catalysts including ZSM-5 based micro-mesoporous catalysts ( Fig. 2) [3], mesoporous Fe-MCM-41 ( Fig. 3), zeolites H-Beta-300 and Fe-Beta-300 ( Fig.…”

Section: Qualitative Kineticsmentioning

confidence: 91%

“…Isomerization of -pinene oxide has been intensively studied in the recent years over several homogeneous and heterogeneous catalysts [1][2][3][4][5][6][7][8][9]. The two main valuable products are campholenic aldehyde and trans-carveol finding applications in perfumes and flavors [10].…”

Section: Introductionmentioning

confidence: 99%

“…It was, however, observed very recently, that very high selectivity to campholenic aldehyde can be achieved over MCM-22 in -pinene oxide isomerization in a basic solvent, N,N-dimethylacetamide at 140 °C [8]. Recently ZSM-5 based micromesoporous materials were demonstrated to have moderate selectivity to both campholenic aldehyde and trans-carveol, around 30-50% [3]. Effect of solvents has been scarcely investigated in -pinene oxide isomerization apart from few studies [2,7].…”

Section: Introductionmentioning

confidence: 99%

“…In that work [9] kinetic modelling was done for experimental data in the temperature range of 298-358 K over Zn-triflate supported on three different supports K60, K100 and hexagonal mesoporous silica HMS 24 . Scheme 1 Reaction scheme for -pinene oxide isomerization adapted from [3] Thermodynamic analysis was limited to calculations of Gibbs free energy for formation of campholenic aldehyde at 25 °C. The aim in this work was to compare kinetic results with thermodynamic evaluation, which done by the Joback's method [13,14] in order to elucidate the effect of different parameters, such as temperature, solvent polarity and basicity in -pinene oxide isomerization.…”

Section: Introductionmentioning

confidence: 99%

“…The aim in this work was to compare kinetic results with thermodynamic evaluation, which done by the Joback's method [13,14] in order to elucidate the effect of different parameters, such as temperature, solvent polarity and basicity in -pinene oxide isomerization. A generic kinetic model was developed for -pinene oxide isomerization and applied for modelling of experimental data made in this work and taken from [5,6] for a range of iron and iron-free catalysts with different acidity, including Fe-H-MCM-41 [6], mildly acidic H-Beta-300 (the number denotes SiO 2 /Al 2 O 3 ratio) [6], iron modified H-Beta-300 [5] and micro-mesoporous ZSM-5 [3] based catalysts. The rate constants obtained from kinetic modelling were compared with the initial rates calculated from the kinetic results in order to assess the ability of the generic kinetic model to quantitatively describe the kinetic data.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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Kinetics and thermodynamics of-pinene oxide isomerization was investigated both theoretically and experimentally in different solvents in the temperature range of 50-140 °C using different zeolites, iron modified zeolites, Fe-H-MCM-41 and micro-mesoporous ZSM-5 derived catalysts. The aim was to elucidate the effect of solvent basicity and polarity on the product distribution in this reaction giving as the main value-added products campholenic aldehyde and trans-carveol, which are used as fragrances and perfumes. A generic kinetic first order model was developed composed of both parallel and consecutive routes. A thermodynamic analysis showed that product selectivity is determined by kinetic control and not by thermodynamics. Formation of campholenic aldehyde was favored in non-polar solvents, whereas basic solvents promoted formation of trans-carveol independent on temperature.

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Section: Qualitative Kineticsmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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Sustainable Isomerization of α‐Pinene Oxide to trans‐Carveol using Formic Acid/Aniline System at Room Temperature

Ravi

Naikwadi

Biradar

2021

Advanced Sustainable Systems

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trans‐Carveol is an essential and expensive chemical used as valencia orange essence oil in the fragrance industry, and can be obtained through Brønsted acid‐catalyzed isomerization of α‐pinene oxide (APO) using hazardous solvent at higher temperatures. Therefore the development of a simple, metal‐free, and cost‐effective, sustainable method for isomerization of APO at milder conditions is desired. In this study, in situ formed formanilide (IFF) and tetrahydrofuran are used as active solvents and formic acid used as a Brønsted acid catalyst for selective isomerization of APO. Under the optimized conditions, the maximum 80% selectivity of trans‐carveol is achieved with complete APO conversion in 30 min at room temperature. The solvent system's practical utility is demonstrated at a 10 g scale with complete conversion and 76% selectivity at room temperature within 60 min. Furthermore, isotopic labeling experiments show donation of a proton from the IFF solvent.

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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 over ZSM-5 based micro-mesoporous materials

Cited by 33 publications

References 48 publications

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

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

Sustainable Isomerization of α‐Pinene Oxide to trans‐Carveol using Formic Acid/Aniline System at Room Temperature

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

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