- Efficient nitriding reagent and application thereof
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The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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Paragraph 0233-0235
(2021/03/31)
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- Copper-Catalyzed One-Pot Synthesis of Quinazolinones from 2-Nitrobenzaldehydes with Aldehydes: Application toward the Synthesis of Natural Products
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A novel, efficient, and atom-economical approach for the construction of quinazolinones from 2-nitrobenzaldehydes has been unveiled via copper-catalyzed nitrile formation, hydrolysis, and reduction in one pot for the first time. In this reaction, urea is used as a source of nitrogen for nitrile formation, hydrazine hydrate is used for both the reduction of the nitro group and the hydrolysis of nitrile, and atmospheric oxygen is used as the sole oxidant. The method portrays a wide substrate scope with good functional group tolerances. Moreover, this method was applied for the synthesis of schizocommunin, tryptanthrin, phaitanthrin-A, phaitanthrin-B, and 8H-quinazolino[4,3-b]quinazolin-8-one.
- Pal, Shantanu,Sahoo, Subrata
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p. 18067 - 18080
(2021/12/06)
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- Nitration of deactivated aromatic compounds via mechanochemical reaction
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A variety of deactivated arenes were nitrated to their corresponding nitro derivatives in excellent yields under high-speed ball milling condition using Fe(NO3)3·9H2O/P2O5 as nitrating reagent. A radical involved mechanism was proposed for this facial, eco-friendly, safe, and effective nitration reaction.
- Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
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supporting information
(2021/05/05)
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- Photoinduced Iron-Catalyzed ipso-Nitration of Aryl Halides via Single-Electron Transfer
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A photoinduced iron-catalyzed ipso-nitration of aryl halides with KNO2 has been developed, in which aryl iodides, bromides, and some of aryl chlorides are feasible. The mechanism investigations show that the in situ formed iron complex by FeSO4, KNO2, and 1,10-phenanthroline acts as the light-harvesting photocatalyst with a longer lifetime of the excited state, and the reaction undergoes a photoinduced single-electron transfer (SET) process. This work represents an example for the photoinduced iron-catalyzed Ullmann-type couplings.
- Wu, Cunluo,Bian, Qilong,Ding, Tao,Tang, Mingming,Zhang, Wenkai,Xu, Yuanqing,Liu, Baoying,Xu, Hao,Li, Hai-Bei,Fu, Hua
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p. 9561 - 9568
(2021/08/06)
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- Unprecedented Catalysis of Cs+Single Sites Confined in y Zeolite Pores for Selective Csp3-H Bond Ammoxidation: Transformation of Inactive Cs+Ions with a Noble Gas Electronic Structure to Active Cs+Single Sites
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We report the transformation of Cs+ ions with an inactive noble gas electronic structure to active Cs+ single sites chemically confined in Y zeolite pores (Cs+/Y), which provides an unprecedented catalysis for oxidative cyanation (ammoxidation) of Csp3-H bonds with O2 and NH3, although in general, alkali and alkaline earth metal ions without a moderate redox property cannot activate Csp3-H bonds. The Cs+/Y catalyst was proved to be highly efficient in the synthesis of aromatic nitriles with yields >90% in the selective ammoxidation of toluene and its derivatives as test reactions. The mechanisms for the genesis of active Cs+ single sites and the ammoxidation pathway of Csp3-H bonds were rationalized by density functional theory (DFT) simulations. The chemical confinement of large-sized Cs+ ions with the pore architecture of a Y zeolite supercage rendered the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap reduction, HOMO component change, and preferable coordination arrangement for the selective reaction promotion, which provides a trimolecular assembly platform to enable the coordination-promoted concerted ammoxidation pathway working closely on each Cs+ single site. The new reaction pathway without involvement of O2-dissociated O atom and lattice oxygen differs from the traditional redox catalysis mechanisms for the selective ammoxidation.
