- Erratum: Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate (Org. Biomol. Chem. (2015) 13 (8322-8329))
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Correction for 'Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate' by Lianpeng Zhang et al., Org. Biomol. Chem., 2015, 13, 8322-8329.
- Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
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Read Online
- Zinc chloride-catalyzed expeditious route to nitriles
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Zinc chloride has been found to be an excellent catalyst for a one-pot synthesis of nitriles from araldehydes and hydroxylammonium chloride under solvent-free conditions. The features of the present method are short reaction time, easy workup procedure, and good yields of the nitriles.
- Paesha,Nizam, Aatika
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Read Online
- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
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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
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supporting information
p. 21479 - 21485
(2021/08/23)
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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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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.
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Paragraph 0034-0039; 0202-0207
(2020/09/16)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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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
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p. 378 - 385
(2020/10/02)
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- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
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The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
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Paragraph 0048; 0049
(2020/09/12)
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- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
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p. 1397 - 1405
(2020/02/04)
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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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supporting information
p. 1484 - 1488
(2019/07/15)
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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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- Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
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A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
- Nandi, Jyoti,Leadbeater, Nicholas E.
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supporting information
p. 9182 - 9186
(2019/11/05)
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- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
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A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
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supporting information
p. 1434 - 1436
(2019/05/01)
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- Uniform silver nanoparticles on tunable porous N-doped carbon nanospheres for aerobic oxidative synthesis of aryl nitriles from benzylic alcohols
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Tunable N-doped carbon nanospheres from sucrose as carbon source and Tris(2-aminoethyl)amine (TAEA) as nitrogen source by a simple and easily reproducible method were prepared. It was demonstrated that the tunable N-doping of carbon spheres could be realized by altering the ratio of TAEA in the raw materials. The content of doped nitrogen, surface area, pore volume and pore size of carbon nanospheres were increased with the increasing of TAEA amount in the hydrothermal process. Prepared N-doped carbon nanospheres act as solid ligand for anchoring of Ag NPs which generated via chemical reduction of Ag ions. Benzylic alcohols and aldehydes were converted into the aryl nitriles by using Ag/N-CS-1 nanospheres as the catalyst and O2 as the oxidant, efficiently. This catalyst was stable and could use for 6 successful runs.
- Hashemi, Alireza Nemati,Eshghi, Hossein,Lamei, Kamran
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- Enhanced catalytic activity of cobalt nanoparticles encapsulated with an N-doped porous carbon shell derived from hollow ZIF-8 for efficient synthesis of nitriles from primary alcohols in water
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A cobalt catalyst derived from a unique core-shell structure based on hollow ZIF-8 and ZIF-67 (ZIF-67@ZIF-8) is prepared, which exhibits excellent catalytic efficiency for the synthesis of nitriles from alcohols in water under mild conditions (1 atm O2, 50 °C) owing to its large BET surface area, high pore volume, high basicity and hydrophilicity.
- Sun, Kang-Kang,Sun, Jia-Lin,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 4334 - 4340
(2019/08/21)
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- Design and Synthesis of Marine Phidianidine Derivatives as Potential Immunosuppressive Agents
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A series of novel marine phidianidine derivatives were designed, synthesized, and evaluated for their immunosuppressive activities during our search of potential immunosuppressive agents with high efficacy and low toxicity from marine sources. These compounds were tested for their inhibitory activity on Con A-induced T cell and lipopolysaccharide-induced B cell proliferation. Compounds 14a and 18c, displaying the most promising inhibitory effects and low toxicities, were further found to possess immune-regulatory activities upon cross-linking of T cell receptor (TCR) and B cell receptor (BCR) on purified T and B cells, respectively.
- Liu, Jin,Li, Heng,Chen, Kai-Xian,Zuo, Jian-Ping,Guo, Yue-Wei,Tang, Wei,Li, Xu-Wen
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p. 11298 - 11308
(2019/01/04)
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- Direct Conversion of Benzyl Ethers into Aryl Nitriles
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A direct method was developed for the conversion of benzyl ethers into aryl nitriles by using NH 4 OAc as the nitrogen source and oxygen as the terminal oxidant with catalysis by TEMPO/HNO 3; the method is valuable for both the synthesis of aromatic nitriles and for the deprotection of ether-protected hydroxy groups to form nitrile groups in multistep organic syntheses.
