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.
Mechanochemical Synthesis of Primary Amides
Gómez-Carpintero, Jorge,Sánchez, J. Domingo,González, J. Francisco,Menéndez, J. Carlos
, p. 14232 - 14237 (2021/10/20)
Ball milling of aromatic, heteroaromatic, vinylic, and aliphatic esters with ethanol and calcium nitride afforded the corresponding primary amides in a transformation that was compatible with a variety of functional groups and maintained the integrity of a stereocenter α to carbonyl. This methodology was applied to α-amino esters and N-BOC dipeptide esters and also to the synthesis of rufinamide, an antiepileptic drug.
Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
, p. 7284 - 7296 (2021/05/29)
The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.