Hydrolysis of Amides. Alkaline and General Acid Catalyzed Alkaline Hydrolysis of Some Substituted Acetamides and Benzamides.

Meresaar, Urve; Bratt, Louise; Alakuijala, P.; Oinonen, L.

doi:10.3891/acta.chem.scand.28a-0715

Cited by 13 publications

(7 citation statements)

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“…The mechanism of the alkaline amide hydrolysis has been intensively investigated. [14][15][16][17][18][19][20][21] It is similar to that of the esters, with the exception that the tetrahedral intermediate, formed after the addition of the hydroxide, could regenerate the amide than give the hydrolysis products. The loss of the hydroxide anion is the thermodynamically preferred route and the accompanying oxygen exchange is generally faster than hydrolysis (Scheme 1).…”

Section: Introductionmentioning

confidence: 52%

A mild alkaline hydrolysis of N- and N,N-substituted amides and nitriles

Théodorou¹,

Paraskevopoulos²,

Skobridis³

2015

Arkivoc

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A mild protocol for the alkaline hydrolysis of secondary and tertiary amides in non-aqueous conditions, by the use of NaOH in methanol/dichloromethane or methanol/dioxane (1:9) at room temperature or under reflux, has been developed and a plausible reaction mechanism is discussed. Primary amides are hydrolyzed much slower than with the classical procedure, while nitriles are converted selectively to primary amides.

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Section: Introductionmentioning

confidence: 52%

A mild alkaline hydrolysis of N- and N,N-substituted amides and nitriles

Théodorou¹,

Paraskevopoulos²,

Skobridis³

2015

Arkivoc

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“…concentrations of base, a second equivalent of hydroxide may deprotonate the anionic tetrahedral intermediate, promoting decomposition to form the 6-aminocaproate anion directly (375,376). At 47-67 °C, in 1 N sodium hydroxide, pyrrolidone hydrolyzed about 2.3 times faster than caprolactam.…”

Section: Base-catalyzed Hydrolysis Of Pyrrolidones and Caprolactamsmentioning

confidence: 99%

Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault

2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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Pyrrolidones and caprolactams are important structural components of solvents, surfactants, polymers, natural products, and pharmaceuticals. This chapter provides an introduction to the structure, conformation, physical properties and reactivity of pyrrolidones and caprolactams. It begins with an overview of the nomenclature of lactams since there are several systems of nomenclature in practice, plus common names and various syncretisms. Next, the structures of pyrrolidone and caprolactam are discussed, starting with the X-ray crystal structures of pyrrolidone, N-methylpyrrolidone (NMP) and caprolactam. The conformational flexibility and ring strain of the two ring systems are also covered.Physical properties, such as dipole moments, the enthalpies of formation, vaporization and fusion, boiling points and melting points, are described. An attempt is made to put the properties of pyrrolidones and caprolactams into context with those of other lactams, amides and even lactones and cyclic ketones. Brønsted and Lewis basicity, acidity, hydrogen bonding and solubility are covered.Finally, a brief description of the basic reactivity of pyrrolidones and caprolactams is given. Topics covered are N-, O-, and α-C-alkylation, hydrolysis, reactions with organometallics, reduction, oxidation, and ring-opening polymerization. The intent is to give a concise physical organic perspective on reactivity (and stability) more than an extended treatise on synthetic elaborations. Definition and Nomenclature of LactamsLactams are cyclic amides in which both the carbonyl carbon and nitrogen atom of the amide group are part of a ring. The name, lactam, is a portmanteau of lactone (cyclic ester) and amide.Nomenclature of lactams follows a variety of conventions (Figure 1 and Table 1). The International Union of Pure and Applied Chemistry (IUPAC) recommends naming lactams as heterocyclic pseudoketones (IUPAC method 1) or by substituting lactam for the

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“…By using the synthetic method developed by 3M, 2 Although the amide bond is normally very stable toward abiotic environmental degradation, it is possible the electron withdrawing fluorinated chain could enhance reactivity and allow hydrolysis to proceed under mild conditions. 14 There has been little published literature on PFAMs. Several monosubstituted amides including MeFOA and EtFOA were synthesized and analyzed with regards to their surfactant properties.…”

Section: ■ Introductionmentioning

confidence: 99%

Polyfluorinated Amides as a Historical PFCA Source by Electrochemical Fluorination of Alkyl Sulfonyl Fluorides

Jackson

Mabury

2012

Environ. Sci. Technol.

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Polyfluorinated amides (PFAMs) are a class of compounds produced as byproducts of polyfluorinated sulfonamide synthesis by electrochemical fluorination (ECF). We measured four PFAM derivatives of perfluorooctanoic acid (PFOA) in a wide range of compounds, experimental materials, and commercial products synthesized by ECF. Initial screening was performed using headspace solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), and quantification using in-house synthesized standards was accomplished with GC-MS using positive chemical ionization. Two monosubstituted PFAMs, N-methylperfluorooctanamide (MeFOA) and N-ethylperfluorooctanamide (EtFOA), were detected in the majority of materials that were analyzed. Two disubstituted PFAMs, N-methyl-N-(2-hydroxyethyl)perfluorooctanamide (MeFOAE) and N-ethyl-N-(2-hydroxyethyl)perfluorooctanamide (EtFOAE), were not detected in any sample, likely because they were never synthesized. The concentrations of PFAMs in the sulfonamide compounds under study ranged from 12 to 6736 μg/g, suggesting their historical importance as PFCA precursors. In each case, branched isomers for PFAMs were detected, providing further support for their link to an ECF source. A hydrolysis study performed at pH 8.5 showed no degradation of EtFOA to PFOA after 8 days due to the stability of the amide bond. The environmental fate of PFAMs is suggested to be volatilization to the atmosphere followed by oxidation by hydroxyl radical with a predicted lifetime of 3-20 days. Subsequent PFAM exposure to biota will likely lead to enzymatic hydrolysis of the amide linkage to give a PFCA. Human exposure to PFAMs may have contributed to the presence of branched PFOA isomers in blood by serving as an indirect source. The decline in PFOA concentrations in human blood is consistent with a significant drop in PFAM production concurrent with the POSF phase-out in 2000-2001.

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Hydrolysis of Amides. Alkaline and General Acid Catalyzed Alkaline Hydrolysis of Some Substituted Acetamides and Benzamides.

Cited by 13 publications

References 0 publications

A mild alkaline hydrolysis of N- and N,N-substituted amides and nitriles

A mild alkaline hydrolysis of N- and N,N-substituted amides and nitriles

Introduction to Pyrrolidone and Caprolactam Chemistry

Polyfluorinated Amides as a Historical PFCA Source by Electrochemical Fluorination of Alkyl Sulfonyl Fluorides

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