- Acharyya, Shankha S.,Ghosh, Shilpi,Iwasawa, Yasuhiro,Kaneko, Takuma,Sasaki, Takehiko,Yoshida, Yusuke
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p. 6698 - 6708
(2021/06/25)
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- Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
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Facilitated by the dual role of Ceric Ammonium Nitrate (CAN), herein we report a cost-effective approach for the cyanation of aryl iodides/bromides with CAN-DMF as an addition to the existing pool of combined cyanation sources. In addition to being an oxidant, CAN acts as a source of nitrogen in our protocol. The reaction is catalyzed by a readily available Cu(ii) salt and the ability of CAN to generate ammonia in the reaction medium is utilized to eliminate the additional requirement of a nitrogen source, ligand, additive or toxic reagents. The mechanistic study suggests an evolution of CN?leading to the synthesis of a variety of aryl nitriles in moderate to good yields. The proposed mechanism is supported by a series of control reactions and labeling experiments.
- Saikia, Rakhee,Park, Kwihwan,Masuda, Hayato,Itoh, Miki,Yamada, Tsuyoshi,Sajiki, Hironao,Mahanta, Sanjeev P.,Thakur, Ashim J.
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p. 1344 - 1351
(2021/02/27)
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- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
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Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
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p. 311 - 315
(2020/01/25)
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- Acetic Anhydride-Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals
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Glycals, 1,2-unsatrated carbohydrates, are versatile building blocks for the synthesis of various scaffolds. Despite their potential to serve as suitable precursors in diversity-oriented synthesis, 2-cyanoglycals are less explored in terms of their synthesis and derivatization. Herein, we report a combination of Ac 2 O and AcOH as new and efficient dehydrating agent of aldoximes for the synthesis of 2-cyanoglycals. In comparison to the conventional dehydrating system of Ac 2 O-base (such as NaOH, NaOAc and K 2 CO 3), the current protocol provides superior yields and faster reaction rates. The scope and limitations of the dehydrating system are investigated.
- Kinfe, Henok H.,Mabasa, Jackie,Mabasa, Tommy F.,Makhubela, Banothile C. E.,Simelane, Mthokozisi,Vatsha, Banele
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p. 991 - 996
(2020/06/10)
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- Method for synthesizing aryl cyanide by taking aryl carboxylic acid as raw material
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The invention discloses a method for synthesizing aryl cyanide by taking aryl carboxylic acid as a raw material, which is characterized in that aryl cyanide is synthesized by taking aryl carboxylic acid as a raw material, taking a combination of NH4X and N, N-dimethylformamide as a cyanide source and taking silver sulfate and copper acetate as catalysts under the action of acid and oxygen. Compared with a conventional aryl cyanide synthesis method, the method disclosed by the invention has the advantages that reaction raw materials (aryl carboxylic acid, NH4X and N, N-dimethylformamide) are cheap and easy to obtain, and the dosage of a metal catalyst is small; meanwhile, oxygen is used as an oxidizing agent, so that the method has the obvious advantages of small environmental pollution, good tolerance to various functional groups on an aromatic ring, high yield and the like; the method disclosed by the invention can be widely applied to synthesis of medicines, functional materials, natural products and other fields in the industry and academic circles.
- -
-
Paragraph 0071-0073
(2020/08/22)
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- Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
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This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
- Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
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supporting information
p. 14070 - 14074
(2020/10/12)
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- An aerobic and green C-H cyanation of terminal alkynes
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This study describes a benign C-H cyanation of terminal alkynes with α-cyanoesters serving as a nontoxic cyanide source. In situ generation of the key copper cyanide intermediate is proposed by a sequence of α-C-H oxidation and copper-mediated β-carbon elimination of α-cyanoesters, releasing the α-ketoester byproduct observed experimentally. The ensuing reaction of copper cyanide with terminal alkynes delivers preferentially cyanoalkynes and surpasses the possible Glaser type dimerization of terminal alkynes or the undesired accumulation of HCN under protic conditions. The presence of the co-oxidant K2S2O8 is crucial to this selectivity, probably by promoting oxidative transmetalation and the resulting formation of the Cu(iii)(acetylide)(CN) intermediate. All the reagents and salts used are commercially available, cheap and nontoxic, avoiding the use of highly toxic cyanide salts typically required in cyanation studies. The scope of this reaction is demonstrated with a set of alkynes and α-cyanoesters. The application of this method to late-stage functionalization of the terminal alkyne group in an estrone derivative is also feasible, showing its practical value for drug design.