- Tian, Xinzhe,Ren, Yun-Lai,Ren, Fangping,Cheng, Xinqiang,Zhao, Shuang,Wang, Jianji
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p. 2444 - 2448
(2018/11/23)
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- Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
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A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
- Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
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supporting information
p. 4816 - 4820
(2018/07/13)
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- Synthesis method of benzonitrile compounds
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The invention provides a preparation method of benzonitrile compounds. The preparation method comprises the steps: carrying out a reaction in an organic solvent at 0-50 DEG C for 4-12h under the action of an oxidant by taking phenylacetylene as shown in the formula (I) and a derivative of phenylacetylene as raw materials and nitrite as a nitrogen source, and separating and purifying the obtained reaction liquid to prepare the benzonitrile compound as shown in the formula (II); and the amount-of-substance ratio of the nitrogen source to phenylacetylene as shown in the formula (I) and the derivative of phenylacetylene is (1-3):1. The preparation method is simple and available in raw material, mild in reaction condition, good in functional group tolerance, simple in operation and environment-friendly so as to be a novel method for synthesizing benzonitrile containing various substituent groups.
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Paragraph 0072; 0073; 0074
(2018/04/02)
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- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
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Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
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p. 885 - 889
(2018/12/10)
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- Magnetically recoverable lanthanum hydroxide as an efficient catalyst for Aerobic Oxidative Conversions of primary alcohols to the nitriles
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Herein we report a novel magnetically recoverable lanthanum hydroxide nanoparticles for oxidative synthesis of nitriles directly from corresponding alcohols with ammonia as nitrogen source. The procedure for the preparation and characterization of La(OH)3/Fe3O4 magnetic nanoparticles were investigated and the scope and generality of the method was explored for a series of structurally diverse primary alcohols with electron-donating and electron-withdrawing groups. The best result was observed when 5?mol% of La with respect to the benzyl alcohol was used at reflux condition under O2 atmosphere. The La(OH)3/Fe3O4 magnetic nanoparticles could be easily isolated from the reaction mixture with an external magnet and reused at least 5 times without significant loss in activity.
- Ziaee, Fariborz,Gholizadeh, Mostafa,Seyedi, Seyed Mohammad
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- Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
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A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
- Hu, Yongke,Chen, Lei,Li, Bindong
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supporting information
p. 464 - 466
(2017/11/13)
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- An efficient synthesis of nitrile, tetrazole and urea from carbonyl compounds
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An efficient conversion of carbonyl compounds (aldehydes and ketones) to nitrile, tetrazole, and urea was developed with the use of a POCl3 and sodium azide mixture using a convergent and microwave method. This is the first report on the direct conversion of ketone to urea. The synthesized compounds were characterized by 1H NMR, 13C NMR, mass and IR spectroscopies and were found to be in agreement with reported compounds.
- Sribalan, Rajendran,Sangili, Arumugam,Banuppriya, Govindharasu,Padmini, Vediappen
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p. 3414 - 3421
(2017/07/13)
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- Copper (II)-catalysed direct conversion of aldehydes into nitriles in acetonitrile
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A mild one-pot method for the direct conversion of aryl, heteroaryl and alkyl aldehydes into nitriles was achieved by forming the corresponding oximes in situ with NH2OH and allowing them to react with CuO and acetonitrile. Yields of the 13 nitriles prepared were moderate to very good (62–91%).
