Arenediazonium o-Benzenedisulfonimides: Some Kinetics of Azo Coupling Reactions with Naphthols

Boga, Carla; Degani, Jacopo; Vecchio, Erminia Del; Fochi, Rita; Forlani, Luciano; Todesco, P. E.

doi:10.1002/1099-0690(200211)2002:22<3837::aid-ejoc3837>3.0.co;2-x

Cited by 6 publications

(4 citation statements)

References 8 publications

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“…[7] The explosive character is diminished when prepared by employing high molecular weight complex anions, for example, X À ¼ BF À 4 , leading to a significant improvement in their use and manipulation because they can be stored safely under proper conditions for a long time with negligible decomposition, [10,11] and in fact some of them are commercially available. The synthesis of arenediazonium o-benzenedisulfonimides [12] and arenediazonium trifluoroacetates [13] has also been proposed because of their significant stability under proper storage conditions.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of the reaction between 4‐hexadecylbenzenediazonium ions and vitamin C in emulsions: further evidence of the formation of diazo ether intermediates in the course of the reaction

Pastoriza-Gallego¹,

Fernández-Alonso²,

Losada‐Barreiro³

et al. 2008

J of Physical Organic Chem

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The kinetics and mechanism of the reaction between hydrophobic 4-hexadecylarenediazonium ions, 16-ArN R 2 and vitamin C, VC, in a model emulsion prepared by mixing octane, acidic (HCl) water and the non-ionic surfactant hexaethyleneglycol monododecyl ether, C 12 E 6 , were investigated. Because emulsions are opaque, linear sweep voltammetry, LSV, was employed to monitor the reaction. Voltammograms of 16-ArN R 2 in emulsions show two reduction peaks as in aqueous systems. The half-life for the spontaneous decomposition of 16-ArN R 2 in the emulsion was estimated as t 1/2 ¼ 14.5 h at T ¼ 25 -C. Upon addition of VC to the system, the first reduction peak of 16-ArN R 2 disappears almost immediately and a new reduction peak is detected at E p ¼ S0.25 V. Electrochemical titration of 16-ArN R 2 shows that the new peak corresponds to the formation of a 1:1 adduct. The i P (E p ¼ S0.25 V) values can be linearly correlated with [16-ArN R 2 ] and the observed rate constants, k obs , were determined by fitting the (i p , t) data to the integrated first order equation. The variation of k obs with [VC] follows a saturation kinetics profile, consistent with the formation of an intermediate in a pre-equilibrium step. All the evidence is consistent with a reaction mechanism comprising two competitive pathways, the spontaneous D N R A N mechanism and the unimolecular decomposition of a transient diazo ether (DE) formed in a pre-equilibrium step. The data allowed estimations of the interfacial rate constant for the reaction between 16-ArN R 2 and VC S but did not allow the determination of the equilibrium constant for the DE formation.

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Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of the reaction between 4‐hexadecylbenzenediazonium ions and vitamin C in emulsions: further evidence of the formation of diazo ether intermediates in the course of the reaction

Pastoriza-Gallego¹,

Fernández-Alonso²,

Losada‐Barreiro³

et al. 2008

J of Physical Organic Chem

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“…3 ( Z )-4-Hydroxy-3-((2-hydroxynaphthalen-1-yl)diazenyl)-7-nitronaphthalene-1-sulfonic acid (HHDN) is the crucial intermediate for the synthesis of acid black 172 dye. , As shown in Scheme , the 7-nitronaphtho[2,1- d ][1,2,3]oxadiazole-5-sulfonic acid (NOSA) and 2-naphthol are used as reactants for the synthesis of HHDN in a typical industrial process. Water is selected as the solvent in both the preparation of 1-hydroxy-6-nitro-4-sulfonaphthalene-2-diazonium salt (HNSD) and the HHDN . In polar solvents, the NOSA with an unstable functional group (-[1,2,3]oxadiazole) is completely formed as the diazone isomer (DNOD), and it is easy to transform into the resonance structure of diazonium salt (HSDN) in the presence of hydrogen ions at room temperature .…”

