Kinetics and Mechanism of the Oxidation of Aliphatic Amines

Gragerov, I. P.; Skrunts, L. K.; Geller, B. A.

doi:10.1070/rc1982v051n01abeh002799

Cited by 16 publications

(5 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[4] and [5] fully agree with the experimental results. However, it has been much discussed whether the oxidation of amines occurs through transfer of an electron, of a hydrogen atom, or of a hydride ion (45,46). Obviously, from the kinetic data found for the reaction, the type of particle transferred to permanganate ion from methylamine does not directly follow, since the three kinds of transfer would lead to the same rate law (see eq.…”

Section: Discussionmentioning

confidence: 94%

Kinetics and mechanisms of oxidation of methylamine by permanganate ion

Mata-Pérez¹,

Perez‐Benito²

1987

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 65, 2373 (1987). The oxidation of methylamine by permanganate ion in aqueous phosphate buffers is autocatalyzed by a soluble form of colloidal manganese dioxide temporarily stabilized in solution by adsorption of phosphate ions on its surface. The dependence of the rate constants of both the noncatalytic and catalytic mechanisms on the concentrations of both methylammonium and hydroxyl ions and on temperature has been determined. The activation parameters have been obtained. Mechanisms in agreement with the experimental data are proposed.FERNANDO MATA-PEREZ et JOAQUIN F. PEREZ-BENITO. Can. J. Chem. 65, 2373 (1987). L'oxydation de la mithylamine par l'ion permanganate, en solution dans des tampons de phosphates, est autocatalyste par une forme soluble du bioxyde de manganese colloidal qui est temporairement stabiliste en solution par adsorption des ions phosphates sur sa surface. On a dttermini les relations qui existent entre les constantes de vitesse, tant des micanismes catalysis que ceux des mtcanismes non-catalysts, et soit les concentrations tant des ions mithylammonium que des ions hydroxyles soit la temptrature. On a obtenu les paramttres d'activation. On propose des micanismes qui sont en accord avec les donntes expirimentales.[Traduit par la revue]

show abstract

Section: Discussionmentioning

confidence: 94%

Kinetics and mechanisms of oxidation of methylamine by permanganate ion

Mata-Pérez¹,

Perez‐Benito²

1987

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…21 Furthermore, although nonpolar solvents are generally associated with higher rates of amine oxidation, 22 oxidations in polar solvents (e.g., methanol, water) operate by a different mechanism. 23 These processes favor the formation of N-oxides 24 and have even been shown to facilitate desilylation in electrochemical and photoinduced oxidations, 21c,25 which may explain the original observations of low yields and side-products in alcohols. Consequently, functionalizations of the α -silylsubstituted amine hydrochlorides 11 and 43 , once considered challenging (e.g., reductive aminations of ketones, peptide couplings), were rendered easily accessible by the simple exclusion of oxygen in non-coordinating solvents, and N- alkylated products were prepared in high yields and with excellent purities.…”

Section: Discussionmentioning

confidence: 98%

“…However, it is well known that the oxidation potential of amines is strongly influenced by substitution, and the effect of α-substitution by Group 14 elements like silicon is to increase susceptibility to oxidation . Furthermore, although nonpolar solvents are generally associated with higher rates of amine oxidation, oxidations in polar solvents (e.g., methanol, water) operate by a different mechanism . These processes favor the formation of N-oxides and have even been shown to facilitate desilylation in electrochemical and photoinduced oxidations, , which may explain the original observations of low yields and side-products in alcohols.…”

Section: Discussionmentioning

confidence: 99%

Synthesis, Reactivity, Functionalization, and ADMET Properties of Silicon-Containing Nitrogen Heterocycles

Barraza

Denmark

2018

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Silicon-containing compounds have been largely ignored in drug design and development, despite their potential to improve not only the potency but also the physicochemical and ADMET (absorption, distribution, metabolism, excretion, toxicity) properties of drug-like candidates because of the unique characteristics of silicon. This deficiency is in large part attributable to a lack of general methods for synthesizing diverse organosilicon structures. Accordingly, a new building block strategy has been developed that diverges from traditional approaches to incorporation of silicon into drug candidates. Flexible, multi-gram-scale syntheses of silicon-containing tetrahydroquinoline and tetrahydroisoquinoline building blocks are described, along with methods by which diversely functionalized silicon-containing nitrogen heterocycles can be rapidly built using common reactions optimized to accommodate the properties of silicon. Furthermore, to better clarify the liabilities and advantages of silicon incorporation, select compounds and their carbon analogues were challenged in ADMET-focused biological studies.

show abstract

“…138 Nonaromatic aminium radicals were first reported in the early 1880s by A. W. Wawzonek during the Hofmann−Loffler preparation of N-methylgranatanine. 143,765 In this seminal publication, he reported that the treatment of 1-bromo-2propylpiperidine with hot sulfuric acid, followed by basic workup, resulted in the formation of a cyclized tertiary amine, which was later identified as octahydroindolizine (Scheme 263). 766 This reaction was extensively studied by K. Lofer and C. proceed by a radical chain process.…”

Section: Thermal-and Photoinduced Set Mediated By Amine Donorsmentioning

confidence: 99%