- A “universal” catalyst for aerobic oxidations to synthesize (hetero)aromatic aldehydes, ketones, esters, acids, nitriles, and amides
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Functionalized (hetero)aromatic compounds are indispensable chemicals widely used in basic and applied sciences. Among these, especially aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides represent valuable fine and bulk chemicals, which are used in chemical, pharmaceutical, agrochemical, and material industries. For their synthesis, catalytic aerobic oxidation of alcohols constitutes a green, sustainable, and cost-effective process, which should ideally make use of active and selective 3D metals. Here, we report the preparation of graphitic layers encapsulated in Co-nanoparticles by pyrolysis of cobalt-piperazine-tartaric acid complex on carbon as a most general oxidation catalyst. This unique material allows for the synthesis of simple, functionalized, and structurally diverse (hetero)aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides from alcohols in excellent yields in the presence of air.
- Bartling, Stephan,Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Rabeah, Jabor,Rockstroh, Nils,Senthamarai, Thirusangumurugan
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supporting information
p. 508 - 531
(2022/02/11)
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- Acid-promoted palladium(II)-catalyzed ortho-halogenation of primary benzamides: En route to halo-arenes
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Br?nsted acid-promoted palladium(II)-catalyzed regioselective installation of halogens (Br, Cl, and I) to the aromatic ring of benzamide derivatives has been achieved using primary amides. A wide variety of benzamides were compatible under established conditions to afford the halogenated products without installing any external auxiliary. Mild reaction conditions, use of primary amide as a directing group, external additive-free conditions, and gram-scale reaction are some appealing features of this protocol. Detailed experimental results revealed that Br?nsted acid plays a critical role in this transformation.
- Jaiswal, Yogesh,Kumar, Amit
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- Nickel-catalyzed regioselective C-H halogenation of electron-deficient arenes
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A straightforward Ni(ii)-catalyzed general strategy was developed for the ortho-halogenation of electron-deficient arenes with easily available halogenating reagents N-halosuccinimides (NXS; X = Br, Cl and I). The transformation was highly regioselective and a wide substrate scope and functional group tolerance were observed. This discovery could be of great significance for the selective halogenation of amides, benzoic esters and other substances with guiding groups. Mechanistic investigations were also described.
- Li, Ze-Lin,Wu, Peng-Yu,Cai, Chun
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supporting information
p. 3462 - 3468
(2019/02/25)
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- A halogenated benzamide compound preparation method (by machine translation)
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The invention discloses a halogenated benzamide compound preparation method. The preparation method, comprises the following steps: adding the hydrogen peroxide to type I compounds, water and alkali are mixed to obtain a mixed solution of, shown in the following reaction; wherein X is halogen, n is 1, 2, 3, 4 or 5; states the type I compound charging capacity of at least 8 g, the hydrogen peroxide and the formula I compound in a molar ratio of 1:1 - 1.6: 1; the hydrogen peroxide addition time is 2 - 10 and H. The invention for the preparation of the water as the reaction solvent, to avoid the use of organic solvent, and in reducing the amount on the basis of raw materials, can still reach the higher yield and the product quality is good, the operation is simple, three wastes, economic effect is high, and is suitable for industrial production. (by machine translation)
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Paragraph 0028; 0029
(2018/10/27)
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- Design, synthesis, DFT study and antifungal activity of the derivatives of pyrazolecarboxamide containing thiazole or oxazole ring
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Pyrazolecarboxamide fungicides are one of the most important classes of agricultural fungicides, which belong to succinodehydrogenase inhibitors (SDHIS). To discover new pyrazolecarboxamide analogues with broad spectrum and high activity, a class of new compounds of pyrazole carboxamide derivatives containing thiazole or oxazole ring were designed by scaffold hopping and bioisosterism, and 36 pyrazole carboxamide derivatives with antifungal activity were synthesized. Those compounds were evaluated against five phytopathogenic fungi, Gibberella zeae, Phytophythora capsici, Sclerotonia sclerotiorum, Erysiphe graminis and Puccinia sorghi. The results indicated that most of the compounds displayed good fungicidal activities, especially against E. graminis. Theoretical calculations were carried out at the B3LYP/6-31G (d, p) level and the full geometry optimization was carried out using the 6-31G (d, p) basis set, and the frontier orbital energy, atomic net charges, molecular docking were discussed, and the structure-activity relationships were also studied.
