- CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
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Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
- Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
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- Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation
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The performances of heterogeneous catalysts can be effectively tuned by changing the catalyst structures. Here we report a controllable nitrile synthesis from alcohol ammoxidation, where the nitrile hydration side reaction could be efficiently prevented by changing the manganese oxide catalysts. α-Mn2O3 based catalysts are highly selective for nitrile synthesis, but MnO2-based catalysts including α, β, γ, and δ phases favour the amide production from tandem ammoxidation and hydration steps. Multiple structural, kinetic, and spectroscopic investigations reveal that water decomposition is hindered on α-Mn2O3, thus to switch off the nitrile hydration. In addition, the selectivity-control feature of manganese oxide catalysts is mainly related to their crystalline nature rather than oxide morphology, although the morphological issue is usually regarded as a crucial factor in many reactions.
- Hui, Yu,Luo, Qingsong,Qin, Yucai,Song, Lijuan,Wang, Hai,Wang, Liang,Xiao, Feng-Shou
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p. 2164 - 2172
(2021/09/20)
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- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
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p. 6299 - 6308
(2020/07/21)
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- Copper (II)-catalysed direct conversion of aldehydes into nitriles in acetonitrile
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A mild one-pot method for the direct conversion of aryl, heteroaryl and alkyl aldehydes into nitriles was achieved by forming the corresponding oximes in situ with NH2OH and allowing them to react with CuO and acetonitrile. Yields of the 13 nitriles prepared were moderate to very good (62–91%).
- Ma, Xiaoyun,Ao, Jun,Chen, Zhengjian,Liu, Yi
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p. 465 - 468
(2017/08/18)
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- Clean synthesis of furfural oxime through liquid-phase ammoximation of furfural over titanosilicate catalysts
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The clean synthesis of furfural oxime (FO) has been realized through titanosilicate-catalyzed liquid-phase ammoximation of furfural with ammonia and hydrogen peroxide. A detailed investigation of furfural ammoximation over three representative titanosilicates Ti-MOR, TS-1 and Ti-MWW reveals that the reaction involves the hydroxylamine route and the imine route. The hydroxylamine route accounts for the formation of the target product (FO), while the imine route leads to the formation of undesired products such as 2-furylamide and 2-furoic acid. With a high efficiency for hydroxylamine formation, Ti-MOR proves to be superior to TS-1 and Ti-MWW. The catalytic performance of Ti-MOR depends greatly on the operating conditions of the reaction, which is closely related to its activity in catalyzing hydroxylamine decomposition. The decomposition of hydroxylamine and the non-catalytic oxidation of furfural can be effectively suppressed in Ti-MOR-catalyzed ammoximation when employing water as the solvent and adding H2O2 dropwise into the reaction system. Under optimized conditions, Ti-MOR is capable of providing furfural conversion and oxime selectivity both above 97%.
- Lu, Xinqing,Guan, Yejun,Xu, Hao,Wu, Haihong,Wu, Peng
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p. 4871 - 4878
(2017/10/23)
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- Nanocrystalline CeO2 as a Highly Active and Selective Catalyst for the Dehydration of Aldoximes to Nitriles and One-Pot Synthesis of Amides and Esters
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The dehydration of aldoximes into nitriles has been performed in the presence of various metal oxides with different acid-base properties (Al2O3, TiO2, CeO2, MgO). The results showed that a nanocrystalline CeO2 was the most active catalyst. An in situ IR spectroscopy study supports a polar elimination mechanism in the dehydration of aldoxime on metal oxide catalysts, in which Lewis acid sites and basic sites are involved. The Lewis acid sites intervene in the adsorption of the oxime on the catalyst surface while surface base sites are responsible for the C1-H bond cleavage. Thus, the acid-base properties of nanocrystalline CeO2 are responsible for the high catalytic activity and selectivity. A variety of aldoximes including alkyl and cycloalkyl aldoximes have been dehydrated into the corresponding nitriles in good yields (80-97%) using nanosized ceria which moreover resulted in a stable and reusable catalyst. Additionally, it has been showed that a variety of pharmacologically important products such as picolinamide and picolinic acid alkyl ester derivatives can be obtained in good yields from 2-pyridinaldoxime in a one-pot process using the nanoceria as catalyst.
- Rapeyko, Anastasia,Climent, Maria J.,Corma, Avelino,Concepción, Patricia,Iborra, Sara
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p. 4564 - 4575
(2016/07/12)
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- Stannous chloride dihydrate-mediated efficient access to secondary and primary amides from oximes
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Highly selective, efficient and expeditious Beckmann rearrangement of a wide range of ketoximes to secondary amides (20 examples) has been accomplished using stoichiometric amount of stannous chloride dihydrate in the presence of nucleophilic additive, tetra-n-butylammonium iodide (TBAI) (10 moI%) and 4 ? MS in dry acetonitrile at reflux temperature. Aldoximes delivered primary amides through intermediacy of nitriles upon heating with an equimolar amount of SnCl2·2H2O and DBU in dry toluene at reflux in good to acceptable yields (12 examples). Utilization of mild Lewis acid, inexpensive rack reagents and procedural simplicity including easy isolation of products are key advantageous features of the protocol.
- Ganguly, Nemai C.,Nayek, Subhasis,Chandra, Sumanta
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p. 1695 - 1702
(2014/01/17)
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- Cu(I)/TEMPO-catalyzed aerobic oxidative synthesis of imines directly from primary and secondary amines under ambient and neat conditions
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By catalyst and condition screening, a simple Cu(I)/TEMPO-catalyst system was found to be an active and highly effective catalyst for the aerobic oxidation of amines to imines in open air at room temperature under neat conditions. This new method provided a mild, efficient, and practical alternative for the synthesis of the useful imines directly from primary and secondary amines.
