- Green and efficient Beckmann rearrangement by Cu(II) contained nano-silica triazine based dendrimer in water
-
In this research, a Cu(II) contained nano-silica triazine based dendrimer was prepared, characterized, and utilized as a retrievable catalytic system (Cu(II)-TrDen@nSiO2) for green formation of primary amides in water at room temperature. The structure of nanoparticles was fully characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetry analysis (TGA). The results revealed that the nanoparticles have spherical morphology and an average size of around 40 nm. The analysis also illustrated that the copper nanoparticles had been successfully loaded on the nitrogen-rich dendritic structure with a uniform distribution. The inductively coupled plasma analysis showed that about 0.67 mmol/g of Cu was loaded on the Cu(II)-TrDen@nSiO2 support. Mild reaction conditions, excellent yields, environment-friendly synthesis, and easily prepared starting materials are the key features of the present method. The catalyst is easily removed from the reaction media using a simple filtration and can be re-used at least five times without any considerable loss of its catalytic activity.
- Bahreininejad, Mohammad Hasan,Moeinpour, Farid
-
p. 893 - 901
(2021/01/12)
-
- Ring Opening/Site Selective Cleavage in N-Acyl Glutarimide to Synthesize Primary Amides
-
A LiOH-promoted hydrolysis selective C-N cleavage of twisted N-acyl glutarimide for the synthesis of primary amides under mild conditions has been developed. The reaction is triggered by a ring opening of glutarimide followed by C-N cleavage to afford primary amides using 2 equiv of LiOH as the base at room temperature. The efficacy of the reactions was considered and administrated for various aryl and alkyl substituents in good yield with high selectivity. Moreover, gram-scale synthesis of primary amides using a continuous flow method was achieved. It is noted that our new methodology can apply under both batch and flow conditions for synthetic and industrial applications.
- Govindan, Karthick,Lin, Wei-Yu
-
supporting information
p. 1600 - 1605
(2021/03/03)
-
- Unlocking Amides through Selective C–N Bond Cleavage: Allyl Bromide-Mediated Divergent Synthesis of Nitrogen-Containing Functional Groups
-
We report a new set of reactions based on the unlocking of amides through simple treatment with allyl bromide, creating a common platform for accessing a diverse range of nitrogen-containing functional groups such as primary amides, sulfonamides, primary amines, N-acyl compounds (esters, thioesters, amides), and N-sulfonyl esters. The method has potential industrial applicability, as demonstrated through gram-scale syntheses in batch and in a continuous flow system.
- Govindan, Karthick,Chen, Nian-Qi,Chuang, Yu-Wei,Lin, Wei-Yu
-
supporting information
p. 9419 - 9424
(2021/11/30)
-
- Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)?H Bonds**
-
The metal-free activation of C(sp3)?H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as l-menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
- Murugesan, Kathiravan,Donabauer, Karsten,K?nig, Burkhard
-
supporting information
p. 2439 - 2445
(2020/12/07)
-
- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
-
Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
- Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
-
supporting information
p. 21479 - 21485
(2021/08/23)
-
- Nano-construction of CuO nanorods decorated with g-C3N4 nanosheets (CuO/g-C3N4-NS) as a superb colloidal nanocatalyst for liquid phase C[sbnd]H conversion of aldehydes to amides
-
Herein, we describe an intelligent strategy to fabricate nanosheets of graphitic carbon nitride (g-C3N4) decorated with nanorods copper oxide (CuO NRs). Then, the catalytic activity of CuONRs/g-C3N4-NS was developed for the synthesis of primary amides in water. The morphology of CuO and its synergetics effect with nanosheets g-C3N4 a major role in the yield of products. Furthermore, hydroxylamine hydrochloride (NH2OH·HCl) due to availability and affordability was used as a suitable substitute for ammonia source. The findings demonstrate that this layer nanostructure is a superb catalyst for converting various derivatives of aldehyde to their corresponding amides. The current protocol can be useful criterion in the synthesis and stabilization of metal oxides and provides new insight in organic transformation.
