Dimethoxyethane as an Alternative Solvent for Schmidt Reactions. Preparation of Homochiral N-(5-Oxazolyl)oxazolidinones from N-Acetoacetyl Derivatives of Oxazolidinones

Galvez, N.; Moreno‐Mañas, Marcial; Sebastián, Rosa Marı́a; Vallribera, Adelina

doi:10.1016/0040-4020(95)00989-2

Cited by 34 publications

(11 citation statements)

References 8 publications

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“…In many cases, Schmidt reactions were carried out in halogenated solvents; this is potentially dangerous as polyhalogenated alkanes can give rise to explosive polyazides. Moreno-Man ˜as et al 6 proposed the use of DME as a safer solvent than chloroform and dichloromethane for performing reactions involving azides. Using their reaction conditions, NaN 3 and methanesulfonic acid in DME, ketones were converted to amides in high yield, e.g.…”

Section: The Schmidt Reaction With Ketonesmentioning

confidence: 99%

Azide rearrangements in electron-deficient systems

2006

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The azide group has a diverse and extensive role in organic chemistry, reflected in the power of azide anion as a strong nucleophile, the role of organic azides as excellent substrates for cycloaddition reactions, the uses of azides as precursors of amines and nitrenes, and azide rearrangements known as the Curtius and Schmidt reactions. In recent years the scope of the Schmidt reaction has begun to be explored in depth, so that it now represents an important reaction in synthetic chemistry. This tutorial review analyses and summarises key recent developments in the field of Schmidt reactions.

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Section: The Schmidt Reaction With Ketonesmentioning

confidence: 99%

Azide rearrangements in electron-deficient systems

2006

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“…In the synthesis of phosphonitrilic hydroquinone prepolymers, the carcinogenic and ozone-depleting solvent carbon tetrachloride was replaced with cyclohexane with a slight increase in yield (108). Chloroform was considered an explosive hazard in solvating Schmidt reactions involving azides, and it was replaced with dimethoxyethane (109). Dichloromethane, or methylene chloride, is one of the most popular synthesis solvents, but it is a suspected carcinogen and is highly volatile (bp=40°C).…”

Section: Altenative Solvents For Synthesismentioning

confidence: 99%

Solvent replacement for green processing.

Sherman

Chin

Huibers

et al. 1998

Environ Health Perspect

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The implementation of the Montreal Protocol, the Clean Air Act, and the Pollution Prevention Act of 1990 has resulted in increased awareness of organic solvent use in chemical processing. The advances made in the search to find "green" replacements for traditional solvents are reviewed, with reference to solvent alternatives for cleaning, coatings, and chemical reaction and separation processes. The development of solvent databases and computational methods that aid in the selection and/or design of feasible or optimal environmentally benign solvent alternatives for specific applications is also discussed.ImagesFigure 2Figure 3

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“…Recent advances in flow chemistry, in particular microreactor technology, have demonstrated the safe utilization of hazardous reagents such as HN 3 within small-volume enclosed reactors such that only small quantities are present at any one time. − Recently reported was a Schmidt protocol using methanesulfonic acid–1,2-dimethoxyethane (MsOH–DME) that proved to be efficient at rearrangements of cyclohexanone and a range of acetophenones . Rearrangements of aryl carboxylic acids using superacidic TMSN 3 /triflic acid conditions, microwave-assisted intramolecular Schmidt rearrangements, and Beckmann rearrangements using trifluoroacetic acid and visible light have also recently been demonstrated in continuous-flow microreactors, providing safer protocols and precedent for the scalable use of these chemistries.…”

Section: Introductionmentioning

confidence: 99%

Toward the Scale-Up of a Bicyclic Homopiperazine via Schmidt Rearrangement and Photochemical Oxaziridine Rearrangement in Continuous-Flow

Brown

Aljarah

Asiki

et al. 2020

Org. Process Res. Dev.

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The scale-up of a chiral bicyclic homopiperazine of pharmaceutical interest was investigated. The outcome and safety profile of a key batch ring-expansion step via Schmidt rearrangement was improved using continuous-flow chemistry. The selectivity of nitrogen insertion for the ring expansion was improved via an alternative photochemical oxaziridine rearrangement under mild conditions, which when converted to continuous-flow in a simple and efficient flow reactor allowed the first photochemical scale-up of a homopiperazine.

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Dimethoxyethane as an Alternative Solvent for Schmidt Reactions. Preparation of Homochiral N-(5-Oxazolyl)oxazolidinones from N-Acetoacetyl Derivatives of Oxazolidinones

Cited by 34 publications

References 8 publications

Azide rearrangements in electron-deficient systems

Azide rearrangements in electron-deficient systems

Solvent replacement for green processing.

Toward the Scale-Up of a Bicyclic Homopiperazine via Schmidt Rearrangement and Photochemical Oxaziridine Rearrangement in Continuous-Flow

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