- Si, Yi-Xin,Zhang, Song-Lin,Zhu, Peng-Fei
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supporting information
p. 9216 - 9220
(2020/12/03)
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- Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
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Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
- Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
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supporting information
p. 8381 - 8385
(2020/11/05)
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- Method for preparing aryl primary amide by adopting metal-catalyzed one-pot method
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The invention discloses a method for synthesizing aryl primary amide by adopting a metal-catalyzed one-pot method. The method comprises the steps of: taking aryl bromidess as raw materials, allowing the aryl bromidess to react with a cyanide source under the action of a palladium catalyst, substituting bromine on an aromatic ring with cyano to obtain cyano aromatic hydrocarbon, directly adding anaqueous solution of alkali into the reaction solution without aftertreatment, and carrying out hydrolysis reaction to obtain aryl primary amide. Compared with the prior art, the method for preparing aryl primary amide from the aryl bromides has the advantages of the short synthesis route, fewer reaction steps, simple operation, mild conditions, the high conversion rate, low toxicity and industrialproduction potential.
- -
-
Paragraph 0041; 0042
(2020/04/06)
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- Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
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Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.
- Gurjar, Jitendra,Bater, Jorick,Fokin, Valery V.
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supporting information
p. 1906 - 1909
(2019/01/24)
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- Highly Efficient Microwave-assisted One-Pot Synthesis of Aromatic Nitriles from Aromatic Aldehydes
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A highly efficient and environmentally benign protocol is described for the microwave-assisted one-pot synthesis of aromatic nitriles from aromatic aldehydes by the reaction with hydroxylamine hydrochloride in DMSO, which involves the intermediate formation of aldoximes and subsequent dehydration. The developed synthetic methodology can be readily accomplished with various aldehydes containing both electron-donor and electron-acceptor groups, providing excellent yields of the target products in shorter reaction times (1–2 min) compared to previously reported methodologies.
- Pujari,Thorat,Mahipal,Bhondwe
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p. 702 - 706
(2019/07/17)
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- Continuous-flow synthesis of nitriles from aldehydes via Schmidt reaction
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A continuous-flow synthesis of nitriles by Schmidt reaction has been developed. Using this procedure, a variety of aldehydes could be smoothly transformed into the desired nitriles in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.
- Zhan, Wei,Tong, Meng,Ji, Ling,Zhang, Han,Ge, Zemei,Wang, Xin,Li, Runtao
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p. 973 - 976
(2019/01/29)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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p. 3190 - 3194
(2019/05/21)
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- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
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p. 1484 - 1488
(2019/07/15)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Organosuperbase dendron manganese complex grafted on magnetic nanoparticles; heterogeneous catalyst for green and selective oxidation of ethylbenzene, cyclohexene and oximes by molecular oxygen
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Magnetic Fe3O4 nanoparticles as a support were modified with an amino-terminated organosilicon and cyanoric choloride ligands. The novel manganese complex was grafted on modified magnetic support (Mn(II)-Met@MMNPs). The nanocatalyst structure, particle size, morphology and surface properties was well characterized by elemental analysis, ICP-AES, AAS, EDS, FT-IR, SEM, TEM, DLS, VSM, TGA, XRD and XPS. In order to develop an effective heterogeneous nanocatalyst for eco-friendly aerobic, highly active and selective catalytic reactions, synthesized nanocatalyst was applied in oxidation of various organic compounds. The catalytic performance of the manganese nanocatalyst in the aerobic oxidation of ethylbenzene (EB), cyclohexene (CYHE) and various aldoximes and ketoxime were studied. Selective aerobic oxidation of EB and CYHE and various oximes were catalyzed by the Mn-nanocatalyst using N-hydroxyphthalimide (NHPI) with molecular oxygen as the green oxidant without the need of any reducing agent, and respectively the acetophenone (AcPO) as a benzylic product, 2-cyclohexene-1-one (CYHE[dbnd]O) as an allylic product and corresponding carbonyl compounds were obtained. The oxidation process has been optimized for Mn-nanocatalyst by considering the effect of different parameters such as the ratio and amount of Mn-nanocatalyst/NHPI, reaction time and solvent for achieving maximum conversion and selectivity to products. Due to their significant low cost, informal preparation, easy magnetically separation from reaction mixture, excellent catalytic performance, simple recovery and reusability without any metal leaching, the Mn-nanocatalyst has huge application prospect in selective and green oxidation process.