- Ma, Xiaoyun,Ao, Jun,Chen, Zhengjian,Liu, Yi
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p. 465 - 468
(2017/08/18)
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- The effect of regioisomerism on the mesomorphic and photophysical behavior of oxadiazole-based tris(: N -salicylideneaniline)s: Synthesis and characterization
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Two new regioisomeric star-shaped tris(N-salicylideneaniline)s are synthesized and characterized. The arms of these star-shaped mesogens differ from each other with respect to the substitution on the 3,5-positions of the central 1,2,4-oxadiazole moieties. The unsymmetrical nature of substitution leads to a change in the distribution of electron density, which will have an effect on the type of columnar self-assembly. One of these molecules stabilizes the columnar hexagonal phase, while the other one stabilizes the columnar rectangular phase. The columnar rectangular phase, which requires enhanced intermolecular interactions, is observed in the case of the star-shaped molecule, where the trialkoxy phenyl group is connected at the 5-position of the heterocycle, whereas the columnar hexagonal phase is observed in the case of the star-shaped molecule, where the trialkoxy phenyl group is connected at the 3-position of the heterocycle. These compounds showed reduced melting points, clearing points and an enhanced mesophase range with respect to their symmetric counterpart (1,3,4-oxadiazole derivative) reported earlier. All the molecules exhibited green light emission in solution, with good quantum yield. The emission of 1,2,4-oxadiazole derivatives was considerably red-shifted in comparison to those of 1,3,4-oxadiazole derivatives. This study emphasizes how a minor change in the molecular structure brings about a beneficial change in the self-assembly characteristics of star-shaped molecules.
- Pathak, Suraj Kumar,Nath, Subrata,De, Joydip,Pal, Santanu Kumar,Achalkumar, Ammathnadu S.
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supporting information
p. 9908 - 9917
(2017/09/18)
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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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- A primary alcohol nitrile method (by machine translation)
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The invention discloses a catalytic oxidation of primary alcohol nitrile method, said method comprising the following steps: formula (I) or formula (III) as shown in the primary alcohol as the raw material, in order to copper salt as catalyst, in order to air as the oxidizing agent, in order to TEMPO (2, 2, 6, 6 - tetramethyl piperidine nitrogen oxide) and help the oxidizing agent, ammonia as cocatalyst and solvent, for 80 - 120 °C reaction under 15 - 30h, after the reaction, the resulting reaction solution by the following formula (II) after treatment of the formula (IV) is shown in the nitriles; the reaction of the invention conversion, high yield, easy operation, low cost, safe reaction, the whole process is friendly to the environment, pollution-free. (by machine translation)
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Paragraph 0110; 0111; 0112; 0113; 0114
(2017/07/22)
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- Method for preparing nitrile by alcohol oxidation
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The invention provides a method for preparing nitrile by alcohol oxidation. The method comprises the following steps: mixing substrate alcohol which is shown as formula (I), a catalyst, a cocatalyst TEMPO, a ligand, an alkaline matter, 25 weight percent to 28 weight percent of ammonium hydroxide and a solvent; reacting for 2 to 24 hours with stirring in an oxygen atmosphere at 25 to 100 DEG C, and performing aftertreatment on reaction liquid to obtain a product nitrile which is shown in a formula (II). The method provided by the invention is environment friendly, wide in substrate application range, high in yield and mild in reaction conditions, has the preparation scale from grams to over hundreds of grams, and also has relatively high practical application value.
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Paragraph 0043; 0046; 0047
(2017/01/23)
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- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
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The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
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p. 8657 - 8667
(2015/09/15)
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- Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate
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The copper-mediated cyanation of indoles with DMF as a single surrogate has been realized. This approach could be applied for the cyanation of some electron-rich arenes and aryl aldehydes as well. Aryl aldehydes were demonstrated to be the key intermediates in the cascade process of cyanation of indoles and electron-rich arenes.
- Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
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p. 8322 - 8329
(2015/08/03)
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- Unprecedented Transformation of a Directing Group Generated in Situ and Its Application in the One-Pot Synthesis of 2-Alkenyl Benzonitriles
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An unprecedented protocol for the transformation of benzoyl azides into benzonitrile derivatives via iminophosphoranes generated in situ is described. The strategy was successfully applied to the de-novo synthesis of 2-alkenylated benzonitrile derivatives from benzoyl azides through ortho CH activation/alkenylation followed by subsequent rearrangement. The salient features of this protocol involve incorporation of two important functionalities through cyanation and olefination in one pot under mild reaction conditions by using a less expensive Ru catalyst. The mechanism was established by isolating and characterising (using 31PNMR) an intermediate with two ortho functionalities, iminophosphorane and olefin, under specific reaction conditions. Directly functional! Cyanation and olefination was accomplished in one pot from benzoyl azides through an unprecedented directing group transformation. The method generates benzonitriles and can be used for the synthesis of 2-alkenylated benzonitrile derivatives (see scheme).