- Huang, Bo,Tian, Haiwen,Lin, Shoushuai,Xie, Meihua,Yu, Xiaochun,Xu, Qing
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supporting information
p. 2861 - 2864
(2013/06/05)
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- Conversion of aldoximes into nitriles catalyzed by simple transition metal salt of the fourth period in acetonitrile
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Conversion of aldoximes into nitriles catalyzed by simple transition metal catalysts, such as copper salts, nickel salts, cobalt salts, zinc salts, iron salts, and manganese salts in acetonitrile was investigated. All the metal salts display catalytic property in the conversion of aldoximes into nitriles and cupric acetate exhibits much higher activity than other catalysts. The corresponding amide was detected in almost all cases and acetonitrile was found to be involved in the conversion of aldoximes into nitriles.
- Ma, Xiao-Yun,He, Ying,Lu, Ting-Ting,Lu, Ming
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p. 2560 - 2564
(2013/03/28)
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- Oxidation of amidoximes with IBX and IBX/TEAB
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Biologically important process of oxidation of amidoximes has been investigated using IBX (oiodoxybenzoic acid) and combination of IBX with TEAB (tetraethylammonium bromide). The reaction proceeds with high % conversion leading to selective formation of amide and nitrile depending upon the combination of reagents. ARKAT USA, Inc.
- Deshmukh, Swapnil S.,Huddar, Sameerana N.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
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experimental part
p. 118 - 126
(2010/09/05)
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- Cannizzaro-type disproportionation of aromatic aldehydes to amides and alcohols by using either a stoichiometric amount or a catalytic amount of lanthanide compounds
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Aromatic aldehydes can be directly converted to the corresponding amides and alcohols in good to excellent yields by the treatment of aromatic aldehydes with lithium amide LiN(SiMe3)2 in the presence of catalytic lanthanide chlorides LnCIs or by the treatment of aromatic aldehydes with a stoichiometric amount of lanthanide amides [(Me3Si)2N]3Ln(μ-Cl) Li(THF)3 at ambient temperature. The effects of solvents, substitutents on the phenyl ring, and lanthanide metals on the reaction have been examined. The mechanism of the disproportionation reaction was proposed based on the experimental results.
- Zhang, Lijun,Wang, Shaowu,Zhou, Shuangliu,Yang, Gaosheng,Sheng, Enhong
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p. 3149 - 3153
(2007/10/03)
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- An in-depth study of the biotransformation of nitriles into amides and/or acids using Rhodococcus rhodochrous AJ270
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A variety of aliphatic, aromatic and heterocyclic nitriles have been readily hydrolysed into the corresponding amides and/or acids under very mild conditions using Rhodococcus sp. AJ270. The nitrile hydratase involved in this novel nitrile-hydrolysing microorganism efficiently hydrates most nitriles tested, irrespective of the electronic and steric effects of the substituents, to form the amides. Conversion of amides into acids catalysed by the associated amidase is rapid and efficient in most cases. Substrates bearing an adjacent substituent (which may be an ortho substituent on an aromatic nitrile, an adjacent heteroatom in a heterocyclic ring or a geminal substituent in an α,β-unsaturated nitrile) undergo slow hydrolysis of the amides allowing efficient amide isolation. The scope, limitations and reaction mechanism of this enzymatic process have been systematically studied. A molecular size of >7 A diameter and the presence of functions capable of metal complexation near to the nitrile inhibit hydrolysis.
- Meth-Cohn, Otto,Wang, Mei-Xiang
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p. 1099 - 1104
(2007/10/03)
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- A Powerful New Nitrile Hydratase For Organic Synthesis-Aromatic And Heteroaromatic Nitrile Hydrolyses- A Rationalisation
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A powerful new nitrile hydratase organism, Rhodococcus rhodocrous AJ270 has been isolated that efficiently hydrolyses all kinds of nitriles to amides and/or acids.This paper shows that aromatic and heterocyclic nitriles are readily hydrolysed to acids but, that those bearing an adjacent-substituent (which may be an ortho substituent or an adjacent heteroatom in the ring) give amides in good yield but only slowly proceed to acids.
- Meth-Cohn, Otto,Wang, Mei-Xiang
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p. 9561 - 9564
(2007/10/02)
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- SYNTHESIS OF 2-ARYL AND 2-HETARYLOXAZOLES FROM THE OXAZOLINES AND OXAZOLIDINES
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Treatment of 2-phenyl-, 2-(2-furyl)-, and 2-(2-thienyl)oxazolines with nickel peroxide has been found to give, in addition to the dehydrogenation products (2-substituted oxazoles),the fragmentation products (amides of benzoic, furan-2-carboxylic, and thiophen-2-carboxylic acids).This fragmentation appears to give initially the nitriles, which are then converted into the amides by the nickel peroxide.Catalytic dehydrogenation of 2-phenyloxazoline gives low yields of 2-phenyloxazole, the principal product being benzonitrile.Treatment of the Schiff's bases obtained from ethanolamine and aldehydes (benzaldehyde, furfural, and thiophen-2-aldehyde) with nickel peroxide gives trace amounts of the oxazoles, the principal products being the aldehydes, with smaller amounts of the nitriles.
- Belen'kii, L. I.,Cheskis, M. A.,Ryashentseva, M. A.
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p. 650 - 653
(2007/10/02)
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