- Faraji, Ali Reza,Ashouri, Fatemeh,Hekmatian, Zahra,Heydari, Somayyeh,Mosazadeh, Sima
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- Ag/Cu-mediated decarboxylative cyanation of aryl carboxylic acids with K4Fe(CN)6 under aerobic conditions
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A method for facile synthesis of aryl nitriles has been well established via Ag/Cu-mediated decarboxylative cyanation of benzoic acids with K4Fe(CN)6 under aerobic conditions. The approach of using readily accessible aryl carboxylic acids and green K4Fe(CN)6 as starting material provides a feasible alternative to previous cyanation protocols. Control experiments revealed the key role of Cu for the process and excluded the possibility of a radical mechanism for the transformation.
- Fu, Zhengjiang,Jiang, Ligao,Li, Zhaojie,Jiang, Yongqing,Cai, Hu
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supporting information
p. 917 - 924
(2019/03/17)
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- Combining Oxoammonium Cation Mediated Oxidation and Photoredox Catalysis for the Conversion of Aldehydes into Nitriles
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A method to oxidize aromatic aldehydes to nitriles has been developed. It involves a dual catalytic system of 4-acetamido-TEMPO and visible-light photoredox catalysis. The reaction is performed using ammonium persulfate as both the terminal oxidant and nitrogen source.
- Nandi, Jyoti,Witko, Mason L.,Leadbeater, Nicholas E.
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supporting information
p. 2185 - 2190
(2018/09/29)
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
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supporting information
p. 266 - 273
(2018/01/12)
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- Design, synthesis and evaluation of novel hybrids between 4-anilinoquinazolines and substituted triazoles as potent cytotoxic agents
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In this research several series of novel dioxygenated ring fused 4-anilinoquinazolines (10a-d) and 4-anilinoquinazoline-substituted triazole hybrid compounds (11–14) have been designed and synthesized. Their biological significance was highlighted by evaluating in vitro for anticancer activities, wherein several compounds displayed excellent activity specifically against three human cancer cell lines (KB, epidermoid carcinoma; HepG2, hepatoma carcinoma; SK-Lu-1, non-small lung cancer). Especially, compound 13a exhibited up to 100-fold higher cytotoxicity in comparison with erlotinib. Docking the most cytotoxic compounds (11d, 13a, 13b, and 14c) into the ATP binding site of different EGFR tyrosine kinase domains was perfomed to predict the analogous binding mode of these compounds to the EGFR targets.
- Le-Nhat-Thuy, Giang,Dinh, Thuy Van,Pham-The, Hai,Nguyen Quang, Hung,Nguyen Thi, Nga,Dang Thi, Tuyet Anh,Hoang Thi, Phuong,Le Thi, Tu Anh,Nguyen, Ha Thanh,Nguyen Thanh, Phuong,Le Duc, Trung,Nguyen, Tuyen Van
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p. 3741 - 3747
(2018/10/20)
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- Diisopropylethylammonium acetate (DIPEAc): An efficient and recyclable catalyst for the rapid synthesis of 5-substituted-1H-tetrazoles
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A simple and efficient protocol developed for the synthesis of 5-substituted 1H-tetrazole derivatives through [2+3] cycloaddition reaction between benzonitriles and sodium azide using diisopropylethylammonium acetate as a recyclable reaction medium is described. The reactions proceed well at 80 °C and provide the corresponding tetrazoles in good to excellent yields (up to 94% yield). Developed method has notable advantages, such as simple and mild conditions, easy workup, reusability with consistent catalytic activity, and safer alternative to hazardous, corrosive conventional Lewis acid catalysts.
- Bhosle, Manisha R.,Shaikh, Dastgir S.,Khillare, Lalit D.,Deshmukh, Amarsinh R.,Mane, Ramrao A.
