A study of some molecularly imprinted polymers as protic catalysts for the isomerisation of α-pinene oxide to trans-carveol

Motherwell, William B.; Bingham, Matilda; Pothier, Julien; Six, Yvan

doi:10.1016/j.tet.2004.02.016

Cited by 45 publications

(37 citation statements)

References 31 publications

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“…it is usually commercially available as an expensive mixture of isomers. [7] The acid-catalyzed isomerization of a-pinene oxide can result in a large variety of products, as this substrate is highly reactive and sensitive: over 200 compounds have been found at temperatures above 100 8C. [8] Therefore, the development of the reaction, which is selective for one particular product, is a very challenging task.…”

Section: Introductionmentioning

confidence: 99%

“…The highest previously reported yield of trans-carveol (3; 45 %) was obtained by using acidic molecularly imprinted polymers as protic catalysts in amounts that are equimolar to 1. [7] We have decided to study the isomerization of 1 in the presence of H 3 PW 12 O 40 in various solvents, as solvent effects have been reported to strongly influence the performance of both Lewis and Brønsted acid catalysts. [7,9] Heteropoly acids (HPAs) have attracted much interest as catalysts for the clean synthesis of fine and specialty chemicals in homogeneous and heterogeneous systems.…”

Section: Introductionmentioning

confidence: 99%

“…[7] We have decided to study the isomerization of 1 in the presence of H 3 PW 12 O 40 in various solvents, as solvent effects have been reported to strongly influence the performance of both Lewis and Brønsted acid catalysts. [7,9] Heteropoly acids (HPAs) have attracted much interest as catalysts for the clean synthesis of fine and specialty chemicals in homogeneous and heterogeneous systems. [16][17][18] In particular, HPAs have been recently applied in various reactions of terpenoids, such as hydration, acetoxylation, [19][20][21] and isomerization.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Phosphotungstic Acid as a Versatile Catalyst for the Synthesis of Fragrance Compounds by α‐Pinene Oxide Isomerization: Solvent‐Induced Chemoselectivity

Rocha

Hoehne

Gusevskaya

2008

Chemistry A European J

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The remarkable effect of the solvent on the catalytic performance of H3PW12O40, the strongest heteropoly acid in the Keggin series, allows direction of the transformations of alpha-pinene oxide (1) to either campholenic aldehyde (2), trans-carveol (3), trans-sobrerol (4 a), or pinol (5). Each of these expensive fragrance compounds was obtained in good to excellent yields by using an appropriate solvent. Solvent polarity and basicity strongly affect the reaction pathways: nonpolar nonbasic solvents favor the formation of aldehyde 2; polar basic solvents favor the formation of alcohol 3; whereas in polar weakly basic solvents, the major products are compounds 4 a and 5. On the other hand, in 1,4-dioxane, which is a nonpolar basic solvent, both aldehyde 2 and alcohol 3 are formed in comparable amounts. The use of very low catalyst loading (0.005-1 mol %) and the possibility of catalyst recovery and recycling without neutralization are significant advantages of this simple, environmentally benign, and low-cost method. This method represents the first example of the synthesis of isomers from alpha-pinene oxide, other than campholenic aldehyde, with a selectivity that is sufficient for practical usage.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Phosphotungstic Acid as a Versatile Catalyst for the Synthesis of Fragrance Compounds by α‐Pinene Oxide Isomerization: Solvent‐Induced Chemoselectivity

Rocha

Hoehne

Gusevskaya

2008

Chemistry A European J

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“…trans-Carveol (34) was obtained by isomerization of epoxypinane 26 using specially synthesized molec-ularly imprinted polymers (MIPs) as catalysts [44] (MIPs contain sockets possessing a high affinity for definite molecules). The reaction of epoxide 26 with water saturated with carbon dioxide gave sobrerol 35 in quantitative yield [45].…”

Section: Transformations Of α-And β-Pinene Epoxidesmentioning

confidence: 99%

10.1007/s11178-008-1001-3

2010

CrossRef Listing of Deleted DOIs

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“…The high yield of trans -carveol was also obtained using molecularly imprinted polymers as a protic catalyst with N , N -dimethylformamide as a solvent [6]. …”

Section: Introductionmentioning

confidence: 99%

Selective Preparation of trans-Carveol over Ceria Supported Mesoporous Materials MCM-41 and SBA-15

et al. 2013

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Ce-modified mesoporous silica materials MCM-41 and SBA-15, namely 32 wt % Ce–Si–MCM-41, 16 wt % Ce–H–MCM-41 and 20 wt % Ce–Si–SBA-15, were prepared, characterized and studied in the selective preparation of trans-carveol by α-pinene oxide isomerization. The characterizations of these catalysts were performed using scanning electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption and FTIR pyridine adsorption. Selective preparation of trans-carveol was carried out in the liquid phase in a batch reactor. The activity and the selectivity of catalyst were observed to be influenced by their acidity, basicity and morphology of the mesoporous materials. The formation of trans-carveol is moreover strongly influenced by the basicity of the used solvent and in order to achieve high yields of this desired alcohol it is necessary to use polar basic solvent.

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A study of some molecularly imprinted polymers as protic catalysts for the isomerisation of α-pinene oxide to trans-carveol

Cited by 45 publications

References 31 publications

Phosphotungstic Acid as a Versatile Catalyst for the Synthesis of Fragrance Compounds by α‐Pinene Oxide Isomerization: Solvent‐Induced Chemoselectivity

Phosphotungstic Acid as a Versatile Catalyst for the Synthesis of Fragrance Compounds by α‐Pinene Oxide Isomerization: Solvent‐Induced Chemoselectivity

10.1007/s11178-008-1001-3

Selective Preparation of trans-Carveol over Ceria Supported Mesoporous Materials MCM-41 and SBA-15

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