- Mohammadi, Robabeh,Gholipour, Behnam,Alamgholiloo, Hassan,Rostamnia, Sadegh,Mohtasham, Hamed,Zonouzi, Afsaneh,Ramakrishna, Seeram,Shokouhimehr, Mohammadreza
-
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
-
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- Cu(II)–metformin immobilized on graphene oxide: an efficient and recyclable catalyst for the Beckmann rearrangement
-
Abstract: In this study, for the first time, the copper(II) nanoparticles (NPs) have been immobilized on metformin-functionalized graphene oxide and then its catalytic applications have been investigated in synthesis of amides from aldoximes (Beckmann rearrangement). The chemical structure of prepared catalyst has been characterized by various analyses like FT-IR, TGA, TEM, SEM, EDX, and ICP. All analyses confirm the successful and stable immobilization of copper NPs on functionalized graphene oxide. This synthesized heterogeneous nanocatalyst showed excellent catalytic activity with high product yields and short reaction times. Also, the suggested catalyst could be recycled ten times without a drastic decrease in its catalytic activity. Graphic abstract: [Figure not available: see fulltext.].
- Solaiman Hamed, Ahmed,Mohammad Ali, Ehab
-
p. 701 - 714
(2019/11/03)
-
- Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides
-
A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
-
supporting information
p. 902 - 909
(2020/11/30)
-
- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
-
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
- -
-
Paragraph 0034-0039; 0243-0248
(2020/09/16)
-
- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
-
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
-
p. 378 - 385
(2020/10/02)
-
- Isothiazole bisoxadiazole biphenyl amide derivatives and preparation method and application thereof
-
The invention provides isothiazole bisoxadiazole biphenyl amide derivatives and a preparation method and application thereof, and particularly relates to 3, 4-dichloroisothiazole bisoxadiazole biphenyl amide derivatives. The general formula of the chemical structure is shown in the formula IV. The invention discloses a structural general formula, a synthesis method and application of the compoundas an insecticide, a bactericide and an anti-plant virus agent, and application and preparation method of the compound in preventing and treating agricultural, forestry and horticultural plant insectpests, diseases and virus diseases in combination with agriculturally acceptable auxiliaries or synergists and commercial insecticides, bactericides, plant virus resisting agents and acaricides.
- -
-
Paragraph 0028-0030
(2020/07/21)
-
- Transamidation for the Synthesis of Primary Amides at Room Temperature
-
Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.
- Chen, Jiajia,Lee, Sunwoo,Xia, Yuanzhi
-
supporting information
(2020/05/05)
-
- Acyl Cyanides as Bifunctional Reagent: Application in Copper-Catalyzed Cyanoamidation and Cyanoesterification Reaction
-
Cu-catalyzed domino decyanation and cyanation reaction of acyl cyanides with amines or alcohols have been developed. The cyano sources were generated in situ via C-CN cleavage yielding the corresponding cyano substituted amides or esters in moderate to excellent yields. This approach features a cheap copper catalyst, domino decyanation and cyanation reaction, readily available starting materials, broad substrate scope, operational simplicity, and the potential for further transformation of the cyano group.
- Chen, Zhengwang,Wen, Xiaowei,Zheng, Weiping,He, Ruolan,Chen, Dou,Cao, Dingsheng,Long, Lipeng,Ye, Min
-
p. 5691 - 5701
(2020/04/10)
-
- Supported palladium catalyzed aminocarbonylation of aryl iodides employing bench-stable CO and NH3surrogates
-
A simple, efficient and phosphine free protocol for carbonylative synthesis of primary aromatic amides under polystyrene supported palladium (Pd?PS) nanoparticle (NP) catalyzed conditions has been demonstrated. Herein, instead of using two toxic and difficult to handle gases simultaneously, we have employed the solid, economical, bench stable oxalic acid as the CO source and ammonium carbamate as the NH3source in a single pot reaction. For the first time, we have applied two non-gaseous surrogates simultaneously under heterogeneous catalyst (Pd?PS) conditions for the synthesis of primary amides using an easy to handle double-vial (DV) system. The developed strategy showed a good functional group tolerance towards a wide range of aryl iodides and afforded primary aromatic amides in good yields. The Pd?PS catalyst was easy to separate and can be recycled up to four consecutive runs with small loss in catalytic activity. We have successfully extended the scope of the methodology to the synthesis of isoindole-1,3-diones from 1,2-dihalobenzene, 2-halobenzoates and 2-halobenzoic acid following double and single carbonylative cyclization approaches.