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p. 695 - 703
(2017/03/27)
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- Synthesis of nitriles from aldehydes with trimethylphenylammonium tribromide and ammonium acetate
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Various aromatic and heterocyclic aldehydes were easily converted to respective nitriles with the combination of trimethylphenylammonium tribromide and ammonium acetate in good yields at room temperature.
- Sayama, Shinsei
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p. 1796 - 1802
(2016/11/06)
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- Direct synthesis of nitriles from aldehydes with hydroxylamine-O-sulfonic acid in acidic water
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Herein is reported the selective transformation of aldehydes to nitriles in the presence of hydroxylamine-O-sulfonic acid (NH2OSO3H) as a source of the N atom and acidic water. The reaction works with high yields for a large array of aromatic and aliphatic aldehydes, as well as hindered aldehydes and conjugated aldehydes without purification. The reaction conditions are very mild and tolerate a wide array of functional groups. In principle, the reaction can be completed in vinegar.
- Quinn, Dylan J.,Haun, Graham J.,Moura-Letts, Gustavo
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supporting information
p. 3844 - 3847
(2016/08/02)
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- Aerobic Copper-Promoted Radical-Type Cleavage of Coordinated Cyanide Anion: Nitrogen Transfer to Aldehydes to Form Nitriles
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We have disclosed for the first time the copper-promoted C≡N triple bond cleavage of coordinated cyanide anion under a dioxygen atmosphere, which enables a nitrogen transfer to various aldehydes. Mechanistic study of this unprecedented transformation suggests that the single electron-transfer process could be involved in the overall course. This protocol provides a new cleavage pattern for the cyanide ion and would eventually lead to a more useful synthetic pathway to nitriles from aldehydes.
- Wu, Qian,Luo, Yi,Lei, Aiwen,You, Jingsong
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supporting information
p. 2885 - 2888
(2016/03/19)
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- A copper catalyzed novel method for synthesizing benzonitrile derivatives (by machine translation)
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The invention relates to a copper catalyzed novel method for synthesizing benzonitrile derivatives. The method is to Benzylether or benzaldehyde compound as a substrate, the copper salt as catalyst condition, with the nitrogen source at certain temperature to prepare the benzonitrile derivatives. Synthesis of of the present invention compared with the previous method, only the one-step reaction steps, reaction time is relatively short, simple treatment after the mild reaction conditions. The present invention uses wider range of the substrate, including benzaldehyde class Benzylether and, in ethers as the substrate is used to synthesize a nitrile compounds has never been reported before, and the reaction time as the substrate benzaldehyde class without side reaction to occur, the separation of product to reach the highest yield 94%. (by machine translation)
- -
-
Paragraph 0137; 0138; 0139; 0140
(2016/10/09)
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- Copper Iodide Mediated Cyanation of Arylboronic Acids and Aryl Iodides with Ethyl (Ethoxymethylene)cyanoacetate as Cyanating Agent
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An efficient copper iodide mediated cyanation of arylboronic acids and aryl iodides with ethyl (ethoxymethylene)cyanoacetate as cyanating agent has been developed. The reaction involves a C(sp2)-CN bond cleavage and tolerates a wide range of functional groups, affording the corresponding aryl nitriles in moderate to excellent yields.
- Qi, Chaorong,Hu, Xiaohan,He, Haitao
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supporting information
p. 1979 - 1982
(2016/08/09)
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- Highly efficient and active silver nanoparticle catalyzed conversion of aldehydes into nitriles: A greener, convenient, and versatile 'NOSE' approach
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The greener, expedient, and unambiguous potency of catalytic action of Aloe vera mediated silver nanoparticles (AgNPs-Av) for the conversion of aldehydes into nitriles in good to high yields has been reported. The catalyst remained recyclable up to the third consecutive run without significant loss in its action.
