Structure du chloro-3 méthyl-2 4H-pyrazino[1,2-a]pyrimidinone-4

Sablayrolles, C.; Chapat, Jean‐Pierre; Ducourant, C.; Fourcade, R.

doi:10.1107/s010827018709262x

Cited by 4 publications

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References 4 publications

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“…Ionic concentrations in the reverse micelles are referred to that of water, i.e., [NaBH 4]w ) 0.1 M. When the surfactant concentration is changed at a given value of W 0, total amounts of water and NaBH4 differ in every case, but the ratio is always the same. The concentration of hydride species was assumed to be four times that of the analytical concentration 31,32 due to the presence in the BH4ion of four identical hydrogen atoms. Kinetics.…”

Section: Methodsmentioning

confidence: 99%

Reverse Micellar Aggregates: Effect on Ketone Reduction. 2. Surfactant Role

et al. 2004

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Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface.

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Section: Methodsmentioning

confidence: 99%

Reverse Micellar Aggregates: Effect on Ketone Reduction. 2. Surfactant Role

et al. 2004

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“…The concentration of hydride species was assumed to be four times that of the analytical concentration , due to the presence in the BH 4 - ion of four identical hydrogen atoms.…”

Section: Methodsmentioning

confidence: 99%

Reverse Micellar Aggregates: Effect on Ketone Reduction. 1. Substrate Role

et al. 2004

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The reduction of three aromatic ketones, acetophenone (AF), 4-methoxyacetophenone (MAF), and 3-chloroacetophenone (CAF), by NaBH(4) was followed by UV-vis spectroscopy in reverse micellar systems of water/AOT/isooctane at 25.0 degrees C (AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate). The first-order rate constants, k(obs), increase with the concentration of surfactant due to the substrate incorporation at the reverse micelle interface, where the reaction occurs. For all the ketones the reactivity is lower at the micellar interface than in water, probably reflecting the low affinity of the anionic interface for BH(4)(-). Kinetic profiles upon water addition show maxima in k(obs) at W(0) approximately 5 probably reflecting a strong interaction between water and the ionic headgroup of AOT; at W(0) < 5 by increasing W(0) BH(4)(-) is repelled from the anionic interface once the water pool forms. The order of reactivity was CAF >> AF > MAF. Application of a kinetic model based on the pseudophase formalism, which considers distribution of the ketones between the continuous medium and the interface, and assumes that reaction take place only at the interface, gives values of the rate constants at the interface of the reverse micellar system. At W(0) = 5, we conclude that NaBH(4) is wholly at the interface, and at W(0) = 10 and 15, where there are free water molecules, the partitioning between the interface and the water pool has to be considered. The results were used to estimate the ketone and borohydride distribution constants between the different pseudophases as well as the second-order reaction rate constant at the micellar interface.

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