- Bains, Rohit,Das, Pralay,Kumar, Ajay,Ram, Shankar,Shaifali,Sheetal
-
supporting information
p. 7193 - 7200
(2020/10/02)
-
- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
-
The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
- -
-
Paragraph 0018; 0104
(2019/03/28)
-
- A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
-
The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
- -
-
Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0120
(2019/05/08)
-
- Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
-
The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
- Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
-
p. 3360 - 3365
(2019/03/26)
-
- Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
-
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.
-
supporting information
p. 1906 - 1909
(2019/01/24)
-
- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
-
Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
-
p. 11823 - 11838
(2019/10/02)
-
- Design and Synthesis of Iminosydnones for Fast Click and Release Reactions with Cycloalkynes
-
Emerging applications in the field of chemical biology are currently limited by the lack of bioorthogonal reactions allowing both removal and linkage of chemical entities on complex biomolecules. We recently discovered a novel reaction between iminosydnones and strained alkynes leading to two products resulting from ligation and fragmentation of iminosydnones under physiological conditions. We now report the synthesis of a panel of substituted iminosydnones and the structure reactivity relationship between these compounds and strained alkyne partners. This study identified the most relevant substituents, which allow to increase the rate of the transformation and to develop a bifunctional cleavable linker with improved kinetics.
- Riomet, Margaux,Decuypere, Elodie,Porte, Karine,Bernard, Sabrina,Plougastel, Lucie,Kolodych, Sergii,Audisio, Davide,Taran, Frédéric
-
supporting information
p. 8535 - 8541
(2018/05/30)
-
- Modulation of Nitrile Hydratase Regioselectivity towards Dinitriles by Tailoring the Substrate Binding Pocket Residues
-
The regioselective hydration of dinitriles is one of the most attractive approaches to prepare ω-cyanocarboxamides or diamides and such regioselectivity is often beyond the capability of chemical catalysts. The use of nitrile hydratase to biotransform dinitriles selectively would be highly desirable. Molecular docking of two aliphatic dinitriles and two aromatic dinitriles into the active site of a nitrile hydratase (NHase) from Rhodococcus rhodochrous J1 allowed the identification of proximal NHase substrate binding pocket residues. Four residues (βLeu48, βPhe51, βTyr68, and βTrp72) were selected for single- and double-point mutations to modulate the NHase regioselectivity towards dinitriles. Several NHase mutants with an altered regioselectivity were obtained, and the best one was Y68T/W72Y. Docking experiments further indicated that the poor binding affinity of aliphatic and aromatic ω-cyanocarboxamides to the NHase variants resulted in distinct regioselectivity between wild-type and mutated NHases.
- Cheng, Zhongyi,Cui, Wenjing,Xia, Yuanyuan,Peplowski, Lukasz,Kobayashi, Michihiko,Zhou, Zhemin
-
p. 449 - 458
(2017/12/15)
-
- Novel design of recyclable copper(II) complex supported on magnetic nanoparticles as active catalyst for Beckmann rearrangement in poly(ethylene glycol)
-
Copper complex-functionalized magnetic core–shell nanoparticles (Fe3O4@SiO2-Lig-Cu) were prepared and characterized using various techniques. The activity of the new catalyst was tested for the Beckmann rearrangement. The reaction conditions allow for the conversion of a wide variety of aldoximes, including aromatic and heterocyclic ones, to amides in good to excellent yields. High efficiency, mild reaction conditions, easy work-up, use of poly(ethylene glycol) as a green medium and simple purification of products are important advantages of this system. Moreover, the eco-friendly heterogeneous nanocatalyst could be easily recovered from the reaction mixture using an external magnet and reused several times.
