Phosphate ester hydrolysis catalyzed by metallomicelles

Menger, F. M.; Gan, L. H.; Johnson, E.; Durst, D. H.

doi:10.1021/ja00243a038

Cited by 225 publications

(109 citation statements)

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“…Menger et al (1) found that the critical micelle concentration (crnc) of their tetradecyl micelle was 0.18 mM. From conductance measurements as a function of detergent concentration we conclude that the crnc of the hexadecyl micelle in the absence of any additives is about 0.8 mM.…”

Section: Buffer Effectsmentioning

confidence: 80%

“…The pK, of a copper-bound water molecule has been variously estimated (1 1) to be as high as 9 or to be as low as 6.8 (12) depending on the ligand attached to the copper ion and on the geometry of the complex. Menger et al (1) found that in the presence of the copper-containing cationic micelle the hydrolysis rate of their phosphate ester was insensitive to pH between 6.0 and 8.3. They thus concluded that the copper-bound water molecule was completely ionized at pH = 6.0.…”

Section: Salt Effectsmentioning

confidence: 99%

“…Menger et al (1) have reported the preparation of the copper(I1) complex of N, N, N '-trimethyl-N '-tetradecylethylenediamine and have studied its effect on the hydrolysis of phosphate esters. Tonellato and co-workers (2) have reported the preparation of metal chelating micelles containing copper(I1) or zinc@) and have studied their effect on the hydrolysis of p-nitrophenylpicolinate.…”

Section: Introductionmentioning

confidence: 99%

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Micellar catalysis of organic reactions. Part 33. Amide hydrolysis in neutral solution in the presence of a copper-containing micelle

Broxton¹,

Coa²

1993

Can. J. Chem.

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. Can. J. Chem. 71, 670 (1993).The hydrolysis of 5-nitro-2-(trifluoroacety1amino)benzoic acid (1) has been studied at pH 7 in water and in the presence of micelles of cetyltrimethylammonium bromide (ctab) and of copper-containing micelles formed from the reaction of N, N,Nf-trimethyl-N'-hexadecylethylenediamine and cupric chloride. It has been found that the hydrolysis of 1 is inhibited by micelles of ctab but strongly catalysed by the copper-containing micelle at this pH. At a higher pH where the hydroxide ion reaction becomes important the reaction is catalysed by micelles of ctab as well, but the catalysis is stronger by the copper-containing micelle. The effect of added sodium chloride on the rate of reaction is shown to be larger for reaction in the presence of ctab than for reaction in the presence of the copper micelles. Also reported are the effects of the buffer concentration on the rate of reaction at various pH for both micelles. It is concluded that the mechanism of reaction in the copper-containing micelle involves a metal-bound hydroxyl rather than a free hydroxide ion loosely associated with the cationic micelle surface. It is interesting that the catalysis of this reaction by the copper-containing micelle is large enough to allow amide hydrolysis at a reasonable rate at neutral pH at ambient temperature. On a CtudiC I'hydrolyse de I'acide 5-nitro-2-(trifluoroacCty1arnino)benzoi'que (1) dans l'eau B un pH de 7 et en presence de micelles de bromure de c~tyltrim~thylammonium (bcta) ou de micelles contenant du cuivre formCes par la reaction de la N,N,N1-trimethyl-N'-hexad6cylCthylknediamine et le chlorure cuivrique. On a trouv6 que I'hydrolyse de 1 est inhibee par la presence de micelles de bcta, mais que, B ce pH, elle est fortement catalysee par la micelle contenant le cuivre. A un pH plus ClevC, quand la reaction de I'ion hydroxyde devient importante, la reaction est aussi catalyske par les micelles de bcta; toutefois, la catalyse est plus forte avec la micelle contenant le cuivre. On montre que l'addition de chlorure de sodium provoque un effet plus grand sur la reaction rCalisCe en presence de bcta que sur celle realisee en presence de micelles de cuivre. On rapporte aussi les effets de la variation de la concentration du tampon sur les vitesses des reactions 2 divers pH, en presence des deux micelles. On en conclut que la mecanisme de la reaction avec la micelle contenant du cuivre implique un groupe hydroxyle lie au metal plut6t qu'un ion hydroxyde libre faiblement associe avec la surface micellaire cationique. I1 est intkressant de rkaliser que la catalyse de cette reaction par les micelles contenant le cuivre est suffisamment importante pour permettre I'hydrolyse de l'amide a une vitesse raisonnable, B un pH neutre, a la temperature ambiante.[Traduit par la redaction] Introduction The preparation and the catalytic activity of metallomicelles on various organic reactions is currently of interest. Menger et al.(1) have reported the preparation of the copper(I1) complex of N, N, N '-trimethyl-N...

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Section: Buffer Effectsmentioning

confidence: 80%

Section: Salt Effectsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Micellar catalysis of organic reactions. Part 33. Amide hydrolysis in neutral solution in the presence of a copper-containing micelle

Broxton¹,

Coa²

1993

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…1,2 Among these, surfactants with counterions acting as active catalysts form a special class. [3][4][5][6][7][8][9] Metallo-micelles have been reported as catalysts for several types of reactions. [3][4][5]8,9 Other examples include catalysis of DNA hydrolysis by cerium phosphate bilayers 10 and catalysis of aldol reactions by lanthanide dodecyl sulfate dispersions.…”

mentioning

confidence: 99%

“…[3][4][5][6][7][8][9] Metallo-micelles have been reported as catalysts for several types of reactions. [3][4][5]8,9 Other examples include catalysis of DNA hydrolysis by cerium phosphate bilayers 10 and catalysis of aldol reactions by lanthanide dodecyl sulfate dispersions. 6,11 Herein, we report efficient catalysis of a Diels-Alder reaction by vesicles, composed of a phosphate surfactant, with copper(II) as the active counterion.…”

mentioning

confidence: 99%