Nitrosation of 2-hydroxyethylpiperidine

Magro, Jacir Dal; Meijide, Francisco; Provost, Sigrid; Tato, José Vázquez; Yunes, Rosendo A.

doi:10.1039/b009439k

Cited by 4 publications

(4 citation statements)

References 15 publications

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“…Thus, many reactions described in the literature involve intramolecular transfer of the nitroso group. Typical examples are the O-NOǞN-NO migrations observed in the nitrosation of amides and ureas, [14] amino acids [15] in acidic media, and hydroxylamines; [16] the C-NOǞN-NO migrations found in the nitrosation of indoles [17] in acidic media; and the N-NOǞC-NO migrations observed in the Fischer-Hepp rearrangement. [18] Also, S-NOǞN-NO migrations are common when studying nitrosation of cysteine in acidic [19] and basic or neutral [20] media, thioureas [21] and thioproline or thiomorpholine.…”

Section: Resultsmentioning

confidence: 97%

Enol Nitrosation Revisited: Determining Reactivity of Ambident Nucleophiles

et al. 2009

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Enols are one of the most important types of ambident nucleophiles being widely used as reagents in organic chemistry. The relevance of enols has led to considerable interest in developing methods to determine the reactivity of their nucleophilic centers. In this sense, the mainstream literature works on this topic make use of a combination of overall rate constants together with the analysis of the reaction products. By knowing the product ratio it is possible to determine the ratio between the reaction rates on each site. Thus, the reactivity for each nucleophilic position can be obtained. This is a reliable approach as long as the isolation or in situ characterization of the reaction products can be carried out. In the case of unstable and/or interconvertible products where the use of identification techniques is not possible, an alternative methodology must be found. For that reason, our research group has developed a model that allows us to study and quantify separately the reaction rates of enol nucleophilic centers even if only one final reaction product is obtained. This model is based on the fact that nitrosation of enols shows well‐differentiated behavior depending on whether the reaction proceeds through the carbon or the oxygen atom. The present study provides insights into the ambident nature of enols as well as a methodology for determining the chemical reactivity of their nucleophilic centers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultsmentioning

confidence: 97%

Enol Nitrosation Revisited: Determining Reactivity of Ambident Nucleophiles

et al. 2009

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“…Nitrosation of 2-hydroxyethylpiperidine in acidic media proceeds via an initial fast attack at the OH group to an alkyl nitrite in the protonated amine. 91 Rate-limiting loss of a proton from this intermediate is followed by a fast internal nitroso group transfer from the O to the N atom to give the corresponding N-nitroso derivative.…”

Section: Reviewmentioning

confidence: 99%

Secondary Targets of Nitrite-Derived Reactive Nitrogen Species: Nitrosation/Nitration Pathways, Antioxidant Defense Mechanisms and Toxicological Implications

d’Ischia

Napolitano

Manini

et al. 2011

Chem. Res. Toxicol.

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Nitrite, the primary metabolite of nitric oxide (NO) and a widely diffused component of human diet, plays distinct and increasingly appreciated roles in human physiology. However, when exposed to acidic environments, typically in the stomach, or under oxidative stress conditions, it may be converted to a range of reactive nitrogen species (RNS) which in turn can target a variety of biomolecules. Typical consequences of toxicological relevance include protein modification, DNA base deamination and the formation of N-nitrosamines, among the most potent mutagenic and carcinogenic compounds for humans. Besides primary biomolecules, nitrite can cause structural modifications to a variety of endogenous and exogenous organic compounds, ranging from polyunsaturated fatty acids to estrogens, tocopherol, catecholamines, furans, retinoids, dietary phenols, and a range of xenobiotics. The study of the interactions between nitrite and key food components, including phenolic antioxidants, has therefore emerged as an area of great promise for delineating innovative strategies in cancer chemoprevention. Depending on substrates and conditions, diverse reaction pathways may compete to determine product features and distribution patterns. These include nitrosation and nitration but also oxidation, via electron transfer to nitrosonium ion or nitrogen dioxide. This contribution aims to provide an overview of the main classes of compounds that can be targeted by nitrite and to discuss at chemical levels the possible reaction mechanisms under conditions that model those occurring in the stomach. The toxicological implications of the nitrite-modified molecules are finally addressed, and a rational chemical approach to the design of potent antinitrosing agents is illustrated.

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“…Likewise, many reactions described in the literature involve intramolecular transfer of the nitroso group. Typical examples are the O -NO→ N -NO migrations observed in the nitrosation of amides and ureas, amino acids in acidic media, and hydroxylamines; the C -NO→ N -NO migrations found in the nitrosation of indoles in acidic media, and the N -NO→ C -NO migrations observed in the Fischer-Hepp rearrangement. Also, S -NO→ N -NO migrations are common when studying nitrosation of cysteine in acidic and basic or neutral media, thioureas, and thioproline or thiomorpholine …”

Section: Resultsmentioning

confidence: 99%

First Kinetic Discrimination Between Carbon and Oxygen Reactivity of Enols

et al. 2008

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Nitrosation of enols shows a well-differentiated behavior depending on whether the reaction proceeds through the carbon (nucleophilic catalysis is observed) or the oxygen atom (general acid-base catalysis is observed). This is due to the different operating mechanisms for C- and O-nitrosation. Nitrosation of acetylacetone (AcAc) shows a simultaneous nucleophilic and acid-base catalysis. This simultaneous catalysis constitutes the first kinetic evidence of two independent reactions on the carbon and oxygen atom of an enol. The following kinetic study allows us to determine the rate constants for both reaction pathways. A similar reactivity of the nucleophilic centers with the nitrosonium ion is observed.

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Nitrosation of 2-hydroxyethylpiperidine

Cited by 4 publications

References 15 publications

Enol Nitrosation Revisited: Determining Reactivity of Ambident Nucleophiles

Enol Nitrosation Revisited: Determining Reactivity of Ambident Nucleophiles

Secondary Targets of Nitrite-Derived Reactive Nitrogen Species: Nitrosation/Nitration Pathways, Antioxidant Defense Mechanisms and Toxicological Implications

First Kinetic Discrimination Between Carbon and Oxygen Reactivity of Enols

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