- Yan, Zhongzhong,Liu, Aiping,Huang, Mingzhi,Liu, Minhua,Pei, Hui,Huang, Lu,Yi, Haibo,Liu, Weidong,Hu, Aixi
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p. 170 - 181
(2018/03/08)
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
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supporting information
p. 266 - 273
(2018/01/12)
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- Silica-sulfuric acid: Novel, simple, efficient and reusable catalyst for hydration of nitrile to amide
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Silica-sulfuric acid efficiently catalyzes conversion of aliphatic, substituted aromatic and hetero aromatic nitriles to their corresponding amides in good to excellent yields under reflux condition. Products obtained were purified by column chromatography method and characterized by 1H NMR, 13C NMR and mass spectral analysis.
- Chandrashekharappa, Sandeep,Venugopala, Katharigatta N.,Venugopala, Rashmi,Odhav, Bharti
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p. 2177 - 2180
(2016/07/21)
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- Design, synthesis and fungicidal activity of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide
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To find a new lead compound with high biological activity, a series of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide were designed using linking active substructures method. The target compounds were synthesized from substituted benzoic acid by four steps and their structures were confirmed by 1H NMR, IR spectrum and elemental analysis. The in vitro bioassay results indicated that some target compounds exhibited excellent fungicidal activities, and the position of the substituents played an important role in fungicidal activities. Especially, compound 5n, exhibited better fungicidal activities than the commercial fungicide flutolanil against two tested fungi Valsa Mali and Sclerotinia sclerotiorum, with EC50 values of 3.44 and 2.63 mg/L, respectively. And it also displayed good in vivo fungicidal activity against S. sclerotiorum with the EC50 value of 29.52 mg/L.
- Lei, Peng,Xu, Yan,Du, Juan,Yang, Xin-Ling,Yuan, Hui-Zhu,Xu, Gao-Fei,Ling, Yun
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p. 2544 - 2546
(2016/07/07)
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- Visible Light-Induced Iodine-Catalyzed Transformation of Terminal Alkynes to Primary Amides via C≡C Bond Cleavage under Aqueous Conditions
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The visible light-induced iodine-catalyzed oxidative cleavage of the C≡C bond for transforming terminal alkynes into primary amides in the presence of ammonia under aqueous conditions is described. This metal-free protocol which ensued via initial hydroamination of the acetylene bond followed by liberation of diiodomethane (CH2I2) was found to be applicable to aromatic, heteroaromatic and aliphatic alkynes.
- Dighe, Shashikant U.,Batra, Sanjay
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supporting information
p. 500 - 505
(2016/02/12)
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- Ferric perchlorate-mediated one-step reaction of [60]fullerene with primary amides for the synthesis of fullerooxazoles
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The facile one-step reaction of [60]fullerene with primary amides promoted by cheap and easily available ferric perchlorate afforded a series of interesting fullerooxazole derivatives. The reaction was tolerant of a large variety of primary amides containing aryl, alkyl, and cinnamyl groups. A possible reaction mechanism for product formation was proposed.
- Zhang, Xiao-Feng,Li, Fa-Bao,Shi, Ji-Long,Wu, Jun,Liu, Li
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p. 1626 - 1632
(2016/02/19)
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- Synthesis, antitumor activity and mechanism of action of novel 1,3-thiazole derivatives containing hydrazide–hydrazone and carboxamide moiety
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A series of novel 2,4,5-trisubstituted 1,3-thiazole derivatives containing hydrazide–hydrazine, and carboxamide moiety including 46 compounds T were synthesized, and evaluated for their antitumor activity in vitro against a panel of five human cancer cell lines. Eighteen title compounds T displayed higher inhibitory activity than that of 5-Fu against MCF-7, HepG2, BGC-823, Hela, and A549 cell lines. Especially, T1, T26 and T38 exhibit best cytotoxic activity with IC50values of 2.21?μg/mL, 1.67?μg/mL and 1.11?μg/mL, against MCF-7, BCG-823, and HepG2 cell lines, respectively. These results suggested that the combination of 1,3-thiazole, hydrazide–hydrazone, and carboxamide moiety was much favorable to cytotoxicity activity. Furthermore, the flow cytometry analysis revealed that compounds T1 and T38 could induce apoptosis in HepG2 cells, and it was confirmed T38 led the induction of cell apoptosis by S cell-cycle arrest.
