103-81-1Relevant articles and documents
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Dauben et al.
, p. 121,123 (1950)
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Bennett,Yoshida
, p. 3030 (1973)
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Light-induced hydrolysis of nitriles by photoproduced α-MnO 2 nanorods on polystyrene beads
Jana, Subhra,Praharaj, Snigdhamayee,Panigrahi, Sudipa,Basu, Soumen,Pande, Surojit,Chang, Chien-Hsiang,Pal, Tarasankar
, p. 2191 - 2193 (2007)
A green chemistry approach has been furnished for photochemical deposition of α-MnO2 nanorods onto the surface of functionalized polystyrene beads through immobilization of MnO+4- in alkaline condition under visible light. Then the composite material was exploited as a fruitful and novel solid-phase catalyst for the one-step and facile synthesis of amide compounds from nitriles under visible light in weakly basic medium.
Choline chloride based eutectic solvent: An efficient and reusable solvent system for the synthesis of primary amides from aldehydes and from nitriles
Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
, p. 1102 - 1106 (2014)
Choline chloride: a 2ZnCl2 based deep eutectic solvent was found to be a simple, green, efficient and new solvent system for the preparation of primary amides from aldehydes. The same catalytic system is also applicable for the preparation of amides from nitriles. Good to excellent yields of primary amides were obtained in both these transformations.
Visible Light-Induced Iodine-Catalyzed Transformation of Terminal Alkynes to Primary Amides via C≡C Bond Cleavage under Aqueous Conditions
Dighe, Shashikant U.,Batra, Sanjay
, p. 500 - 505 (2016)
The visible light-induced iodine-catalyzed oxidative cleavage of the C≡C bond for transforming terminal alkynes into primary amides in the presence of ammonia under aqueous conditions is described. This metal-free protocol which ensued via initial hydroamination of the acetylene bond followed by liberation of diiodomethane (CH2I2) was found to be applicable to aromatic, heteroaromatic and aliphatic alkynes.
Isolation of deoxybilianic acid, phenylacetic acid and ferulic acid from normal human urine
Dirscherl,Pelzer
, p. 1151 - 1153 (1970)
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Selective hydration of nitriles to amides promoted by an Os-NHC catalyst: Formation and X-ray characterization of κ2-amidate intermediates
Buil, Maria L.,Cadierno, Victorio,Esteruelas, Miguel A.,Gimeno, Jose,Herrero, Juana,Izquierdo, Susana,Onate, Enrique
, p. 6861 - 6867 (2012)
The complex [Os(η6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO 3) reacts with benzonitrile and acetonitrile to afford the κ2-amidate derivatives [Os(η6-p-cymene) {κ2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η6-benzene)(OH)(CH3CN)IMe] + (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.
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Dauben et al.
, p. 2117 (1946)
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Sodium azide as a catalyst for the hydration of nitriles to primary amides in water
Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Roostaei, Mohsen
, p. 267 - 269 (2015)
The selective conversion of aromatic nitriles to primary amides has been accomplished using sodium azide. The corresponding amides were obtained efficiently in excellent yields. This reaction was carried out under eco-friendly conditions using water in the absence of organic solvents.
Silica-supported 2,4,6-trichloro-1,3,5-triazine as an efficient reagent for direct conversion of carboxylic acids to amides under solvent-free conditions
Khalafi-Nezhad, Ali,Zare, Abdolkarim,Parhami, Abolfath,Rad, Mohammad Navid Soltani,Nejabat, Gholam Reza
, p. 657 - 666 (2007)
A very simple and efficient solvent-free method for the direct conversion of carboxylic acids to primary, secondary, tertiary alkyl, and aromatic amides in the presence of the corresponding ammonium salts, silica-supported 2,4,6-trichloro-1,3,5-triazine, and triethylamine is described. The reactions proceed rapidly at room temperature, and the products are obtained in moderate to excellent yields. Copyright Taylor & Francis Group, LLC.
The hydration of nitriles catalyzed by water-soluble rhodium complexes
Djoman, Marie Charlotte Koffi-Bié,Ajjou, Abdelaziz Nait
, p. 4845 - 4849 (2000)
The water-soluble rhodium complex generated in situ from [Rh(COD)Cl]2 and P(m-C6H4SO3Na)3 has been found to be a very effective catalyst for the hydration of nitriles, under basic conditions. (C) 2000 Elsevier Science Ltd.
2-Diphenylphosphanyl-4-pyridyl(dimethyl)amine as an effective ligand for the ruthenium(II) complex catalyzed homogeneous hydration of nitriles under neutral conditions
Muranaka, Makoto,Hyodo, Isao,Okumura, Wataru,Oshiki, Toshiyuki
, p. 552 - 555 (2011)
New homogeneous catalyst comprised of [Ru(methallyl)2(cod)] (cod = 1,5-cyclooctadiene) (1) and 2-diphenylphosphanyl-4-pyridyl(dimethyl)amine (2) is shown to efficiently catalyze the hydration of various nitriles under neutral conditions. The hydration proceeds in the presence of 0.5 mol% of the ruthenium catalyst at 80 °C in 1,2-dimethoxyethane solution and the corresponding amide is obtained within few hours without the formation of byproducts. Comparison of some phosphine ligands for the hydration reveals that the dimethylamino moiety of 2 improves the catalytic performance dramatically.