- Das, Vijay K.,Harsh,Karak
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supporting information
p. 549 - 553
(2016/01/20)
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- Copper-free Sandmeyer cyanation of arenediazonium o-benzenedisulfonimides
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Arene and heteroarenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sandmeyer cyanation. This work reports such reactions carried out by us under very mild conditions using tetrabutyl ammonium cyanide as a safe cyanide source and, interestingly, without the need for a Cu catalyst. The reactions have given rise to aryl nitriles in good yields (25 examples, average yield 75%). A good amount of o-benzenedisulfonimide was recovered from each reaction and then reused to prepare other salts. Mechanistic insights have allowed us to highlight the fundamental role of the o-benzenedisulfonimide anion as an electron transfer agent.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 1437 - 1441
(2016/02/03)
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- Half-Sandwich Guanidinate-Osmium(II) Complexes: Synthesis and Application in the Selective Dehydration of Aldoximes
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The novel guanidinate-osmium(II) complexes [OsCl{κ2-(N,N′)-C(NR)(NiPr)NHiPr}(η6-p-cymene)] [R = Ph (3a), 4-C6H4F (3b), 4-C6H4Cl (3c), 4-C6H4CF3 (3d), 3-C6H4CF3 (3e), 3,5-C6H3(CF3)2 (3f), 4-C6H4CN (3g), 4-C6H4Me (3h), 3-C6H4Me (3i), 2-C6H4Me (3j), 4-C6H4tBu (3k), 2,6-C6H3iPr2 (3l), 2,4,6-C6H2Me3 (3m)] have been synthesized in high yields (70-88 %) by treatment of THF solutions of the dimeric precursor [{OsCl(μ-Cl)(η6-p-cymene)}2] (1) with 4 equivalents of the corresponding guanidine (iPrHN)2C=NR (2a-m) at room temperature. The easily separable guanidinium chloride salts [(iPrHN)2C(NHR)]Cl (4a-m) were also formed in these reactions. The structures of 3a, 3d, and 3h were unequivocally confirmed by X-ray diffraction methods. Complexes 3a-m proved to be active in the catalytic dehydration of aldoximes. The best results were obtained with [OsCl{κ2-(N,N′)-C(N-4-C6H4CF3)(NiPr)NHiPr}(η6-p-cymene)] (3d; 5 mol-%), which, in acetonitrile at 80C, was able to convert selectively a large variety of aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes into the corresponding nitriles in high yields and short reaction times. Novel osmium(II)-guanidinate complexes of general composition [OsCl{κ2-(N,N′)-C(NR)(NiPr)NHiPr}(η6-p-cymene)] (R = Ar) have been synthesized and successfully employed as catalysts for the selective conversion of aldoximes into nitriles.
- Francos, Javier,González-Liste, Pedro J.,Menéndez-Rodríguez, Lucía,Crochet, Pascale,Cadierno, Victorio,Borge, Javier,Anti?olo, Antonio,Fernández-Galán, Rafael,Carrillo-Hermosilla, Fernando
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p. 393 - 402
(2016/02/03)
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- Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion
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We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations.
- Xu, Boran,Hartigan, Elizabeth M.,Feula, Giancarlo,Huang, Zheng,Lumb, Jean-Philip,Arndtsen, Bruce A.
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supporting information
p. 15802 - 15806
(2016/12/16)
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- A method for preparing of the benzonitrile derivatives
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The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
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Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057
(2016/10/17)
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- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
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Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
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p. 2794 - 2803
(2016/04/26)
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- Visible light catalysis synthesis method of aryl cyanide
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The invention discloses a visible light catalysis synthesis method of aryl cyanide. The method comprises the following steps: putting aryl halide, potassium ferrocyanide and alkali in an organic solvent; in the condition of magnetic stirring, starting a visible light source with power of 100-500W; irradiating with light intensity of 0.2-0.8W/cm until the reaction is over while controlling the reaction temperature at 25-85 DEG C; and carrying out a catalytic reaction for 1-12h by using a nano precious metal supported photocatalyst to synthesize the aryl cyanide. The photocatalysis cyaniding process can be shown by a general formula (I), wherein the X group is Br or I; and the R group is selected from electron attracting groups such as nitryl, acetyl and carboxyl and electron donating groups such as methoxy and methyl. In the invention, nontoxic green potassium ferrocyanide is used as a cyanogen source for synthesizing aryl cyanide, the highly toxic cyanides widely used in original methods are replaced, and thus the problem of environmental pollution in the aryl cyanide synthesis is reduced. The photocatalysis cyaniding reaction has the advantages of mild reaction conditions, stability and high efficiency, simplicity in operation, environmental friendliness, high product conversion rate and good selectivity.
