Secondary valence force catalysis. XI. Enhanced reactivity and affinity of cyanide ion toward N-substituted 3-carbamoyl-pyridinium ions elicited by ionic surfactants

Baumrucker, J.; Calzadilla, M.; Centeno, MA; Lehrmann, G.; Lindquist, P.; Dunham, David J.; Price, M. F.; Sears, B.; Cordes, E. H.

doi:10.1021/j100700a036

Cited by 14 publications

(6 citation statements)

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“…Zwitterionic surfactants have been little studied in the past, although the one used here has been demonstrated to be an excellent catalyst for the addition of cyanide ion to pyridinium ions. 15 Whatever the source of the rate effects is, they have quite different consequences in the case of these two reactions. There have been several studies of reaction kinetics in the presence of nonionic surfactants.…”

Section: Resultsmentioning

confidence: 99%

Secondary valence force catalysis. XIV. Effect of several surfactants on the kinetics of hydrolysis of a series of 2-(substituted phenoxy)tetrahydropyrans

Armas¹,

Clemente²,

Coronel³

et al. 1972

J. Org. Chem.

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Dilute aqueous solutions of sodium dodecyl sulfate and sodium hexadecyloxyethyl sulfate catalyze the hydrolysis of a series of 2-(substituted phen0xy)tetrahydropyrans. Rate increases from 15-to 50-fold are observed, depending on the nature of surfactant and substrate. Introduction of a methyl group a t the 1 position of the hexadecyloxyethyl sulfate markedly reduces its catalytic effectiveness. Activation parameters for the surfactantdependent reactions vary nonsystematically from those for the same reactions in 50% dioxane-water or in water. In contrast to the behavior of the anionic surfactants, dodecyltrimethylammonium propanesulfonate and dodecyldimethyl phosphine oxide inhibit the hydrolysis of these substrates.

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Section: Resultsmentioning

confidence: 99%

Secondary valence force catalysis. XIV. Effect of several surfactants on the kinetics of hydrolysis of a series of 2-(substituted phenoxy)tetrahydropyrans

Armas¹,

Clemente²,

Coronel³

et al. 1972

J. Org. Chem.

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“…In the latter class of simple chargetransfer molecular complexes ("trisubstituted"), the bonding between M and the halogen molecule has been likened to that in the hydrogen bond.3 The X-X angle is very close to 180°, and the strength of the complex may be related to the deviations of the X-X bond from its natural length. These two classes grade naturally into each other.3 5 In addition to classification as either molecular complexes (MC) or trigonal bipyramids (TB), these molecules may be characterized according to the ionic or covalent nature of the bonds. Organic chemists, in fact, have favored depicting many of these molecules as halosulfonium or haloselenonium halides (3).6 The (5) H. Hope and J. D. McCullough, Acta Crystallogr., 17, 712 (1964).…”

mentioning

confidence: 99%

Secondary valence force catalysis. XII. Enhanced reactivity and affinity of cyanide ion toward N-substituted 3-carbamoylpyridinium ions elicited by ionic surfactants and biological lipids

Baumrucker¹,

Calzadilla²,

Centeno³

et al. 1972

J. Am. Chem. Soc.

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Rate and equilibrium constants for the addition of cyanide ion to a series of N-alkyl-3-carbamoylpyridinium ions are markedly increased by dilute solutions of n-alkyltrimethylammonium bromides. For example, 0.02 M hexadecyl surfactant increases the rate constant for addition of cyanide to the N-hexadecyl substrate 950-fold and increases the corresponding association constant about 25,000-fold. More concentrated solutions of these surfactants also elicit marked increases in rate and equilibrium constants for the same reactions although the increases are not quite so pronounced as with more dilute solutions. This may, in part, reflect inhibition by the surfactant counterion since it has been established that the surfactant-dependent reactions are sensitive to inhibition by anions. The effectiveness of anions as inhibitors increases in the order F-< NO3-< CI-< Br-. The extent of surfactant facilitation of the addition of cyanide ion to the pyridinium ions increases with increasing hydrophobicity in both surfactant and substrate, suggesting that hydrophobic interactions may contribute to the activation energies. The zwitterionic surfactant dodecyldimethylammoniopropane sulfonate increases the rate and equilibrium constants for addition of cyanide ion to N-dodecyl-3-carbanioylpyridinium bromide by 40-and 5000-fold, respectively. Finally, this same reaction is subject to promotion by sonicated aqueous dispersions of lecithin, lysolecithin, and sphingomyelin. series of studies in the past several years has estab-A lished that rate and equilibrium constants for a number of organic reactions are sensitive functions of the concentration of ionic s~r f a c t a n t s .~ In most such cases the observed effects are the consequence of adsorption of one or more of the reacting species onto or into micelles formed from the surfactants. Electrostatic and hydrophobic interactions between the substrates and the components of the micelle dominate both the adsorption process itself and the rate and extent of bond-changing reactions which follow.Since those factors which influence rates and equilibria of organic reactions may not only provide additional insight into the reaction mechanisms concerned but also yield data pertinent to enzyme-catalyzed reactions, it appears profitable to pursue the study of organic reactions in the presence of surfactants more fully. Moreover, recent results suggest that the presence of ionic micelles may be important in determining the course of organic reactions, as well as their rate and extent.4 In this study, the rate and equilibrium constants for the addition of cyanide ion to a series of Nsubstituted 3-carbamoylpyridinium ions have been determined in the presence of a series of n-alkyltrimethylammonium ions, one zwitterionic surfactant, and several biological lipids.

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“…Later, several closely related alkaloids were isolated, such as isopilocarpine, pilocarpidine, and pilosine. The elucidation of the chemical structures of the jaborandi alkaloids is due primarily to Jowett (3), Pinner and Kohlhammer (4), and Pinner and Schwarz (5). There are two asymmetric centers in the lactone part of the molecule, and Jowett (6) assumed the relationship between pilocarpine and isopilocarpine to be stereochemical (cis-trans-isomers).…”

Section: Hydrolysis and Epimerization Kinetics Of Pilocarpine In Aquementioning

confidence: 99%

“…Relationships between the charge on the micelle and the charge on the reactant have been discussed (3, 4) as has secondary valence force catalysis (5). Reviews concerning the effects of surfactants on kinetics have also been presented (6,7).…”

mentioning

confidence: 99%

Hydrolysis Kinetics of Benzocaine and Homologs in the Presence of a Nonionic Surfactant

Smith

Kennedy

Nairn³

1974

Journal of Pharmaceutical Sciences

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Secondary valence force catalysis. XI. Enhanced reactivity and affinity of cyanide ion toward N-substituted 3-carbamoyl-pyridinium ions elicited by ionic surfactants

Cited by 14 publications

References 0 publications

Secondary valence force catalysis. XIV. Effect of several surfactants on the kinetics of hydrolysis of a series of 2-(substituted phenoxy)tetrahydropyrans

Secondary valence force catalysis. XIV. Effect of several surfactants on the kinetics of hydrolysis of a series of 2-(substituted phenoxy)tetrahydropyrans

Secondary valence force catalysis. XII. Enhanced reactivity and affinity of cyanide ion toward N-substituted 3-carbamoylpyridinium ions elicited by ionic surfactants and biological lipids

Hydrolysis Kinetics of Benzocaine and Homologs in the Presence of a Nonionic Surfactant

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