- Keyhaniyan, Mahdi,Shiri, Ali,Eshghi, Hossein,Khojastehnezhad, Amir
-
-
- Magnetic Nanoparticle-Supported Cu–NHC Complex as an Efficient and Recoverable Catalyst for Nitrile Hydration
-
Magnetic nanoparticles supported N-heterocyclic carbene–Cu complex was prepared and authenticated by FT-IR, SEM, EDX, VSM, powder-XRD. The catalytic activity of these magnetically retrievable NPs was investigated for hydration of nitriles as the simplest route for the synthesis of amides in an atom-economical manner. A wide range of nitriles containing various functional groups such as olefin, aldehyde, nitro, carboxylic acid was examined in this transformation to generate their corresponding amides in the aqueous medium. The immobilized catalyst was easily recovered using an external magnet and reused for six times without significant loss of its catalytic activity. Graphical Abstract: [Figure not available: see fulltext.].
- Kazemi Miraki, Maryam,Arefi, Marzban,Salamatmanesh, Arefeh,Yazdani, Elahe,Heydari, Akbar
-
p. 3378 - 3388
(2018/09/11)
-
- Mn(i) organometallics containing the iPr2P(CH2)2PiPr2 ligand for the catalytic hydration of aromatic nitriles
-
The first example of a homogeneous hydration of aromatic nitriles catalyzed by manganese molecular compounds is reported. The Mn(i) organometallics fac-[(CO)3Mn(dippe)(Z)]1-nX1-n (n = 0, 1; Z = Br, OTf, PhCN; X = OTf) were synthesized and characterized, and their reactivity was studied. The species fac-[(CO)3Mn(dippe)(OTf)] (2) was used as a catalyst precursor for the selective hydration of benchmark benzonitrile (2 mol% 2, THF/H2O 1:2 v/v, 18 h, 100 °C) to produce benzamide in 90% isolated yield. A series of (hetero)aromatic nitriles were hydrated to synthesize the corresponding amides in very good to excellent yields (88-94%). Isotopic labeling studies accounted for a proton transfer as the rate-determining step.
- Gardu?o, Jorge A.,Arévalo, Alma,Flores-Alamo, Marcos,García, Juventino J.
-
p. 2606 - 2616
(2018/05/30)
-
- Highly Selective Ruthenium-Catalyzed Direct Oxygenation of Amines to Amides
-
Reports on aerobic oxidation of amines to amides are rare, and those reported suffer from several limitations like poor yield or selectivity and make use of pure oxygen under elevated pressure. Herein, we report a practical and an efficient ruthenium-catalyzed synthetic protocol that enables selective oxidation of a broad range of primary aliphatic, heterocyclic and benzylic amines to their corresponding amides, using readily available reagents and ambient air as the sole oxidant. Secondary amines instead, yield benzamides selectively as the sole product. Mechanistic investigations reveal intermediacy of nitriles, which undergo hydration to afford amide as the final product.
- Ray, Ritwika,Hazari, Arijit Singha,Chandra, Shubhadeep,Maiti, Debabrata,Lahiri, Goutam Kumar
-
supporting information
p. 1067 - 1071
(2018/01/03)
-
- Preparation method of aromatic nitrile compound or heteroaromatic nitrile compound
-
The invention discloses a preparation method of an aromatic nitrile compound or a heteroaromatic nitrile compound. The preparation method comprises: under the protection of an inert gas, in a solvent,under the actions of a nickel catalyst, a ligand, metal zinc and an additive, carrying out a reaction on a cyanation reagent and halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon. According to the present invention, by using the inexpensive and easily-available nickel catalyst and the ligand, the halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon,especially the chlorinated aromatic hydrocarbon or chlorinated heteroaromatic hydrocarbon with characteristics of low price, easy obtaining and low reaction activity can mildly and efficiently react with the cyanation reagent with low toxicity to prepare the aromatic nitrile compound or heteroaromatic nitrile compound; and the preparation method has advantages of simple operation, mildness, high efficiency and the like, and further has characteristics of good functional group compatibility, good universality of substrate and the like.