- He, Haifeng,Wang, Xiaoyan,Shi, Liqiao,Yin, Wenyan,Yang, Ziwen,He, Hongwu,Liang, Ying
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supporting information
p. 3263 - 3270
(2016/07/12)
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- Transition-metal-free hydration of nitriles using potassium tert -butoxide under anhydrous conditions
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Potassium tert-butoxide acts as a nucleophilic oxygen source during the hydration of nitriles to give the corresponding amides under anhydrous conditions. The reaction proceeds smoothly for a broad range of substrates under mild conditions, providing an efficient and economically affordable synthetic route to the amides in excellent yields. This protocol does not need any transition-metal catalyst or any special experimental setup and is easily scalable to bulk scale synthesis. A single-electron-transfer radical mechanism as well as an ionic mechanism have been proposed for the hydration process.
- Midya, Ganesh Chandra,Kapat, Ajoy,Maiti, Subhadip,Dash, Jyotirmayee
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supporting information
p. 4148 - 4151
(2015/05/05)
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- Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
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The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
- Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
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p. 3754 - 3761
(2015/07/01)
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- Manganese oxide promoted liquid-phase aerobic oxidative amidation of methylarenes to monoamides using ammonia surrogates
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In the presence of amorphous MnO2, various methylarenes (even with two or more methyl groups) could be selectively converted into the corresponding primary monoamides in moderate to high yields. The observed catalysis was truly heterogeneous, and the retrieved amorphous MnO2 catalyst could be reused without an appreciable loss of its catalytic performance. Copyright
- Wang, Ye,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information; experimental part
p. 7250 - 7253
(2012/08/28)
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- Ruthenium-catalyzed rearrangement of aldoximes to primary amides in water
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The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium(II) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol %) as catalyst. Reactions proceeded cleanly in pure water at 100 °C without the assistance of any cocatalyst, affording the desired amides in high yields (70-90%) after short reaction times (1-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes and tolerated several functional groups. Reaction profiles and experiments using 18O-labeled water indicate that two different mechanisms are implicated in these transformations. In both of them, nitrile intermediates are initially formed by dehydration of the aldoximes. These intermediates are then hydrated to the corresponding amides by the action of a second molecule of aldoxime or water. A kinetic analysis of the rearrangement of benzaldoxime to benzamide is also discussed.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
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p. 6482 - 6490
(2012/10/30)
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- An efficient InCl3-catalyzed hydration of nitriles to amides: acetaldoxime as an effective water surrogate
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An efficient InCl3-catalyzed hydration protocol of nitriles to amides was developed. The reaction was carried out in toluene at refluxing temperature with the aid of acetaldoxime as an effective water surrogate to produce amides in high yields.
- Kim, Eun Sun,Lee, Hyun Seung,Kim, Sung Hwan,Kim, Jae Nyoung
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scheme or table
p. 1589 - 1591
(2010/04/29)
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- Preparation of primary amides from functionalized organozinc halides
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Organozinc halides, which are prepared either by direct zinc insertion or halogen-magnesium exchange and subsequent transmetalation with ZnCl2, react smoothly with commercially available trichloroacetyl isocyanate to give, after hydrolysis, the corresponding primary amides. This method is compatible with a variety of functional groups such as an ester or a cyano group. Also heterocyclic-, alkenyl, and acetylenic zinc reagents are converted to the corresponding primary amides under these conditions.
- Schade, Matthias A.,Manolikakes, Georg,Knochel, Paul
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supporting information; experimental part
p. 3648 - 3650
(2010/11/04)
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- Synthesis and bioactivity of N-benzoyl-N'-[5-(2'-substituted phenyl)-2-furoyl] semicarbazide derivatives
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In order to find novel chitin synthesis inhibitors (CSIs) with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 15 novel derivatives containing furan moieties were designed by converting the urea linkage of benzoylphenylureas into a semicarbazide and changing the aniline part into furoyl groups. The title compounds were synthesized by the reaction of substituted benzoyl isocyanates with 5-(substituted phenyl)-2-furoyl hydrazine, and the structures were confirmed by IR, 1H-NMR, elemental analysis and single crystal X-ray diffraction analyses (compound E2). The bioassay results indicated that the title compounds exhibit good insecticidal activity, especially towards Plutella xylostella L., but had lower fungicidal activity. Inspiringly, the title compounds possessed obvious anticancer activity against human promyelocytic leukemic cell line (HL-60), and some of the title compounds also had activity against human hepatocellular carcinoma cell line (Bel-7402), human gastric carcinoma cell line (BGC-823), and human nasopharyngeal carcinoma cell line (KB). The results indicated that the linkage in the lead compounds was important to the bioactivity and spectra. The modification on the urea linkage is an effective strategy to discover new pesticide and drug candidates.
