Chemical Reactivity and Basicity of Amines Modulated by Micellar Solutions

Fernandez, Adelaide C.; Iglesias, Edelmiro López; García‐Río, Luis; Leis, Jaan

doi:10.1021/la00006a017

Cited by 48 publications

(31 citation statements)

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“…The oxidation reaction of amines by Fe(CN) 6 3− in basic media takes place through subsequent electron transfer reactions in which the iron(III) center is reduced and the amine is oxidized to an aldehyde and a lower-class amine according to the following equation (9): [1] where, R, R \ , and R \\ are alkyl groups or hydrogen atoms.…”

Section: Resultsmentioning

confidence: 99%

“…Aqueous micelles and similar association colloids constitute a simple system in which one can modulate equilibria and chemical reactivity in solution (1). Aqueous micelles exert a medium effect on spontaneous reactions; they can accelerate or inhibit bimolecular reactions by concentrating or keeping the two reactants apart at the colloid surfaces (1).…”

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confidence: 99%

“…Aqueous micelles exert a medium effect on spontaneous reactions; they can accelerate or inhibit bimolecular reactions by concentrating or keeping the two reactants apart at the colloid surfaces (1).…”

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confidence: 99%

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Study of the kinetics of oxidation of amines by potassium ferricyanide in the presence of N,N‐dimethyldodecylamine N‐oxide

Zourab¹,

Ezzo

El‐Aila³

et al. 2005

J Surfact & Detergents

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This research reports on the oxidation of different amines such as dibutylamine, diethylamine, dipropylamine, ethylamine, ethylmethylamine, propylamine, triethylamine, and trimethylamine by 0.001 M potassium ferricyanide in the presence of 0.03 M NaOH at 25°C in aqueous medium and/or in 0.03 M N,. Oxidation rates were studied with a spectrophotometer at 420 nm. The experimental data showed that the reaction was first-order with respect to [amine] T and [Fe(CN) 6 ] 3− . Also, the rate constant (k obs ) had values within the concentration range of 0.015-0.05 M of NaOH and increased above the critical micelle concentration values of DDAO. The dependence of the reaction rate on the nature of the salt was also investigated, and the thermodynamic parameters ∆G*, ∆H*, and ∆S* were calculated. A pseudo-phase model was applied to the system, and the binding constant of the amine to DDAO micelles was calculated.Paper no. S1376 in JSD 8, 83-89 (January 2005). KEY WORDS:Amines, DDAO, micelles, oxidation, potassium ferricyanide, pseudo-phase.Aqueous micelles and similar association colloids constitute a simple system in which one can modulate equilibria and chemical reactivity in solution (1). Aqueous micelles exert a medium effect on spontaneous reactions; they can accelerate or inhibit bimolecular reactions by concentrating or keeping the two reactants apart at the colloid surfaces (1). Potassium ferricyanide usually reacts with organic substrates by one electron abstraction with a redox potential of +0.36 V (2). Amines were chosen as the organic substrate since they are known to have a strong tendency to be located near the micelle surface (3).Most studies of electron transfer reactions have been carried out in anionic micellar media (4,5). However, knowledge of the kinetics of electron transfer reactions in the presence of cationic micelles is limited due to solubility problems with one of the reactants, and, in particular, negatively charged substrates, in the cationic surfactant solution. For this purpose we used a zwitterionic surfactant, namely, N,N-dimethyldodecylamine N-oxide (DDAO). DDAO is similar to cationic (protonated form) or nonionic surfactants in its catalytic effects on other reactions, depending on the pH of the aqueous solution (6).In this paper, results corresponding to the oxidation of different classes of amines by potassium ferricyanide in the presence of NaOH and an aqueous micellar solution of DDAO are presented. EXPERIMENTAL PROCEDURESReagents and materials. DDAO was a gift from Clariant (Gersthofen, Germany). N-Ethylmethylamine (EMA), dipropylamine (DPA), and propylamine (PA) were obtained from Acros Organics (Fairlawn, NJ). Diethylamine (DEA), di-nbutylamine (DBA), triethylamine (TEA), and trimethylamine (TMA) were purchased from Riedel-de Haën (Seelze, Germany). Ethanol was supplied by Aldrich (Milwaukee, WI). Analytical grades of the other materials were purchased from Fluka (Buchs, Switzerland).Deionized, double-distilled water was used to prepare all solutions, with specific conductivity in ...

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Study of the kinetics of oxidation of amines by potassium ferricyanide in the presence of N,N‐dimethyldodecylamine N‐oxide

Zourab¹,

Ezzo

El‐Aila³

et al. 2005

J Surfact & Detergents

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“…It appears that the micellar surface is not homogeneous in terms of polarity, water concentration 1b,25 and distribution of solubilizates of different hydrophobicity. 19,26 Thus, phthalate ions (with two anionic groups) remain in the micellar region of high water concentration, while benzoate and PS À ions (with only one anionic group) can reach to the micellar region of relatively low water concentration. A similar conclusion has been proposed for related systems.…”

Section: Resultsmentioning

confidence: 99%

Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS?) with piperidine in the presence of cationic micelles

Khan¹,

Yusoff²

2000

J. Phys. Org. Chem.

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“…It is therefore tempting to propose that micellar inhibition of hydrolysis of NPTH at both 0.01 and 0.05 M NaOH is merely due to the medium polarity effect. However, micellar inhibition due to different sites of average location of both the reactants (NPTH M and as not be completely ruled out [41,42].…”

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Kinetics and mechanism of alkaline hydrolysis of 4‐nitrophthalimide in the absence and presence of cationic micelles

Khan

Abdullah

2001

Int J of Chemical Kinetics

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Pseudo-first-order rate constants (k obs ) for alkaline hydrolysis of 4-nitrophthalimide (NPTH) decreased by nearly 8-and 6-fold with the increase in the total concentration of cetyltrimethyl-ammonium bromide ([CTABr] T ) from 0 to 0.02 M at 0.01 and 0.05 M NaOH, respectively. These observations are explained in terms of the pseudophase model and pseudophase ion-exchange model of micelle. The increase in the contents of CH 3 CN from 1 to 70% v/v and CH 3 OH from 0 to 80% v/v in mixed aqueous solvents decreases k obs by nearly 12-and 11-fold, respectively. The values of k obs increase by nearly 27% with the increase in the ionic strength from 0.03 to 3.0 M. The mechanism of alkaline hydrolysis of NPTH involves the reactions between HO Ϫ and nonionized NPTH as well as between HO Ϫ and ionized NPTH. The micellar inhibition of the rate of alkaline hydrolysis of NPTH is attributed to medium polarity effect.

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Chemical Reactivity and Basicity of Amines Modulated by Micellar Solutions

Cited by 48 publications

References 0 publications

Study of the kinetics of oxidation of amines by potassium ferricyanide in the presence of N,N‐dimethyldodecylamine N‐oxide

Study of the kinetics of oxidation of amines by potassium ferricyanide in the presence of N,N‐dimethyldodecylamine N‐oxide

Effects of inert organic and inorganic anions on the rates of intramolecular general base-catalyzed reactions of ionized phenyl salicylate (PS?) with piperidine in the presence of cationic micelles

Kinetics and mechanism of alkaline hydrolysis of 4‐nitrophthalimide in the absence and presence of cationic micelles

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