1452-77-3Relevant articles and documents
Oxidative Coupling between Methylarenes and Ammonia: A Direct Approach to Aromatic Primary Amides
Zhao, Zhenguang,Wang, Tao,Yuan, Lin,Hu, Xu,Xiong, Fei,Zhao, Junfeng
, p. 2566 - 2570 (2015)
A direct oxidative amidation between methylarenes and aqueous ammonia using a tert-butyl hydroperoxide and tetrabutylammonium iodide (TBHP/TBAI) oxidation system with co-catalysis of iron(III) chloride has been developed. Both coupling partners were used in their native form to render prior functionalization unnecessary and afford a facile approach to aromatic primary amides.
Copper-Mediated Reactions of Nitriles with Nitromethanes: Aza-Henry Reactions and Nitrile Hydrations
Kuwabara, Jun,Sawada, Yoshiharu,Yoshimatsu, Mitsuhiro
, p. 1130 - 1133 (2018)
In this study, the first aza-Henry reaction of nitriles with nitromethane in a CuI/Cs2CO3/DBU system is described. The process was conveniently and directly used for the synthesis of β-aminonitroalkenes 2a-x and tolerated aryl-, alkyl-, hetaryl-, alkenyl-, and alkynylnitriles. The resulting aminonitroalkenes 2 could be successfully transformed to the corresponding 2-nitroacetophenones, 2-amino-1-halonitroalkenes, 2-alkylaminonitroalkenes, or 3-nitropyridines. In the presence of H2O, the aza-Henry reaction turned the reaction path to the nitrile hydration to exclusively yield the amides 3a-s.
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Smith,Grave
, p. 609,610 (1969)
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Barnard
, p. 2140 (1969)
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Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base
Wang, Dong-Liang,Liu, Huan,Yang, Da,Wang, Peng,Lu, Yong,Liu, Ye
, p. 4206 - 4211 (2017)
An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH4HCO3. Without addition of auxiliary base, the use of solid and cheap NH4HCO3 dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH3 or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (1J31P–77Se=758 Hz) and wide natural bite angle (βn=111°) was found to be indispensable for the high efficiency of this reaction.
Efficient and substrate-specific hydration of nitriles to amides in water by using a CeO2 catalyst
Tamura, Masazumi,Wakasugi, Hiroko,Shimizu, Ken-Ichi,Satsuma, Atsushi
, p. 11428 - 11431 (2011)
CeO2 acted as a reusable and effective catalyst for the hydration of various nitriles to amides in water under neutral conditions at low temperature (30-100 °C). CeO2 showed notable substrate specificity for nitriles that have a heteroatom adjacent to the α-carbon atom of the CN group (see scheme).
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Watanabe,Murayama
, p. 1948 (1974)
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Enhancements of dimethyl carbonate synthesis from methanol and carbon dioxide: The in situ hydrolysis of 2-cyanopyridine and crystal face effect of ceria
Wang, Sheng-Ping,Zhou, Jing-Jie,Zhao, Shu-Yang,Zhao, Yu-Jun,Ma, Xin-Bin
, p. 1096 - 1100 (2015)
This paper describes the effect of the in situ hydrolysis of 2-cyanopyridine and its derivatives on the synthesis of dimethyl carbonate (DMC) from CO2 and methanol over CeO2. 2-Cyanopyridine, with the highest electronic charge number of the carbon in the cyanogroup, is the most effective agent to accelerate the desired reaction by a decrease of water. CeO2 (1 1 0) planes are active for the hydrolysis of 2-cyanopyridine, further enhancing the DMC formation by in situ removal of water effectively. The DMC yield is improved drastically up to 378.5 mmol g cat-1 from 12.8 mmol g cat-1 with the in situ hydrolysis of 2-cyanopyridine over rod-CeO2 (1 1 0) catalyst.
