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.
Amide bond formation in aqueous solution: Direct coupling of metal carboxylate salts with ammonium salts at room temperature
Nielsen, John,Tung, Truong Thanh
supporting information, p. 10073 - 10080 (2021/12/10)
Herein, we report a green, expeditious, and practically simple protocol for direct coupling of carboxylate salts and ammonium salts under ACN/H2O conditions at room temperature without the addition of tertiary amine bases. The water-soluble coupling reagent EDC·HCl is a key component in the reaction. The reaction runs smoothly with unsubstituted/substituted ammonium salts and provides a clean product without column chromatography. Our reaction tolerates both carboxylate (which are unstable in other forms) and amine salts (which are unstable/volatile when present in free form). We believe that the reported method could be used as an alternative and suitable method at the laboratory and industrial scales. This journal is
Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
, p. 7018 - 7028 (2021/11/17)
Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
Ru(ii)- And Ru(iv)-dmso complexes catalyze efficient and selective aqueous-phase nitrile hydration reactions under mild conditions
Dubey, Santosh Kumar,Kaur, Gurmeet,Rath, Nigam P.,Trivedi, Manoj
, p. 17339 - 17346 (2021/10/08)
New water-soluble ruthenium(ii)- and ruthenium(iv)-dmso complexes [RuCl2(dmso)2(NH3)(CH3CN)] (1), [RuCl2(dmso)3(CH3CN)] (2), and [RuCl2(dmso)3(NH3)]·PF6·Cl (3) have been synthesized and characterized using elemental analyses, IR, 1H and 31P NMR, and electronic absorption spectroscopy. The molecular structures of complexes 1-3 were determined crystallographically. The reactivity of complexes 1-3 has been tested for aqueous-phase nitrile hydration at 60 °C in air, and good efficiency and selectivity are shown for the corresponding amide derivatives. Best performance is achieved with complex 3. Amide conversions of 56-99% were obtained with a variety of aromatic, alkyl, and vinyl nitriles. The reaction tolerated hydroxyl, nitro, bromo, formyl, pyridyl, benzyl, alkyl, and olefinic functional groups. Amides were isolated by simple decantation from the aqueous-phase catalyst. A catalyst loading down to 0.0001 mol% was examined and turnover numbers as high as 990?000 were observed. The catalyst was stable for weeks in solution and could be reused more than seven times without significant loss in catalytic activity. The gram-scale reaction was also performed to produce the desired product in high yields. This journal is
