New cyclization agents for the synthesis of beta-ionone from pseudoionone

Markovich, Yu. D.; Panfilov, A. V.; Platunov, Yu. N.; Zhirov, A. A.; Kosenko, S. I.; Kirsanov, A. T.

doi:10.1007/bf02465835

Cited by 9 publications

(4 citation statements)

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“…16 β-Ionone yields up to 91%, and R-ionone yields as low as 1.5% were observed. Finally, mixtures of trifluoroacetic acid and H 2 SO 4 or trifluoroacetic and fluorosulfonic acids were employed as cyclization agents by Markovich et al 17 with aiming to reduce or eliminate the use of H 2 SO 4 in β-ionone production. The amount of H 2 SO 4 decreases to 1À 1.25 mols per mole PI compared to the case of only H 2 SO 4 where the molar ratio (H 2 SO 4 :PI) of about 5À6 is required.…”

Section: ' Literature Reviewmentioning

confidence: 99%

Cyclization of Pseudoionone to β-Ionone: Reaction Mechanism and Kinetics

Kashid

Yuranov

Raspail

et al. 2011

Ind. Eng. Chem. Res.

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Cyclization of pseudoionone (PI) to β-ionone is an important reaction used in the synthesis of vitamin A and in perfumery. Though the reaction is used for commercial production, its mechanism and kinetics are not known, and the same holds for the optimal performance of the process. This paper deals with experimental investigations of reaction mechanism and kinetics. The inherent characteristics of the reaction such as heat of reaction, thermal stability, and reactants/products distribution in biphasic (sulfuric acid-toluene) system was investigated experimentally. To overcome the mass transfer limitations, the intrinsic kinetics was studied in a batch reactor using a solvent (1-nitropropane) miscible with the reactant and the homogeneous catalyst. It was revealed that the reaction consists of two steps with the first being rapid, while the second is relatively slower. Therefore, the kinetics of only the second step was investigated which was observed to be first order with an activation energy of 65 kJ/mol.

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Section: ' Literature Reviewmentioning

confidence: 99%

Cyclization of Pseudoionone to β-Ionone: Reaction Mechanism and Kinetics

Kashid

Yuranov

Raspail

et al. 2011

Ind. Eng. Chem. Res.

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“…610 Alternatively, pseudoionone 527 can be isomerised to α-ionone 526 by treatment with trifluoroacetic acid, and 526 can then be further isomerised to β-ionone 525 by sulfuric acid. 611 The utilisation of enantioselective protonation procedures in relation to the synthesis of (S)-(Ϫ)-damascone 528 has been reviewed. 612 Ab initio calculations on the two geometrical isomers and the protonated form of the simple Schiff base 529 of β-ionone have been carried out.…”

Section: Thujanesmentioning

confidence: 99%

Monoterpenoids (mid-1997 to mid-1999)

Grayson

2000

Nat. Prod. Rep.

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In situ RNA hybridization and immunocytochemistry were used to establish the cellular distribution of monoterpenoid indole alkaloid biosynthesis in Madagascar periwinkle (Catharanthus roseus). Tryptophan decarboxylase (TDC) and strictosidine synthase (STR1), which are involved in the biosynthesis of the central intermediate strictosidine, and desacetoxyvindoline 4-hydroxylase (D4H) and deacetylvindoline 4-O-acetyltransferase (DAT), which are involved in the terminal steps of vindoline biosynthesis, were localized. tdc and str1 mRNAs were present in the epidermis of stems, leaves, and flower buds, whereas they appeared in most protoderm and cortical cells around the apical meristem of root tips. In marked contrast, d4h and dat mRNAs were associated with the laticifer and idioblast cells of leaves, stems, and flower buds. Immunocytochemical localization for TDC, D4H, and DAT proteins confirmed the differential localiza-tion of early and late stages of vindoline biosynthesis. Therefore, we concluded that the elaboration of the major leaf al-kaloids involves the participation of at least two cell types and requires the intercellular translocation of a pathway intermediate. A basipetal gradient of expression in maturing leaves also was shown for all four genes by in situ RNA hy-bridization studies and by complementary studies with dissected leaves, suggesting that expression of the vindoline pathway occurs transiently during early leaf development. These results partially explain why attempts to produce vin-doline by cell culture technology have failed. INTRODUCTION The organs forming the plant body consist of several different cell types that are organized in relation to each other and that confer specific functions to the resulting organ. Each cell type emerges from an undifferentiated meristem according to a sophisticated and partially understood developmental program (Sylvester et al., 1996; von Arnim and Deng, 1996). The commitment to differentiate into specialized structures involves the perception by cells in the meristem of a complex array of signals, which communicate cellular age, position in relation to other cells, and hormonal balance. Environmental factors, such as light and temperature, also play a critical role in modulating these signals throughout the process of organogenesis (Bernier, 1988; Dale, 1988; Sylvester et al., 1996). In addition to morphogenesis, developmental processes result in biochemical specialization of cells for the biosyn-thesis and/or accumulation of secondary metabolites, such as phenylpropanoids (Ibrahim et al.

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“…Consistently, other authors have reported that concentrated sulfuric acid produces mainly b-ionone [8,9]. Markovich et al [21,22] studied the synthesis of b-ionone using trifluoroacetic acid, fluorosulfonic acid and anhydrous hydrogen fluoride. They postulated that medium strength liquid acids promote the PS protonation forming an enol carbonium that leads to a-ionone by rearrangement.…”

Section: Reaction Mechanismmentioning

confidence: 53%