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Brode,Bremer
, p. 993 (1934)
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Efficient hydration of nitriles promoted by simple amorphous manganese oxide using reduced amounts of water
Yamaguchi, Kazuya,Wang, Ye,Kobayashi, Hiroaki,Mizuno, Noritaka
, p. 574 - 576 (2012)
Hydration of various kinds of nitriles could efficiently be promoted by amorphous MnO2 using reduced amounts of water (2 equiv or less), giving the corresponding primary amides in moderate to high yields. The observed catalysis was truly heterogeneous, and the retrieved MnO2 could be reused without an appreciable loss of its high catalytic performance.
Amidation of aldehydes using mono-cationic half-sandwich rhodium(III) complexes with functionalized phenylhydrazone ligands
Devika, Neelakandan,Ananthalakshmi, Subbiah,Raja, Nandhagopal,Gupta, Gajendra,Therrien, Bruno
, p. 65 - 70 (2019)
A series of mono-cationic half-sandwich rhodium(III) complexes have been synthesized in methanol using phenylhydrazone-derived ligands (L1–L6) and the starting precursor [(η5-C5Me5)2Rh2(μ-Cl)2Cl2] in a 2:1 molar ratio. The N,N′-phenylhydrazone complexes have been isolated as tetraphenylborate salts. All complexes were characterized by elemental analysis, FT-IR, UV–visible, NMR spectroscopy and mass spectrometry. The molecular structure of complex [(η5-C5Me5)Rh(L1)Cl](BPh4) (1) was confirmed by single-crystal X-ray structure analysis. Complex [(η5-C5Me5)Rh(L3)Cl](BPh4) (3) was used as an efficient catalyst for the amide formation reaction, with up to 99% conversion after 2 h in toluene at 110 °C in the presence of hydroxyl amine hydrochloride and sodium bicarbonate.
Direct Oxidative Amination of the Methyl C-H Bond in N-Heterocycles over Metal-Free Mesoporous Carbon
Long, Xiangdong,Wang, Jia,Gao, Guang,Nie, Chao,Sun, Peng,Xi, Yongjie,Li, Fuwei
, p. 10902 - 10912 (2021/09/08)
Direct oxidative amination of the sp3C-H bond is an attractive synthesis route to obtain amides. Conventional catalytic systems for this transformation are based on transition metals and complicated synthesis processes. Herein, direct and efficient oxidative amination of the methyl C-H bond in a wide range of N-heterocycles to access the corresponding amides over metal-free porous carbon is successfully developed. To understand the fundamental structure-activity relationships of carbon catalysts, the surface functional groups and the graphitization degree of porous carbon have been purposefully tailored through doping with nitrogen or phosphorus. The results of characterization, kinetic studies, liquid-phase adsorption experiments, and theoretical calculations indicate that the high activity of the carbon catalyst is attributed to the synergistic effect of surface acidic functional groups (hydroxyl/carboxylic acid/phosphate) and more graphene edge structures exposed on the surface of carbon materials with a high graphitization degree, in which the role of acidic functional groups is to adsorb the substrate molecule and the role of the graphene edge structure is to activate O2
Synthesis of New Ruthenium-CAP Complexes and Use as Catalysts for Benzonitrile Hydration to Benzamide
Guerriero, Antonella,Peruzzini, Maurizio,Gonsalvi, Luca
, p. 4669 - 4675 (2021/11/16)
The new bimetallic [Ru2(μ-Cl)3(CAP)6]Cl (1) and monometallic cis,cis,trans-[RuCl2(dmso-S)2(CAP)2] (2) complexes, bearing the water soluble cage-like phosphine CAP (1,4,7-triaza-9-phosphatricyclo[5.3.2.1]tridecane), were synthesized and characterized in solution by NMR spectroscopy and ESI-MS spectrometry. The complexes, endowed with high solubility and stability in water, were applied as catalysts for the proof-of-concept hydration of benzonitrile to benzamide in neat water at 100 °C, achieving high conversions with only 1 mol % of catalyst, both in single runs and in catalyst recycling experiments.