- Kumar, Ravi,Arigela, Rajesh K.,Kundu, Bijoy
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p. 11807 - 11812
(2015/08/11)
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- Synthesis of aryl nitriles by palladium-assisted cyanation of aryl iodides using tert-butyl isocyanide as cyano source
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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
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p. 4883 - 4887
(2015/08/03)
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- Iodine-catalyzed ammoxidation of methyl arenes
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The development of organic transformation using cheap and readily available substrates under mild conditions will be pivotal for green and sustainable synthetic organic chemistry. Concerning our continued interest in the cyanation reaction, a metal-free direct ammoxidation of readily available methyl arenes leading to nitriles was established under mild conditions. A series of aryl methanes especially heteroaryl methanes (30 examples) were applicable in moderate to good yields with good functionality tolerance.
- Guo, Songjin,Wan, Gen,Sun, Song,Jiang, Yan,Yu, Jin-Tao,Cheng, Jiang
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supporting information
p. 5085 - 5088
(2015/03/30)
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- Nitrile synthesis through catalyzed cascades involving acid-nitrile exchange
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Irreversible acid-nitrile exchange reactions using both glutaronitrile and (phenylsulfonyl)acetonitrile may be catalyzed by Lewis acids. Whereas a cyclization towards imides displaces the equilibria in the reaction with dinitriles, a decarboxylation step is involved when using the (phenylsulfonyl)acetonitrile. Georg Thieme Verlag Stuttgart New York.
- Cartigny, Damien,Dos Santos, Aurelie,El Kaim, Laurent,Grimaud, Laurence,Jacquot, Roland,Marion, Philippe
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p. 1802 - 1806
(2014/07/08)
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- Copper-catalyzed cyanations of aromatic bromides with benzoyl cyanide
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Aromatic nitriles were synthesized through copper-catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source. A series of functional groups were tolerated under the reaction conditions to provide the products in good yields. Moreover, this protocol avoids using of highly toxic alkali cyanides and expensive palladium catalysts.
- Wang, Liang,Pan, Liang,Chen, Qun,He, Mingyang
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supporting information
p. 1221 - 1224
(2015/02/05)
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- Method for producing compounds comprising nitrile functions
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The present invention concerns the production of compounds comprising nitrite functions and cyclic imide compounds. More specifically, the invention relates to the production of compounds comprising nitrile functions from compounds comprising carboxylic functions, advantageously of natural and renewable origin, and from methyl-2 glutaronitrile (MGN) or a mixture N of dinitriles comprising methyl-2 glutaronitrile (MGN), ethyl-2 succinonitrile (ESN) and adiponitrile (AdN).
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Paragraph 0071-0075; 0077-0078
(2014/12/09)
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- NBS mediated nitriles synthesis through CC double bond cleavage
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An NBS mediated nitriles synthesis through CC double bond cleavage has been developed. TMSN3 was employed as the nitrogen source for this Cu(OAc)2 promoted nitrogenation reaction. This transformation has a relatively high regio-selectivity to form aromatic nitriles.
- Zong, Xiaolin,Zheng, Qing-Zhong,Jiao, Ning
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supporting information
p. 1198 - 1202
(2014/03/21)
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- Iron nitrate/TEMPO: A superior homogeneous catalyst for oxidation of primary alcohols to nitriles in air
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A highly practical, one-step, facile synthesis of aromatic, heteroaromatic, allylic and aliphatic nitriles from primary alcohols catalyzed by ferric nitrate [Fe(NO3)3·9H2O] in the presence of TEMPO, aqueous ammonia and air at room temperature is described.
- Dighe, Shashikant U.,Chowdhury, Deepan,Batra, Sanjay
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p. 3892 - 3896
(2015/01/09)
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- Copper-mediated cyanation of aryl boronic acids using benzyl cyanide
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An efficient copper-mediated synthesis of aryl nitriles from aryl boronic acids has been achieved using benzyl cyanide as a user-friendly cyanide source. Various aryl boronic acids underwent the reaction smoothly, affording the corresponding aryl nitriles in moderate to good yields. tert-Butyl hydroperoxide (TBHP) was found to be a critical agent facilitating the cyanation reaction.