- -
-
Paragraph 0043; 0045; 0133-0135
(2018/11/03)
-
- Uniformly dispersed copper nanoparticles onto the modified magnetically recoverable nanocatalyst for aqueous synthesis of primary amides
-
Magnetically recoverable and environmentally friendly Cu-based heterogeneous catalyst has been synthesized for the one-pot conversion of aldehydes to their corresponding primary amides. The Fe3O4@SiO2 nanocomposites were prepared by synthesis of Fe3O4 magnetic nanoparticles (MNPs) which was then coated with a silica shell via St?ber method. Bi-functional cysteine amino acid was covalently bonded onto the siliceous shell of nanocatalyst. The CuII ions were then loaded onto the modified surface of nanocatalyst. Finally, uniformly dispersed copper nanoparticles were achieved by reduction of CuII ions with NaBH4. Amidation reaction of aryl halides with electron-withdrawing or electron-donating groups and hydroxylamine hydrochloride catalyzed with Fe3O4@SiO2@Cysteine-copper (FSC-Cu) MNPs in aqueous condition gave an excellent yield of products. The FSC-Cu MNPs could be easily isolated from the reaction mixture with an external magnet and reused at least 8 times without significant loss in activity.
- Ziaee, Fariborz,Gholizadeh, Mostafa,Seyedi, Seyed Mohammad
-
-
- Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia
-
Mechanistic information on a reliable, palladium-catalyzed aminocarbonylation of aryl chlorides with ammonia is reported. The reaction occurs with ethylene complex 1 as catalyst, and mechanistic information was gained by isolation of catalytic intermediates and kinetic measurements, including the first mechanistic data on the oxidative addition of aryl chloride to a palladium(0) complex in the presence of CO. Arylpalladium and phenacylpalladium halide intermediates were synthesized, and kinetic measurements of the formation and reactions of these intermediates were undertaken to determine the mechanism of the oxidative addition of aryl bromides and chlorides to a Pd(0) dicarbonyl compound in the presence of CO and the mechanism of the reaction of ammonia with a Pd(II) phenacyl complex to form benzamide. The oxidative addition of aryl chlorides and aryl bromides was determined to occur with rate-limiting reaction of the haloarene with a three-coordinate Pd(0) species bearing a bidentate phosphine and one CO ligand. A primary 13C kinetic isotope effect suggested that this step involves cleavage of the carbon-halogen bond. Our data show that the formation of benzamide from the reaction of phenacylpalladium halide complexes with ammonia occurs by a pathway involving reversible displacement of chloride from a phenacylpalladium chloride complex by ammonia, deprotonation of the bound ammonia to form a phenacylpalladium amido complex, and reductive elimination to form the C-N bond. Consistent with this mechanism, the reaction of an aryl palladium amido complex with CO formed the corresponding primary benzamide. A catalyst deactivation pathway involving the formation of a Pd(I) dimer also was elucidated.
- Wang, Justin Y.,Strom, Alexandra E.,Hartwig, John F.
-
supporting information
p. 7979 - 7993
(2018/06/11)
-
- Corresponding amine nitrile and method of manufacturing thereof
-
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
- -
-
Paragraph 0135; 0136; 0137; 0142
(2018/05/07)
-
- Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature
-
Transition-metal-catalyzed nitrile hydration is an atom-economic method for the synthesis of various amides. This work demonstrates for the first time that the addition of non-redox metal ions like Sc3+ dramatically accelerate the hydration of various nitriles to amides at ambient temperature with the simple Pd(OAc)2 salt as catalyst, whereas the reactions with Pd(OAc)2 alone were very sluggish. The formation of a heterobimetallic PdII/ScIII species has been proposed as the key species for the hydration that demonstrates a bimetallic synergistic effect in this process.
- Zhang, Sicheng,Xu, Haosheng,Lou, Chenlin,Senan, Ahmed M.,Chen, Zhuqi,Yin, Guochuan
-
p. 1870 - 1875
(2017/04/21)
-
- Hemilability-Driven Water Activation: A NiII Catalyst for Base-Free Hydration of Nitriles to Amides
-
The NiII complex 1 containing pyridyl- and hydroxy-functionalized N-heterocyclic carbenes (NHCs) is synthesized and its catalytic utility for the selective nitrile hydration to the corresponding amide under base-free conditions is evaluated. The title compound exploits a hemilabile pyridyl unit to interact with a catalytically relevant water molecule through hydrogen-bonding and promotes a nucleophilic water attack to the nitrile. A wide variety of nitriles is hydrated to the corresponding amides including the pharmaceutical drugs rufinamide, Rifater, and piracetam. Synthetically challenging α-hydroxyamides are accessed from cyanohydrins under neutral conditions. Related catalysts that lack the pyridyl unit (i.e., compounds 2 and 4) are not active whereas those containing both the pyridyl and the hydroxy or only the pyridyl pendant (i.e., compounds 1 and 3) show substantial activity. The linkage isomer 1′ where the hydroxy group is bound to the metal instead of the pyridyl group was isolated under different crystallization conditions insinuating a ligand hemilabile behavior. Additional pKa measurements reveal an accessible pyridyl unit under the catalytic conditions. Kinetic studies support a ligand-promoted nucleophilic water addition to a metal-bound nitrile group. This work reports a Ni-based catalyst that exhibits functional hemilability for hydration chemistry.