- Cui, Zining,Ling, Yun,Li, Baoju,Li, Yongqiang,Rui, Changhui,Cui, Jingrong,Shi, Yanxia,Yang, Xinling
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scheme or table
p. 4267 - 4282
(2010/10/03)
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- Synthesis and fungicidal activity of aryl carbamic acid-5-aryl-2- furanmethyl ester
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Chitin, a major structural component of insect cuticle and fungus cell wall but absent in plants and vertebrates, is regarded as a safe and selective target for pest control agents. Chitin synthesis inhibitors (CSIs) have been well-known as insect growth regulators (IGRs) but rarely found as fungicides in agriculture. To find novel CSIs with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 26 novel aryl carbamic acid-5-aryl-2-furanmethyl esters were designed by converting the urea linkages of benzoylphenylureas to carbamic acid esters and changing the aniline parts into furanmethyl groups. The title compounds were synthesized and their structures confirmed by IR, 1H NMR, and elemental analysis. Preliminary insecticidal and fungicidal bioassays were carried out. The results indicated that the title compounds had no insecticidal effect on Culex pipiens pallens and Plutella xylostella Linnaeus, but most compounds exhibited good fungicidal activities against Corynespora cassiicola, Thanatephorus cucumeris, Botrytis cinerea, and Fusarium oxysporum. In particular, compounds V-4, V-6, V-7, and V-8 showed better activities against the four strains than those of the commercialized fungicides. The morphologic result suggested that compound V-21 had disturbed the cell wall formation of C. cassiicola. The results indicated that modification on the urea linkage of benzoylphenylurea was an effective way to discover new candidates for fungicides.
- Ying,Bao-Ju,Ling,Miao, Hong-Jian,Yan-Xia,Yang, Xin-Ling
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scheme or table
p. 3037 - 3042
(2011/07/31)
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- An efficient Pd-catalyzed hydration of nitrile with acetaldoxime
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An efficient palladium-catalyzed protocol for the hydration of nitrile to amide with acetaldoxime has been developed. A plausible mechanism was suggested involving the first Pd(II)-catalyzed nitrile-oxime coupling and the following disruption of the intermediate into amide and acetonitrile in a concerted manner.
- Kim, Eun Sun,Kim, Hoo Sook,Kim, Jae Nyoung
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body text
p. 2973 - 2975
(2009/08/09)
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- Discovering potent small molecule inhibitors of cyclophilin A using de novo drug design approach
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This work describes an integrated approach of de novo drug design, chemical synthesis, and bioassay for quick identification of a series of novel small molecule cyclophilin A (CypA) inhibitors (1-3). The activities of the two most potent CypA inhibitors (3h and 3i) are 2.59 and 1.52 nM, respectively, which are about 16 and 27 times more potent than that of cyclosporin A. This study clearly demonstrates the power of our de novo drug design strategy and the related program LigBuilder 2.0 in drug discovery.
- Ni, Shuaishuai,Yuan, Yaxia,Huang, Jin,Mao, Xiaona,Lv, Maosheng,Zhu, Jin,Shen, Xu,Pei, Jianfeng,Lai, Luhua,Jiang, Hualiang,Li, Jian
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supporting information; experimental part
p. 5295 - 5298
(2010/02/28)
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- Study of the microwave-assisted hydrolysis of nitriles and esters and the implementation of this system in rapid microwave-assisted Pd-catalyzed amination
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Microwave-assisted hydrolysis of benzonitriles and methyl benzoates has been studied using a toluene/concd aq KOH two phase system in the presence and absence of phase transfer catalyst. Conditions to allow and avoid smooth hydrolysis could be identified. Based on the latter, the first microwave protocol which allows the rapid Pd-catalyzed amination of aliphatic amines with chlorobenzenes containing sensitive functional groups has been developed.