- Luo, Yan,Wen, Qiaodong,Wu, Zhiyuan,Jin, Jisong,Lu, Ping,Wang, Yanguang
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supporting information
p. 8400 - 8404
(2013/09/02)
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- An efficient, rapid and facile procedure for conversion of aldoximes to nitriles using triphenylphosphine and N-halo sulfonamides
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N,N,N′,N′-Tetrabromobenzene-1,3-disulfonamide (TBBDA)/triphenylphosphine and N,N,N′,N′-tetrachlorobenzene-1,3- disulfonamide (TCBDA)/triphenylphosphine have been introduced as highly efficient systems for the versatile conversion of aldoxime derivatives into nitriles. The process reported here is operationally simple and reactions have been mildly performed in dichloromethane at room temperature.
- Ghorbani-Vaghei, Ramin,Shiri, Lotfi,Ghorbani-Choghamarani, Arash
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p. 1123 - 1126
(2014/01/06)
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- SOCl 2/β-cyclodextrin: A new and efficient catalytic system for Beckmann rearrangement and dehydration of aldoximes under aqueous condition
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A rapid and efficient synthesis of amides via Beckmann rearrangement of ketoximes and dehydration of aldoximes to corresponding nitriles with good to excellent yields has been carried out in the presence of SOCl 2/β-cyclodextrin under aqueous conditions. The β-cyclodextrin has been recovered and reused. Copyright Taylor & Francis Group, LLC.
- Patil, Dipak,Dalal, Dipak
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p. 118 - 128
(2012/10/30)
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- Conversion of aldoximes into nitriles catalyzed by simple transition metal salt of the fourth period in acetonitrile
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Conversion of aldoximes into nitriles catalyzed by simple transition metal catalysts, such as copper salts, nickel salts, cobalt salts, zinc salts, iron salts, and manganese salts in acetonitrile was investigated. All the metal salts display catalytic property in the conversion of aldoximes into nitriles and cupric acetate exhibits much higher activity than other catalysts. The corresponding amide was detected in almost all cases and acetonitrile was found to be involved in the conversion of aldoximes into nitriles.
- Ma, Xiao-Yun,He, Ying,Lu, Ting-Ting,Lu, Ming
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p. 2560 - 2564
(2013/03/28)
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- Combustion-derived CuO nanoparticles: An effective and environmentally benign catalyst in the synthesis of aromatic nitriles from aromatic aldehydes
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CuO nanoparticles were synthesized using an energy-efficient and rapid solution combustion technique with malic acid employed as a fuel. The combustion-derived CuO nanoparticles were used as catalysts in a one-pot synthesis of aromatic nitriles from aromatic aldehydes and hydroxylamine hydrochloride. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, and Brunauer-Emmett-Teller surface area analysis. The catalytic activity of the CuO nanoparticles in the synthesis of aromatic nitriles from aromatic aldehydes was evaluated. The present protocol offers the advantages of a clean reaction, simple methodology, short reaction duration (1-2 min), and high yield (85%-98%). The catalytic activity of the CuO nanoparticles was found to be higher than that of bulk CuO powder under the same conditions. The catalyst can also be recovered and reused up to four times with no significant loss of catalytic activity. The present approach is inexpensive and is a convenient technique suitable for industrial production of CuO nanoparticles and nitriles.
- Anandakumar, Belladamadu Siddappa,Reddy, Muthukur Bhojegowd Madhusudana,Tharamani, Chikka Nagaiah,Pasha, Mohamed Afzal,Chandrappa, Gujjarahalli Thimmanna
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p. 704 - 710
(2013/08/25)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Molecular iodine in aqueous ammonia: Oxidative fragmentation of oxiranes to nitriles
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Oxiranes undergo oxidative fragmentation, when treated with iodine in aqueous ammonia, to give nitriles. The reaction goes via formation of 1,2-amino alcohols as intermediates followed by CC bond cleavage. Advantages of the method are use of off-the-shelf nonexplosive, unlike previously used potentially explosive o-iodoxybenzoic acid, reagents, mild reaction conditions, and easy work-up procedure.