- Singh, Kuldeep,Sarbajna, Abir,Dutta, Indranil,Pandey, Pragati,Bera, Jitendra K.
-
p. 7761 - 7771
(2017/06/06)
-
- A Convenient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides to Primary Amides under Gas-Free Conditions
-
A convenient procedure for the synthesis of aromatic primary amides through palladium-catalyzed aminocarbonylation of aryl iodides has been developed. With ammonium hydrogen carbonate as the solid nitrogen source and formic acid as the liquid CO source, a variety of primary amides were obtained in moderate to excellent yields under gas-free conditions.
- Qi, Xinxin,Ai, Han-Jun,Cai, Chuang-Xu,Peng, Jin-Bao,Ying, Jun,Wu, Xiao-Feng
-
supporting information
p. 7222 - 7225
(2018/01/02)
-
- 1,3-Dibromo-5,5-dimethylhydantoin mediated oxidative amidation of terminal alkenes in water
-
A variety of terminal alkenes were converted to the corresponding amides in yields of 25 to 86% in water via treatment with 1,3-dibromo-5,5-dimethylhydantoin, followed by reaction with molecular iodine and aq. NH3 (or amine) in one pot. This metal- and organic solvent-free protocol is not only suitable for styrene derivatives, but also, for the first time, works well on terminal aliphatic alkenes.
- Ma, Chunhua,Fan, Guojie,Wu, Ping,Li, Zhi,Zhou, Yang,Ding, Qingjie,Zhang, Wei
-
p. 9889 - 9894
(2017/12/12)
-
- General and Mild Nickel-Catalyzed Cyanation of Aryl/Heteroaryl Chlorides with Zn(CN)2: Key Roles of DMAP
-
A new and general nickel-catalyzed cyanation of hetero(aryl) chlorides using less toxic Zn(CN)2 as the cyanide source has been developed. The reaction relies on the use of inexpensive NiCl2·6H2O/dppf/Zn as the catalytic system and DMAP as the additive, allowing the cyanation to occur under mild reaction conditions (50-80 °C) with wide functional group tolerance. DMAP was found to be crucial for successful transformation, and the reaction likely proceeds via a Ni(0)/Ni(II) catalysis based on mechanistic studies. The method was also successfully extended to aryl bromides and aryl iodides.
- Zhang, Xingjie,Xia, Aiyou,Chen, Haoyi,Liu, Yuanhong
-
supporting information
p. 2118 - 2121
(2017/04/27)
-
- Hexagonal Mesoporous Silica-Supported Copper Oxide (CuO/HMS) Catalyst: Synthesis of Primary Amides from Aldehydes in Aqueous Medium
-
Hexagonal mesoporous silica (HMS)-supported copper oxides (CuO/HMS) have been prepared by a sol–gel method and characterized by X-ray diffraction, FTIR spectroscopy, transmission electron microscopy, N2 sorption, inductively coupled plasma (ICP), X-ray photoelectron spectroscopy (XPS), H2 temperature-programed reduction (TPR), NH3 temperature-programed desorption (TPD), and high-resolution (HR)-TEM techniques. An analysis of these results revealed a mesoporous material system with a high surface area (974 m2 g?1) and uniform pore-size distribution. The catalytic efficacy of CuO on the HMS support with varying Cu loadings (1, 3, 5, 10, and 15 wt %) was investigated for the transformation of aldehydes to primary amides; 3 wt % CuO/HMS exhibited good catalytic performance with good to excellent yields of amides (60–92 %) in benign aqueous medium. The intrinsically heterogeneous catalyst could be recovered after the reaction and reused without any noticeable loss in activity.