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Paragraph 0022; 0023
(2017/02/28)
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- Access to nitriles from aldehydes mediated by an oxoammonium salt
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A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl-imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant.
- Kelly, Christopher B.,Lambert, Kyle M.,Mercadante, Michael A.,Ovian, John M.,Bailey, William F.,Leadbeater, Nicholas E.
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p. 4241 - 4245
(2015/04/14)
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- An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols catalyzed by a polymer supported Cu(II) complex
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A new polymer supported Cu(II) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the direct conversion of benzylic alcohols to aryl nitriles. In this reaction ammonium formate was used as the nitrogen source and O2 as the oxidant. Furthermore, the copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved. The effects of solvents, reaction time and catalyst amount for the aryl nitriles and aryl amides synthesis were reported. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Cu(II) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.
- Molla, Rostam Ali,Ghosh, Kajari,Tuhina,Manirul Islam
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p. 921 - 930
(2015/02/19)
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- Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
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The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
- Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
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p. 3754 - 3761
(2015/07/01)
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- Copper immobilized on aminated ferrite nanoparticles by 2-aminoethyl dihydrogen phosphate (Fe3O4@AEPH2-CuII) catalyses the conversion of aldoximes to nitriles
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CuII immobilized on aminated ferrite nanoparticles by 2-aminoethyl dihydrogen phosphate (Fe3O4@AEPH2-CuII) was prepared and characterized using FT-IR, TGA, TEM, EDX, VSM, XRD, CHN and ICP techniques. The easily prepared heterogeneous nanocatalyst demonstrated a significant catalytic performance for the transformation of aldoximes to nitriles that is far superior to previously reported methods. The reaction allows for the conversion of a wide variety of aldoximes including aromatic, aliphatic and heterocyclic aldoximes in good to excellent yields (50-98%). High efficiency, mild reaction conditions, easy work-up, operational simplicity, simple purification of products and safe handling of the catalyst are important advantages of this method. In addition, the environmentally benign heterogeneous nanocatalyst can be easily recovered from reaction mixtures using an external magnet and reused several times without any loss of activity.
- Zarghani, Monireh,Akhlaghinia, Batool
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p. 683 - 689
(2015/09/28)
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- Copper-catalyzed cyanation of aryl iodides with α-cyanoacetates via C-CN bond activation
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A Cu(i)-catalyzed cyanation reaction of aryl iodides with α-cyanoacetates is reported herein, which uses α-cyanoacetates as the nontoxic and easy-handling CN source through copper-mediated C-CN bond cleavage. This reaction enables access to aryl nitriles with an array of functional groups on the aromatic ring in good to excellent yields.
- Zhang, Song-Lin,Huang, Lu
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supporting information
p. 9963 - 9968
(2015/10/12)
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- Ruthenium and palladium complexes incorporating amino-azo-phenol ligands: Synthesis, characterization, structure and reactivity
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The ligands 2-((2-aminophenyl)diazenyl)phenol, HOL1-NH2, 1a; 2-((2-aminophenyl)diazenyl)-5-methylphenol, HOL2-NH2, 1b; and 2-((2-aminophenyl) diazenyl)-5-chlorophenol, HOL3-NH2, 1c, which are abbreviated as HOL-NH2, 1, afforded the complexes of compositions [(OL-NH)Pd(PPh3)], 2, and [(OL-NH)Ru(CO)(PPh3)2], 3, upon reaction with Na2PdCl4 and Ru(CO)3(PPh3)3 respectively. In all the complexes the metals ions, Pd(II) or Ru(II), are coordinated by deprotonated ligand (OL-NH)2- in tridentate (N, N, O) fashion. X-ray structures of [(OL2-NH)Pd(PPh3)], 2b, and [(OL1-NH)Ru(CO)(PPh3)2], 3a, were determined to confirm the molecular structures. The cyclic voltammograms of [(OL-NH)Ru(CO)(PPh3)2] exhibited two quasi reversible oxidative response near 0.25 and 1.12 V vs. SCE. The nature of HOMO as obtained by DFT calculations has been inspected to have an insight into the redox orbitals. The newly synthesized [(OL-NH)Pd(PPh3)], 2a, complexes exhibited catalytic activity toward the Suzuki, Heck, Cyanation and amination reactions. Catalytic activity of complex [(OL1-NH)Ru(CO)(PPh3)2], 3a, was examined for the conversion of ketones to corresponding alcohols by transfer hydrogen reactions.