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Pattison,Carmack
, p. 2033 (1946)
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A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides
Baig, R. B. Nasir,Varma, Rajender S.
, p. 6220 - 6222 (2012)
One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe 3O4@SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions. The Royal Society of Chemistry 2012.
Cu-catalyzed aerobic oxidative C-CN bond cleavage of benzyl cyanide for the synthesis of primary amides
Chen, Xiuling,Peng, Yanhong,Li, Yan,Wu, Minghu,Guo, Haibing,Wang, Jian,Sun, Shaofa
, p. 18588 - 18591 (2017)
An efficient method via copper-catalyzed aerobic oxidative amidation of benzyl cyanide for primary amides is successfully developed. Using readily available NH4Cl as a nitrogen source and Cu/O2 as a catalytic oxidation system offers new opportunities for C-CN bond cleavage and primary amide bond formation.
Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
, p. 6365 - 6371 (2015)
A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
Efficient and practical transition metal-free catalytic hydration of organonitriles to amides
Tu, Tao,Wang, Zhixun,Liu, Zelong,Feng, Xike,Wang, Qingyi
, p. 921 - 924 (2012)
K2CO3 can act as an efficient catalyst for the hydration of organonitriles in aqueous conditions assisted by microwave irradiation, which represents an inexpensive, practical, atom-economical, and straightforward transition metal-free protocol to various amides.
Amides by microwave-assisted dehydration of ammonium salts of carboxylic acids
Peng, Yanqing,Song, Gonghua
, p. 95 - 97 (2002)
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Ti-superoxide catalyzed oxidative amidation of aldehydes with saccharin as nitrogen source: Synthesis of primary amides
Kamble, Rohit B.,Mane, Kishor D.,Rupanawar, Bapurao D.,Korekar, Pranjal,Sudalai,Suryavanshi, Gurunath
, p. 724 - 728 (2019)
A new heterogeneous catalytic system (Ti-superoxide/saccharin/TBHP) has been developed that efficiently catalyzes oxidative amidation of aldehydes to produce various primary amides. The protocol employs saccharin as amine source and was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, catalyst reusability and operational simplicity are the main highlights. A possible mechanism and the role of the catalyst in oxidative amidation have also been discussed.
Transition metal-free 1,3-dimethylimidazolium hydrogen carbonate catalyzed hydration of organonitriles to amides
Verma, Praveen Kumar,Sharma, Upendra,Bala, Manju,Kumar, Neeraj,Singh, Bikram
, p. 895 - 899 (2013)
An efficient hydration of organonitriles to the corresponding amides was accomplished using 1,3-dimethylimidazolium hydrogen carbonate as an organocatalyst. The developed catalytic method was also applicable for the synthesis of metal phthalocyanines.
A facile hydration of nitriles by dimethyldioxirane
Bose, D. Subhas,Baquer, Syed M.
, p. 3119 - 3123 (1997)
A new and practical method for the conversion of nitriles to amides by employing the dimethyldioxirane, which is prepared in situ from acetone and oxone, is described.
Selective hydrolysis of nitriles to amides using NaOH-PEG under microwave irradiation
Bendale, Pravin M.,Khadilkar, Bhushan M.
, p. 1713 - 1718 (2000)
We describe here an efficient, rapid and selective method for the conversion of nitriles in to their corresponding amides in the presence of PEG-400, aqueous sodium hydroxide system under microwave irradiation.
Direct catalytic formation of primary and tertiary amides from non-activated carboxylic acids, employing carbamates as amine source
Tinnis, Fredrik,Lundberg, Helena,Adolfsson, Hans
, p. 2531 - 2536 (2012)
The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields. Copyright
Synthesis of and catalytic nitrile hydration by a cationic tris(μ-hydroxo)diruthenium(II) complex having PMe3ligands
Kiyota, Sayori,Kobori, Takako,Soeta, Hirofumi,Ichikawa, You-ichi,Komine, Nobuyuki,Komiya, Sanshiro,Hirano, Masafumi
, p. 3 - 10 (2016)
While phenyl vinyl ether does not react with [Ru(η4-1,5-COD)(η6-1,3,5-COT)] (1)/PMe3, the C–O bond cleavage of phenyl vinyl ether occurs by 1/PMe3in the presence of water to give a tris(μ-hydroxo)diruthenium(II) complex [(Me3P)3Ru(μ-OH)3Ru(PMe3)3]+[OPh]?·HOPh (3·HOPh) with evolution of ethylene. The molecular structure of 3·HOPh is unequivocally determined by X-ray analysis. The most likely mechanism for the formation of 3·HOPh is protonation of [Ru(η4-1,5-COD)(PMe3)3] (2c) by water and subsequent insertion of phenyl vinyl ether into the resulting Ru–H bond followed by the β-phenoxide elimination and hydrolysis and dimerization of the phenoxoruthenium(II) species. Complex 3 acts as a catalyst for nitrile hydration. As a typical example, the hydration of benzonitrile was achieved by 3 (1.0 mol%) in 1,4-dioxane at 120 °C for 6 h to give benzamide quantitatively.
Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
, p. 12152 - 12160 (2015)
Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
, (2022/01/20)
C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
, p. 7176 - 7185 (2021/06/30)
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
Ben-David, Yehoshoa,Diskin-Posner, Yael,Kar, Sayan,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
, p. 10239 - 10245 (2021/08/24)
A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.