Section: Introductionmentioning

confidence: 99%

“…Water is selected as the solvent in both the preparation of 1-hydroxy-6-nitro-4-sulfonaphthalene-2-diazonium salt (HNSD) and the HHDN. 6 In polar solvents, the NOSA with an unstable functional group (-[1,2,3]oxadiazole) is completely formed as the diazone isomer (DNOD), and it is easy to transform into the resonance structure of diazonium salt (HSDN) in the presence of hydrogen ions at room temperature. 7 The reaction rate of the diazo coupling between 2-naphthol and HNSD is quite slow compared to the other diazo coupling reactions.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Measurement and Modeling of a Slow-Rate Diazo Coupling Reaction

Zheng

Luo

Wei

2023

Ind. Eng. Chem. Res.

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The reaction network of the diazo coupling between 1hydroxy-6-nitro-4-sulfonaphthalene-2-diazonium salt and 2-naphthol was identified through experimental methods. The kinetic experiments were conducted at the temperature range of 303−323 K. A kinetic model, which takes the decomposition of the diazonium salt into account, was established, and the kinetic parameters were estimated based on the experimental data. The model simulation results showed good agreement with the experimental data. Then, the effects of the reactant concentration, the molar ratio, and the reaction temperature were further investigated using the kinetic model. Finally, this kinetic model was coupled with a plug-flow reactor model and an axial dispersion model to reveal the influence of heat transfer and backmixing. This study can shed some light on the design and optimization of the industrial tubular reactors.

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“…Aromatic rings strongly activated by powerful electron‐donating groups are particularly suitable substrates for investigations of the mechanism of electrophilic aromatic substitution. The carbon–carbon bond‐forming reactions between neutral or charged electrophilic reagents and naphthols, 2‐amino‐1,3‐thiazole derivatives, and 1,3,5‐triaminobenzenes allowed us to isolate and investigate σ complexes, including those that are simultaneously Wheland (W) and Meisenheimer (M) complexes. [2a], , In particular, the reactions between triaminobenzenes and diazonium salts permitted the elucidation of the mechanism of the azo‐coupling reaction through the study of its separate steps, owing to the stability of the W complexes .…”

Section: Introductionmentioning

confidence: 99%

Hydroxy‐ and Methoxybenzene Derivatives with Benzenediazonium Salts ― Chemical Behavior and Tautomeric Problems

et al. 2017

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The azo‐coupling reactions between 4‐nitrobenzenediazonium tetrafluoroborate and a series of benzene derivatives bearing at least one electron‐donating hydroxy or methoxy substituent have been studied. Depending on the nucleophile and its relative ratio with the diazonium salt, it was possible to obtain mono‐ and disubstituted products as well as a trisubstituted product for phloroglucinol. The reactions between 3,5‐diaminoanisole or 3,5‐diaminophenol derivatives and 2 equiv. of diazonium salt gave the monosubstituted product in the first case and a diadduct in the second case; X‐ray diffraction analysis revealed a highly symmetric structure for the latter. The different behaviors of hydroxy‐ and methoxy‐substituted compounds was particularly evident for phloroglucinol and 1,3,5‐trimethoxybenzene and may be rationalized on the basis of the different electronic effects of the substituents. The propensities of the aromatic rings to undergo H/D exchange reactions were investigated for a series of substrates, and a comparison of the results obtained provided new insights into this phenomenon and permitted a better explanation of the findings reported here; a new particular interaction competes with the formation of a proton–phloroglucinol σ complex.

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Arenediazonium o-Benzenedisulfonimides: Some Kinetics of Azo Coupling Reactions with Naphthols

Cited by 6 publications

References 8 publications

Kinetics and mechanism of the reaction between 4‐hexadecylbenzenediazonium ions and vitamin C in emulsions: further evidence of the formation of diazo ether intermediates in the course of the reaction

Kinetics and mechanism of the reaction between 4‐hexadecylbenzenediazonium ions and vitamin C in emulsions: further evidence of the formation of diazo ether intermediates in the course of the reaction

Kinetic Measurement and Modeling of a Slow-Rate Diazo Coupling Reaction

Hydroxy‐ and Methoxybenzene Derivatives with Benzenediazonium Salts ― Chemical Behavior and Tautomeric Problems

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