Preparative access to transformation products (TPs) of furosemide: a versatile application of anodic oxidation

Laurencé, Céline; Rivard, Michaël; Lachaise, Isabelle; Bensemhoun, Julia; Martens, Thierry

doi:10.1016/j.tet.2011.10.006

Cited by 16 publications

(11 citation statements)

References 29 publications

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“…The identified intermediates as aniline (H), the γ‐ketoenal (B), and the pyridinium derivate (C) have also been identified as resulting products from FRSM by metabolic oxidation processes . Furthermore, aniline was obtained as well by electrochemical oxidation of FRSM . On the other hand, it is well known that the addition of • OH to an unsaturated bond (hydroxylation) is one of the main mechanisms of the reaction between • OH and organic compounds with unsaturated bonds .…”

Section: Resultsmentioning

confidence: 99%

Electro‐Oxidation of the Pharmaceutical Furosemide: Kinetics, Mechanism, and By‐Products

Olvera‐Vargas¹,

Oturan²,

Buisson

et al. 2015

CLEAN Soil Air Water

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Furosemide is a widely prescribed diuretic whose unambiguous presence in water appointed it as an emerging pollutant. This work focuses on the electrochemical degradation of this drug in aqueous solutions by electrochemical advanced oxidation processes, electro‐Fenton and anodic oxidation, using Pt/carbon‐felt and boron doped diamond (BDD)/carbon‐felt cells with H2O2 electrogeneration. The higher oxidation power of the electro‐Fenton process using a BDD anode was demonstrated. The oxidative degradation of furosemide by electrochemically generated •OH radicals follows a pseudo‐first order kinetics. The absolute rate constant of the oxidation reaction of furosemide by •OH was determined using a competition kinetics method and found to be 3.4 × 109 M−1 s−1. The evolution of the total organic carbon removal during the treatment as a mineralization efficiency parameter was investigated. It was found that the electrochemical degradation of furosemide yields formation of aromatic by‐products which are oxidized afterwards to aliphatic carboxylic acids before their conversion to CO2 and inorganic ions (NH4+, NO3–, Cl–, and SO42–). The toxicity assessment by the Microtox® method revealed formation of oxidation reaction intermediates more toxic than the parent molecule. Nevertheless, the overall results confirm the high effectiveness of anodic oxidation and electro‐Fenton processes for the removal of furosemide and its by‐products from aqueous media.

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Section: Resultsmentioning

confidence: 99%

Electro‐Oxidation of the Pharmaceutical Furosemide: Kinetics, Mechanism, and By‐Products

Olvera‐Vargas¹,

Oturan²,

Buisson

et al. 2015

CLEAN Soil Air Water

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“…Beyond the scope of this work, various literature reports point out such hetero-Diels-Alder reactions as possibly relevant of bio-orthogonal chemistry because of their selectivity, moderate activation energy and ability to proceed under biological conditions, taking in account e.g., the pH and temperature [66,67,68,69,70]. Besides, since pyridinium-containing compounds are considered as possible exogenous neurotoxins, research efforts have also been undertaken to disclose the formation of such compounds under endogenous (biogenic) conditions [33,34,35,36,37,43,44,45]. In this respect, the biological activity of newly synthesized pyridinium compounds 17 – 19 , are currently under evaluation with promising results to be published in future papers.…”

Section: Discussionmentioning

confidence: 99%

“…For example, 1-methyl-4-phenylpyridinium (MPP+) 1 is the most popular molecule used to induce Parkinsonism in vivo (Scheme 1) [34,35,36]. More recently, pyridinium furosemide (PF) 2 , has been also used as a model in helping to identify specific events of Parkinson’s disease [37].…”

Section: Introductionmentioning

confidence: 99%

Novel Synthesis of Substituted 2-Trifluoromethyl and 2-Perfluoroalkyl N-Arylpyridinium Compounds—Mechanistic Insights

et al. 2019

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We report a new one-pot synthesis of 2-trifluoromethylated/2-perfluoroalkylated N-aryl-substituted pyridiniums, 5,6,7,8-tetrahydroquinoliniums and 6,7,8,9-tetrahydro-5H-cyclohepta[b]-pyridinium compounds starting from an activated β-dicarbonyl analogue (here a perfluoro-alkylated gem-iodoacetoxy derivative), an aromatic amine and a (cyclic or acyclic) ketone. The key step of this multicomponent reaction, involves the formation of a 3-perfluoroalkyl-N,N’-diaryl-1,5-diazapentadiene intermediate, various examples of which were isolated and characterized for the first time, together with investigation of their reactivity. We propose a mechanism involving a concurrent inverse electron demand Diels-Alder or Aza-Robinson cascade cyclisation, followed by a bis-de-anilino-elimination. Noteworthy, a meta-methoxy substituent on the aniline directs the reaction towards a 2-perfluoroalkyl-7-methoxyquinoline, resulting from the direct cyclization of the diazapentadiene intermediate, instead of pyridinium formation. This is the first evidence of synthesis of pyridinium derivatives from activated β-dicarbonyls, ketones, and an aromatic amine, the structures of which (both reactants and products) being analogous to species involved in biological systems, especially upon neurodegenerative diseases such as Parkinson’s. Beyond suggesting chemical/biochemical analogies, we thus hope to outline new research directions for understanding the mechanism of in vivo formation of pyridiniums, hence possible pharmaceutical strategies to better monitor, control or prevent it.

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“…Recently, we described the preparation of an N -arylated pyridinium . Later, the toxicological evaluation of this compound showed its ability to induce cell death by apoptosis on human neuroblastoma cells (SH-SY5Y) .…”

Section: Introductionmentioning

confidence: 76%

Microwaves and Aqueous Solvents Promote the Reaction of Poorly Nucleophilic Anilines with a Zincke Salt

et al. 2016

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The Zincke reaction allows the transformation of primary amines into their respective N-alkylated or N-arylated pyridinium salts. While nucleophilic primary amines (typically, aliphatic primary amines) often lead to quantitative reactions and has been documented profusely, the use of poorly nucleophilic amines still requires an in depth account. To date, the lack of nucleophilicity of the amines is redhibitory. The subject addressed in this article is a series of primary amines deriving from aniline having been engaged in Zincke reactions. Efficient transformations were obtained, even when conducted on electronically deactivated, eventually also sterically hindered, substrates. This was achieved by the combined use of microwave activation and aqueous solvents. Under our conditions, the role of water revealed indeed crucial to avoid the self-degradation of the Zincke salt, the reagent of the reaction.

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Preparative access to transformation products (TPs) of furosemide: a versatile application of anodic oxidation

Cited by 16 publications

References 29 publications

Electro‐Oxidation of the Pharmaceutical Furosemide: Kinetics, Mechanism, and By‐Products

Electro‐Oxidation of the Pharmaceutical Furosemide: Kinetics, Mechanism, and By‐Products

Novel Synthesis of Substituted 2-Trifluoromethyl and 2-Perfluoroalkyl N-Arylpyridinium Compounds—Mechanistic Insights

Microwaves and Aqueous Solvents Promote the Reaction of Poorly Nucleophilic Anilines with a Zincke Salt

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