- Kadam, Ravishankar G.,Rathi, Anuj K.,Cepe, Klara,Zboril, Radek,Varma, Rajender S.,Gawande, Manoj B.,Jayaram, Radha V.
-
p. 467 - 473
(2017/04/13)
-
- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
-
Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
-
supporting information
p. 2889 - 2894
(2016/09/16)
-
- Ruthenium(II) complexes incorporating salicylaldiminato-functionalized N-heterocyclic carbene ligands as efficient and versatile catalysts for hydration of organonitriles
-
We describe a new synthetic procedure for synthesis of ruthenium(II) complexes containing salicylaldiminato functionalized mixed N-heterocyclic carbene (NHC) ligand and phosphine co-ligand. The complexes (3a-3d) have been obtained in good to excellent yields by transmetalation from the corresponding Ag-NHC complexes (2a-2d) as carbene transfer reagents. All the [Ru-NHC] complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The ligands 1a-1d show their versatility by switching to be O,N,C-chelating in these ruthenium(II) complexes. The resulting complexes have been evaluated as potential catalysts for the selective hydration of nitriles to primary amides, and related amide bond forming reactions, in environmentally friendly medium. The reaction tolerated ether, hydroxyl, nitro, bromo, formyl, pyridyl, benzyl and alkyl functional groups. The catalyst was stable for weeks and could be recovered and reused more than six times without significant loss of activity.
- Nirmala, Muthukumaran,Saranya, Gandhi,Viswanathamurthi, Periasamy
-
p. 134 - 144
(2016/01/09)
-
- Direct Transformation of Ethylarenes into Primary Aromatic Amides with N -Bromosuccinimide and I2-Aqueous NH3
-
A variety of ethylarenes were converted into the corresponding primary aromatic amides in good yields via treatment with N-bromosuccinimide in the presence of a catalytic amount of 2,2′-azobis(isobutyronitrile) in a mixture of ethyl acetate and water, acetonitrile and water, or chloroform and water, followed by reaction with molecular iodine and aq NH3 in one pot. It was found that aryl α-bromomethyl ketones and/or aryl methyl ketones were formed at the first reaction step and their iodoform-type reaction occurred at the second reaction step to provide primary aromatic amides. The present reaction is a useful and practical transition-metal-free method for the preparation of primary aromatic amides from ethylarenes. (Chemical Equation Presented).
- Shimokawa, Shohei,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
-
supporting information
p. 784 - 787
(2016/03/01)
-
- Synthesis method of aryl amide compound
-
The invention relates to a synthesis method of an aryl amide compound shown as formula (III) in the specification. The method comprises the steps of: in an organic solvent, in the presence of a catalyst, an oxidant and an assistant, carrying out reaction on a compound shown as formula (I) and a compound shown as formula (II) in the specification, then conducting post-treatment so as to obtain the compound shown as formula (III) (formula (I), formula (II) and formula (III)). Specifically, R is selected from H, C1-C6 alkyl, C1-C6 alkoxy, cyano or halogen. The method adopts an appropriate reaction substrate to obtain the target product with high yield through the comprehensive synergistic effect of the catalyst, the oxidant and the assistant, is very beneficial to industrial production, and has wide application prospects.
- -
-
Paragraph 0049; 0050; 0051; 0052; 0053; 0054
(2017/01/02)
-
- Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
-
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.
- Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
-
p. 6365 - 6371
(2015/02/19)
-
- Sodium azide as a catalyst for the hydration of nitriles to primary amides in water
-
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.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Roostaei, Mohsen
-
p. 267 - 269
(2015/06/02)
-
- Pd/C-catalyzed facile synthesis of primary aromatic amides by aminocarbonylation of aryl iodides using ammonia surrogates
-
Use of Pd/C as an efficient, phosphine free, heterogeneous and recyclable catalyst for one pot carbonylative synthesis of primary aromatic amides has been demonstrated. The developed protocol is simple to perform and employs ammonium carbamate as an in situ solid ammonia source which is feasible and more convenient than direct use of ammonia gas. The applicability of the developed protocol was studied for various aryl iodide substrates and it was found that it provides good to excellent yields of the desired amides. The catalyst is easily separable and shows significant recyclability for up to four consecutive cycles without loss of catalytic activity.