- Van Baelen, Gitte,Maes, Bert U.W.
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p. 5604 - 5619
(2008/09/21)
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- REMEDIES FOR STRESS DISEASES COMPRISING MITOCHONDRIAL BENZODIAZEPINE RECEPTOR ANTAGONISTS
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A pharmaceutical composition for the prophylaxis and/or treatment of diseases induced, exacerbated or reignited by stressors comprising the compound of formula (I) wherein all symbols have the same meanings as described in the specification, etc. as an active ingredient.
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- Rh-catalyzed one-pot and practical transformation of aldoximes to amides
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Wilkinson's complex has been found to catalyze the one-pot transformation of aldoximes to the corresponding amides with high selectivity and efficiency under essentially neutral conditions.
- Park, Soyoung,Choi, Yoon-aa,Han, Hoon,Yang, Soon Ha,Chang, Sukbok
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p. 1936 - 1937
(2007/10/03)
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- Titanium oxide (TiO2) catalysed one-step Beckmann rearrangement of aldehydes and ketones in solvent free conditions
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In the presence of titanium oxide (TiO2) and without any additional organic solvents, Beckmann rearrangement of several ketones and aldehydes was performed in good yield.
- Sharghi, Hashem,Hosseini Sarvari, Mona
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p. 176 - 178
(2007/10/03)
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- One-step Beckmann rearrangement from carbonyl compounds and hydroxylamine hydrochloride in Al2O3/CH3SO3H (AMA) as a new reagent
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A facile and efficient synthetic procedure, for one-step Beckmann rearrangement of aldehydes and ketones with hydroxylamine hydrochloride and Al2O3/CH3SO3H (AMA) has been developed; cyclohexanone has been converted into ε-caprolactam in a quantitative yield.
- Sharghi,Sarvari
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p. 446 - 449
(2007/10/03)
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- An in-depth study of the biotransformation of nitriles into amides and/or acids using Rhodococcus rhodochrous AJ270
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A variety of aliphatic, aromatic and heterocyclic nitriles have been readily hydrolysed into the corresponding amides and/or acids under very mild conditions using Rhodococcus sp. AJ270. The nitrile hydratase involved in this novel nitrile-hydrolysing microorganism efficiently hydrates most nitriles tested, irrespective of the electronic and steric effects of the substituents, to form the amides. Conversion of amides into acids catalysed by the associated amidase is rapid and efficient in most cases. Substrates bearing an adjacent substituent (which may be an ortho substituent on an aromatic nitrile, an adjacent heteroatom in a heterocyclic ring or a geminal substituent in an α,β-unsaturated nitrile) undergo slow hydrolysis of the amides allowing efficient amide isolation. The scope, limitations and reaction mechanism of this enzymatic process have been systematically studied. A molecular size of >7 A diameter and the presence of functions capable of metal complexation near to the nitrile inhibit hydrolysis.
- Meth-Cohn, Otto,Wang, Mei-Xiang
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p. 1099 - 1104
(2007/10/03)
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- INSECT CHITIN FORMATION INHIBITORS. PART I. SYNTHESIS OF 1-(2,6-DICHLOROBENZOYL)-3-(2,4,6-TRICHLOROPHENYL)-UREA
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The synthesis of the title compound, obtained for investigations on its activity as the insect chitin formation inhibitor,is described.
- Biernacki, Wladyslaw,Gdula, Andrzej
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p. 451 - 454
(2007/10/02)
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- Use of 2,6-Dichlorobenzonitrile (Dichlobenil) as Starting Material for Synthesis of Herbicides, Derivatives of Benzoic Acid.
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Results of an investigation are presented in which S//N reactions of dichlobenil and its transformation products were investigated using as nucleophilic agents for chlorine exchange: sodium methanolate and ethanolate, as well as aniline and its derivatives. It has been shown that the ability to enter the reaction of mono- or disubstitution is dependent on the kind of derivative of 2,6-dichloro-3-nitrobenzoic acid, as well as on conditions of reactions. In the manner described above, dichlobenil has been transformed into valuable herbicide, dicamba, i. e. 3,6-dichloro-2-methoxybenzoic acid. A mixture of isomeric acids has been obtained, their herbicide activity having the same range.
- Romanowski,Wituch-Zapalowska,Eckstein
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p. 26 - 31,27, 28, 30
(2007/10/06)
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