Kinetic evidence for the formation of diazo ethers in the course of reactions between arenediazonium ions and antioxidants

Dudzik, Anna; Jaszczuk, Katarzyna; Losada‐Barreiro, Sonia

doi:10.1039/c6nj03670h

Cited by 3 publications

(1 citation statement)

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“…These adducts have been isolated, chemically characterized and identified as the diazoethers. 44 The reaction of aryldiazonium salts with the ascorbate ions occurs in three steps as depicted in Scheme 2b: (1) the rapid formation of the (Z)-diazoether; (2) partial decomposition of the (Z)-diazoether to yield the reduction products, and (3) the slow conversion of the (Z)-diazoether to the thermodynamically more stable (E)-diazoether. Some studies have confirmed that the (Z)-diazoether is formed almost exclusively, and a part of it is transformed to the (E)-isomer by an ionization-recombination mechanism.…”

Section: Resultsmentioning

confidence: 99%

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

et al. 2020

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Section: Resultsmentioning

confidence: 99%

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

et al. 2020

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Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions

Bravo‐Díaz

González-Romero

2022

Aryl Diazonium Salts and Related Compounds

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A novel combined chemical kinetic and trapping method for probing the relationships between chemical reactivity and interfacial H₂O, Br⁻ and H⁺ ion molarities in CTAB/C₁₂E₆ mixed micelles

Dar

Romsted

Nazir

et al. 2017

Phys. Chem. Chem. Phys.

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A delicate balance-of-forces governs the interactions responsible for surfactant self-assembly and chemical reactivity within them. Chemical reactions in micellar media generally occur in the interfacial region of micelles that is a complex mixture of: water, headgroups, counterions, co-ions, acids or bases, organic solvents, and the reactants themselves. We have carried out a detailed study of a complex chemical reaction in mixed CTAB/CE micelles by using the chemical kinetic (CK) and chemical trapping (CT) methods. The results provide a detailed quantitative treatment of the reaction of the anion of the antioxidant t-butylhydroquinone, TBHQ, with 4-hexadecylbenzenediazonium, 16-ArN, within the interfacial region of the mixed micelles in the CE mole fraction range of 0 to 1 at three different total surfactant concentrations. CK experiments showed that this reaction is monophasic in CE micelles, but biphasic in mixed micelles. The results were fully consistent with a complex mechanism in which TBHQ reacts with 16-ArN to give a transient diazoether intermediate that competitively breaks down into products and or reverts to starting materials. The kinetics are the same in mixed micelles of CTAB/CE (grow) and CTAB/CE (don't grow) showing that the rates only depend on micelle composition, not shape. CT results provided estimates of interfacial molarities of HO are approximately constant at ca. 39 and Br decreases from ca. 2.75 to 0.05 moles per liter of interfacial volume as CE mole fraction increases from 0 to 1. Combined CK/CT results provided values for interfacial pH, ranging from ca. 4.25 in cationic micelles to 1.5 in nonionic micelles despite a constant bulk pH of 1.5 and the TBHQ interfacial pK = 3.8 at all CE molar fractions. In totality, these results yielded an extraordinary amount of quantitative information about the relationships between the chemical reactivity and interfacial compositions of the mixed micelles.

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Kinetic evidence for the formation of diazo ethers in the course of reactions between arenediazonium ions and antioxidants

Abstract: Non-zero, pH-dependent, saturation kinetics are observed in the course of the reaction between 3-methylbenzenediazonium ions and hydroxytyrosol.

Cited by 3 publications

References 46 publications

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions

A novel combined chemical kinetic and trapping method for probing the relationships between chemical reactivity and interfacial H₂O, Br⁻ and H⁺ ion molarities in CTAB/C₁₂E₆ mixed micelles

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Kinetic evidence for the formation of diazo ethers in the course of reactions between arenediazonium ions and antioxidants

Abstract: Non-zero, pH-dependent, saturation kinetics are observed in the course of the reaction between 3-methylbenzenediazonium ions and hydroxytyrosol.

Cited by 3 publications

References 46 publications

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

Self-limiting covalent modification of carbon surfaces: diazonium chemistry with a twist

Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions

A novel combined chemical kinetic and trapping method for probing the relationships between chemical reactivity and interfacial H2O, Br− and H+ ion molarities in CTAB/C12E6 mixed micelles

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A novel combined chemical kinetic and trapping method for probing the relationships between chemical reactivity and interfacial H₂O, Br⁻ and H⁺ ion molarities in CTAB/C₁₂E₆ mixed micelles