- Mane, Rajendra S.,Bhanage, Bhalchandra M.
-
p. 76122 - 76127
(2015/09/22)
-
- Synthesis of aryl nitriles by palladium-assisted cyanation of aryl iodides using tert-butyl isocyanide as cyano source
-
Abstract A palladium-catalyzed synthesis of aryl nitriles by the cyanation of aryl iodides with tert-butyl isocyanide as cyano source has been developed. This novel and efficient method avoids the use of toxic cyanides. The reaction is easy-to-handle and shows good functional group compatibility.
- Jiang, Xiao,Wang, Jin-Mei,Zhang, Ying,Chen, Zhong,Zhu, Yong-Ming,Ji, Shun-Jun
-
p. 4883 - 4887
(2015/08/03)
-
- Direct conversion of aromatic aldehydes into benzamides via oxidation with potassium permanganate in liquid ammonia
-
Oxidation of aromatic aldehydes by KMnO4 in liquid ammonia gives amides directly. The reaction proceeds satisfactorily when the aldehydes are activated by electron-withdrawing substituents on the ring.
- Antoniak, Damian,Sakowicz, Arkadiusz,Loska, Rafa?,Makosza, Mieczys?aw
-
supporting information
p. 84 - 86
(2015/02/05)
-
- Efficient and selective copper-grafted nanoporous silica in aqueous conversion of aldehydes to amides
-
The one-pot conversion of aldehydes to their corresponding primary amides has been studied using SBA-15-grafted ethylenediamine copper complexes (En-Cu). The heterogeneous catalyst could be readily isolated from the reaction mixture and reused at least 14 times without significant loss in activity. The influence of reaction parameters was studied and the conditions determining yields and selectivities, including quantity of catalyst, solvent and base, were optimized to afford amides in high yields. The structures of synthesized catalysts were investigated using different characterization techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), CHN, atomic absorption (AA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).
- Rostamnia, Sadegh,Nouruzi, Nasrin,Xin, Hongchuan,Luque, Rafael
-
p. 199 - 205
(2015/02/02)
-
- Synthesis of a copper(ii) complex covalently anchoring a (2-iminomethyl)phenol moiety supported on HAp-encapsulated-α-Fe2O3 as an inorganic-organic hybrid magnetic nanocatalyst for the synthesis of primary and secondary amides
-
A novel hydroxyapatite-encapsulated-α-Fe2O3-based Cu(ii) organic-inorganic hybrid (interphase) catalyst was prepared. The prepared nanocatalyst provided an efficient, useful and green method for the oxidative amidation of aromatic aldehydes with ammonium hydrochloride and aniline hydrochloride, in short reaction times and good yields. The magnetic nature of the catalyst led to its easy recovery by an external magnetic field and convenient reuse.
- Mamaghani,Shirini,Sheykhan,Mohsenimehr
-
p. 44524 - 44529
(2015/06/02)
-
- Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides
-
Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride, and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which proceeds exclusively in aqueous medium under neutral conditions. the Partner Organisations 2014.
- Baig, R. B. Nasir,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
-
p. 2122 - 2127
(2014/04/17)
-
- Direct conversion of aromatic aldehydes into benzamides via oxidation with potassium permanganate in liquid ammonia
-
Oxidation of aromatic aldehydes by KMnO4 in liquid ammonia gives amides directly. The reaction proceeds satisfactorily when the aldehydes are activated by electron-withdrawing substituents on the ring.
- Antoniak, Damian,Sakowicz, Arkadiusz,Loska, Rafa?,Makosza, Mieczys?aw
-
supporting information
(2015/01/08)
-
- High-temperature synthesis of amides from alcohols or aldehydes by using flow chemistry
-
An efficient conversion of aliphatic and aromatic alcohols or aldehydes into the corresponding primary amides was successfully achieved by using flow chemistry. Excellent yields were obtained in very short reaction times, and thus this method offers an efficient alternative to traditional methods for amide formation.
- Ambreen, Nida,Wirth, Thomas
-
p. 7590 - 7593
(2015/04/22)
-