- Pattanayak, Poulami,Parua, Sankar Prasad,Patra, Debprasad,Lai,Brand?o, Paula,Felix, Vitor,Chattopadhyay, Surajit
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p. 122 - 131
(2015/03/04)
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- N3 as an efficient reagent for the Schmidt reactions of ketones, arylaldehydes and aromatic carboxylic acids
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Schmidt reaction of arylaldehydes, ketones and aromatic carboxylic acids using task-specific ionic liquid, [bmim]N3 in the presence of AcOH/H2SO4 proceeds at 50-60 °C within 2-4 h to give the corresponding products. Benzaldehydes containing electron releasing groups afforded to the related benzamide derivatives. Benzonitrile derivatives were formed from the reaction of benzaldehydes containing electron withdrawing groups under these conditions. High yields of the related amides and anilines were obtained from the reaction of a variety of ketones and aromatic carboxylic acids, respectively, utilizing this procedure.
- Valizadeh, Hassan,Gholipour, Hamid,Ahmadi, Mina,Vaghefi, Sevil
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p. 1287 - 1294
(2014/11/07)
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- Chitosan supported ionic liquid: A recyclable wet and dry catalyst for the direct conversion of aldehydes into nitriles and amides under mild conditions
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A green and highly efficient chitosan supported magnetic ionic liquid (CSMIL) was synthesized with chitosan (the most abundant biopolymer in nature and a cheap industrial waste product), methyl imidazole and anhydrous/hydrous FeCl3. The heterogeneous catalyst thus obtained was used for the direct conversion of aldehydes to the corresponding nitriles in the presence of NH2OH·HCl/dry-CSMIL/MeSO2Cl and amides with NH 2OH·HCl/wet-CSMIL/MeSO2Cl. A highlight of our approach is the easy separation of the catalyst from the reaction medium and thus the recyclability of the catalyst. This simple method can be applied to obtain a wide range of aromatic, heterocyclic, and aliphatic nitriles and amides.
- Khalafi-Nezhad, Ali,Mohammadi, Somayeh
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p. 13782 - 13787
(2014/04/17)
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- Ac2O/K2CO3/DMSO: An efficient and practical reagent system for the synthesis of nitriles from aldoximes
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The transformation of aldoximes to nitriles using acetic anhydride as dehydration agent under mild reaction conditions is reported. The reaction, which proceeds under weak alkaline condition, allows for the conversion of a range of aldoximes including aromatic aldoximes, alphatic aldoximes, and heterocyclic aldoximes in good to excellent yields. This method has also been successfully applied to the synthesis of calcium channel blocker nilvadipine in pilot scale.
- Song, Yaoping,Shen, Dongguo,Zhang, Qinghua,Chen, Bo,Xu, Guangyu
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p. 639 - 641
(2014/01/23)
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- Two ways of preparing benzonitriles using BrCCl3-PPh3 as the reagent
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Benzamides were converted into benzonitriles with BrCCl3- PPh3-Et3N in CH2Cl2 in an Appel-type reaction. Benzaldoximes could be transformed to benzonitriles under identical conditions. It was found that the reaction system BrCCl3-(2 equiv.)PPh3 was also suitable for these transformations with PPh 3 replacing Et3N.
- Jasem, Yosef Al,Barkhad, Mohamed,Khazali, Mona Al,Butt, Hifsa Pervez,El-Khwass, Noha Ashraf,Azani, Mariam Al,Hindawi, Bassam Al,Thiemann, Thies
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