Recent developments in dehydration of primary amides to nitriles

Ganesan, Muthupandian; Nagaraaj, P.

doi:10.1039/d0qo00843e

Cited by 48 publications

(34 citation statements)

References 129 publications

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“…14 Dehydration of amides is a green and effective way to prepare nitriles in organic synthesis. 15 Although the formation of 2-alkylthiobenzonitriles from 2-alkylthiobenzamides is already known, the use of excessive amounts of toxic POCl 3 is unavoidable. 16 To our delight, the reaction of 2-(ethylthio)benzamide 1aa and Selectfluor in the presence of HI and NaI gave the dehydrated product 5a in 95% yield (Scheme 6).…”

Section: Resultsmentioning

confidence: 99%

Metal-free and Selectfluor-mediated diverse transformations of 2-alkylthiobenzamides to access 2,3-dihydrobenzothiazin-4-ones, benzoisothiazol-3-ones and 2-alkylthiobenzonitriles

et al. 2022

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Section: Resultsmentioning

confidence: 99%

Metal-free and Selectfluor-mediated diverse transformations of 2-alkylthiobenzamides to access 2,3-dihydrobenzothiazin-4-ones, benzoisothiazol-3-ones and 2-alkylthiobenzonitriles

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“…The dehydration of primary amide (−CONH 2 ) to produce nitrile is a century-old method in organic chemistry. Due to the importance of nitrile and primary amide, continued efforts have been made to date to improve the reaction efficiency and conditions. , The primary amide is a p−π conjugated structure, in which the carbonyl group is the electron-withdrawing group and the nitrogen atom can donate electrons by resonance to the adjacent carbonyl group . Therefore, the NH bond is weakened, while the CN bond is strengthened.…”

Section: Introductionmentioning

confidence: 99%

Probing the Intermediates of Catalyzed Dehydration Reactions of Primary Amide to Nitrile in Plasmonic Junctions

et al. 2022

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Visible light can effectively drive chemical reactions in plasmonic molecular junctions owing to the high reactivity of adatoms at the surface of plasmonic metal nanostructures and the localized surface plasmon resonance (LSPR)-induced energetic charge carriers (electrons and holes) and heat. Here, we investigated the dehydration reaction of primary amides, which is important to generate valuable nitrile molecules, in the visible-light-irradiated self-assembled gold nanoparticle–aromatic primary amide–gold nanoelectrode junctions in aqueous solution under ambient conditions. At present, the research on the dehydration reaction of the primary amide group is only at the macroscopic level, limiting the mechanistic study of reaction dynamics and intermediates. Using time-resolved surface enhanced Raman spectroscopy (SERS) with tens of millisecond time resolution, we successfully followed the evolution of the SERS spectra along with various transient spectral changes during the rise of the nitrile vibration peak. Combined with density functional theory and a picocavity model, we revealed that most pronounced transient spectral changes were from the gold surface adatom-coupled reaction intermediates. The adatoms produced picocavities with a strong atomic size local field, which strongly enhanced the SERS signals of the intermediates down to sub-single-molecule resolution. The active adatoms played critical roles in producing, interacting, and stabilizing the intermediates. We have determined the complex reaction pathway involving multiple proton transfer steps and intermediates with signature carbon–nitrogen double and triple bonds.

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“…They serve as the precursors for the synthesis of different organic molecules and bioactive compounds. In addition, nitriles are key intermediates for the synthesis of various heterocyclic compounds [1] and are also explored as precursors for several amines, [2,3] amides, [4,5] and carboxylic acids. [6] Conventionally nitriles can be synthesized from alcohols, [7][8][9][10] amides, [11] amines, [12,13] aldehydes, [14][15][16] aldoximes, [17] and carboxylic acids (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Electrochemical Synthesis of Nitriles: A Sustainable Approach

et al. 2022

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Nitriles unveil widespread applications in pharmaceuticals, agrochemicals, textiles, rubber, polymers, and constitute a significant intermediate in several organic transformations, necessitating the design of simple and environmentally benign pathways for their synthesis. Over the recent years, electro‐organic reactions have found widespread attention in developing effective and selective organic synthesis. They possess several advantages: high atom economy, selectivity, minimal waste production, and shorter routes to multistep traditional organic reactions. The development of novel strategies for greener and sustainable electro‐organic synthesis of nitriles is therefore commendable. This review focuses on analyzing various methods and strategies used in the electrochemical synthesis of nitriles using phase transfer catalyst, N‐oxoammonium salts mediated electrocatalysis, iodine‐mediated electrocatalysis, and anodic oxidations of aldoximes. In addition, the recent trends including the synthesis of nitriles via C−H cyanation, domino oxidation, bio electrocatalysis, and metal‐ligand cooperative synthesis have been discussed.

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Recent developments in dehydration of primary amides to nitriles

Abstract: Dehydration of amides is an efficient, clean and fundamental route for the synthesis of nitriles in organic chemistry. The two imperative functional groups viz., amide and nitrile have been discussed...

Cited by 48 publications

References 129 publications

Metal-free and Selectfluor-mediated diverse transformations of 2-alkylthiobenzamides to access 2,3-dihydrobenzothiazin-4-ones, benzoisothiazol-3-ones and 2-alkylthiobenzonitriles

Metal-free and Selectfluor-mediated diverse transformations of 2-alkylthiobenzamides to access 2,3-dihydrobenzothiazin-4-ones, benzoisothiazol-3-ones and 2-alkylthiobenzonitriles

Probing the Intermediates of Catalyzed Dehydration Reactions of Primary Amide to Nitrile in Plasmonic Junctions

Recent Advances in Electrochemical Synthesis of Nitriles: A Sustainable Approach

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