Selective Oxidation of Secondary Amines to N,N-Disubstituted Hydroxylamines by Choline Peroxydisulfate

Banan, Alireza; Valizadeh, Hassan; Heydari, Akbar; Moghimi, Abolghasem

doi:10.1055/s-0036-1589089

Cited by 8 publications

(3 citation statements)

References 44 publications

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“…Previous reports suggested that the oxidation impurity of ketamine was nitrogen oxidation impurity 31, which was synthesized via ionic liquid choline peroxydisulfate (ChPS). 14 However, this impurity was actually synthesized via Scheme 5. Side Reactions Involved in the Preparation of 5 hydrogen peroxide and oxidized in ethanol.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…During the forced degradation of ketamine hydrochloride using 3% H 2 O 2 and heating at 90 °C for 2 h, we found that the maximum oxidative degradation impurity was about 1.23%. Previous reports suggested that the oxidation impurity of ketamine was nitrogen oxidation impurity 31 , which was synthesized via ionic liquid choline peroxydisulfate (ChPS) . However, this impurity was actually synthesized via hydrogen peroxide and oxidized in ethanol.…”

Section: Results and Discussionmentioning

confidence: 99%

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Optimized Process and Quality Evaluation for Ketamine Hydrochloride

Jiang,

Pan,

Liu

et al. 2023

Org. Process Res. Dev.

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In this study, we developed an enhanced and efficient kilogram-scale synthesis method for ketamine hydrochloride. We discovered that using N-bromosuccinimide (NBS) instead of HBr/H 2 O 2 improved the conversion rate of the bromination reaction from 88% to 99% and led to a milder and steadier reaction. Besides, CH 3 NH 2 /K 2 CO 3 was used in the methylamination reaction to shorten the reaction time from 80 to 15 h, with an 80% yield of 1-((2-chlorophenyl) (methylimino) methyl) cyclopentanol hydrochloride (6) and 99.5% purity. Furthermore, the residue on ignition of ketamine hydrochloride decreased from 3.00% to below 0.10% with extra aqueous base washing. Several related impurities of ketamine hydrochloride were also assessed, and the clarity and color of the ketamine hydrochloride solution were investigated. In summary, the optimized process was industrially scalable and able to control the final quality of ketamine hydrochloride.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Optimized Process and Quality Evaluation for Ketamine Hydrochloride

Jiang,

Pan,

Liu

et al. 2023

Org. Process Res. Dev.

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“…In particular, unsymmetrical secondary hydroxylamines often require indirect syntheses, most often achieved by oxidation of a primary amine followed by alkylation. , In this context, methods based on the oxidation of amines are attractive and can provide access to secondary hydroxylamines in fewer steps. Indeed, secondary hydroxylamines have been synthesized via various oxidative methods (Scheme ), including the direct oxidation of secondary amines (Scheme A). , While reported procedures are direct, they often suffer from limitations, including poor chemoselectivity, overoxidation, narrow substrate scope, variable or low yields, or specialized or unstable reagents. Thus, alternative two-step sequences featuring an oxidation step are commonly employed, such as the oxidation of suitable tertiary amines followed by Cope elimination or oxidation of secondary amines with peroxide derivatives to form O -benzoyl hydroxylamines, which can then be cleaved under basic conditions (Scheme B) …”

Section: Introductionmentioning

confidence: 99%

Oxidative Syntheses of N,N-Dialkylhydroxylamines

Barriault,

Ly,

Allen

et al. 2024

J. Org. Chem.

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Despite the wide utility of hydroxylamines in organic synthesis, relatively few are commercially available, and there is a need for direct, efficient, and selective methods for their synthesis. Herein, we report two complementary methods to accomplish direct oxidation of secondary amines using UHP as an oxidant. The first method uses 2,2,2-trifluoroethanol (TFE) and a large excess of amine. Isolation of hydroxylamine products is enabled by selective salt formation, and recovery of excess amine is demonstrated. The second method uses hexafluoroacetone as an additive and is highlighted by the 1:1 stoichiometry between the oxidant and amine.

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Metal‐Free, Persulfate‐Mediated Oxidative Radical CH Functionalizations

Gupta

Laha

2022

Handbook of CH-Functionalization

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Carbon–carbon/carbon–heteroatom bond formation via oxidative CH functionalization is a novel approach which shifts the focus from the standard organic synthesis involving selective reactions at functional groups. The new logic relies on the controlled functionalization of specific CH bonds, even in the presence of supposedly more reactive functional groups and is currently a heavily explored topic. Peroxydisulfate oxidants have risen as an economical and readily available choice of inorganic oxidant, catalyzing a wide range of oxidative transformations, varying from laboratory experiments to industrial processes. The current article provides a comprehensive analysis of significant oxidative transformations brought about by persulfates, with or without the aid of any additives, under transition‐metal‐free conditions. The report focuses on the critical assessment of the reactions involved, the explored substrate scopes, and the underlying mechanisms. This article can be a useful guide for the organic chemists interested in the expedient synthesis of new chemical entities, formulation of mechanistic manifolds involving the sulfate radical anion, or designing of novel oxidative transformations. However, a thorough understanding of the unsolved mechanisms can further reinforce the field.

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Selective Oxidation of Secondary Amines to N,N-Disubstituted Hydroxylamines by Choline Peroxydisulfate

Abstract: N,N-Disubstituted hydroxylamines were prepared directly from secondary amines by a reliable method using an oxidizing task-specific ionic liquid, choline peroxydisulfate. The operational simplicity, high selectivity, and green reaction conditions, make this method efficient and practical.

Cited by 8 publications

References 44 publications

Optimized Process and Quality Evaluation for Ketamine Hydrochloride

Optimized Process and Quality Evaluation for Ketamine Hydrochloride

Oxidative Syntheses of N,N-Dialkylhydroxylamines

Metal‐Free, Persulfate‐Mediated Oxidative Radical CH Functionalizations

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