- Jadhav, Ravindra R.,Akamanchi, Krishnacharya G.
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p. 162 - 164
(2013/03/28)
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- Chemoselective Schmidt reaction mediated by triflic acid: Selective synthesis of nitriles from aldehydes
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An excellent utility of Schmidt reaction of aldehydes to access corresponding nitriles in an instantaneous reaction is demonstrated. The reaction of aldehydes with NaN3 and TfOH furnishes the corresponding nitriles in near quantitative yields and tolerates a variety of electron-withdrawing and electron-donating substituents on the substrates. Formanilides, a common side product in Schmidt reaction, is not observed in this reaction. Besides these advantages, the salient feature of this reaction is that it exhibits a remarkable chemoselectivity, as acid and ketone functionalities are well tolerated under the reaction conditions. The reaction is easily scalable, high yielding, and nearly instantaneous.
- Rokade, Balaji V.,Prabhu, Kandikere Ramaiah
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experimental part
p. 5364 - 5370
(2012/09/07)
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- A non-metal catalysed oxidation of primary azides to nitriles at ambient temperature
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A novel non-metal catalyzed oxidation of organic azides to nitriles under solvent-free conditions is presented employing catalytic amounts of KI, and DABCO in aq. TBHP at room temperature. This non-metal catalyzed oxidation of azides provides good selectivity as double and triple bonds were not oxidized under the present reaction conditions. The Royal Society of Chemistry 2012.
- Lamani, Manjunath,Devadig, Pradeep,Prabhu, Kandikere Ramaiah
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p. 2753 - 2759
(2012/11/07)
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- Facile transformation of esters to nitriles
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Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.
- Suzuki, Yusuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 7956 - 7962
(2011/11/07)
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- Direct transformation of N,N-disubstituted amides and isopropyl esters to nitriles
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Various N,N-dimethyl amides, N-methoxy-N-methyl amides, and isopropyl esters were smoothly transformed into the corresponding nitriles in good to moderate yields by the treatment with diisobutylaluminium hydride, followed by treatment with molecular iodine in aq ammonia. The present reactions are novel one-pot and practical methods for the transformation of N,N-disubstituted amides and isopropyl esters into nitriles, through the formation of hemiaminal O-AlBu2 and hemiacetal O-AlBu2, respectively.
- Suzuki, Yusuke,Yoshino, Takumi,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 3809 - 3814
(2011/06/25)
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- SUBSTITUTED NAPHTHYRIDINES AND THEIR USE AS SYK KINASE INHIBITORS
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The invention relates to new substituted naphthyridines of formula (1), as well as pharmacologically acceptable salts, diastereomers, enantiomers, racemates, hydrates or solvates thereof, wherein R1 is selected from among -O-R3 or -NR3R4, R3 is C1-6-alkyl which is substituted by R5 and R6 R5 is selected from hydrogen, branched or linear C1-6-alkyl, C2-6-alkenyl, -C1-6-alkylen-O-C1-3-alkyl, C1-3-haloalkyl, R6 is ring X wherein n is either 0 or 1, and Formula (I) is a either a single or a double bond and wherein A, B, D and E are each independently from one another selected from CH2, CH, C, N, NH, O or S and wherein ring X is attached to the molecule either via position A, B, D or E, wherein said ring X may optionally be further substituted by one, two or three residues each selected individually from the group consisting of -oxo, hydroxy, -C1-3-alkyl, -C1-3-haloalkyl, -O-C1-3-alkyl, -C1-3-alkanol and halogen, and wherein R4, R2, R7, R8, R9, R10, R11 and Q may have the meanings as given in claim 1, as well as pharmaceutical compositions containing these compounds.
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Page/Page column 45
(2011/08/21)
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- Environment friendly protocol for the synthesis of nitriles from aldehydes
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A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic, non-corrosive and reusable zinc oxide (ZnO) as the catalyst under solvent-free microwave irradiation. The present approach offers the advantages of a clean reaction, simple methodology, employing readily available catalyst, short reaction duration (1. min), high selectivity; and high yield (90-98%).
- Madhusudana Reddy,Pasha
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experimental part
p. 1025 - 1028
(2011/10/08)
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