- Hypervalent iodine catalyzed transamidation of carboxamides with amines
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This protocol describes the catalytic use of diacetoxyiodobenzene (DIB) for the efficient transamidation of carboxamides with amines under mild conditions.
- Vanjari, Rajeshwer,Kumar Allam, Bharat,Nand Singh, Krishna
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Read Online
- Silica supported perchloric acid catalyzed rapid N-formylation under solvent-free conditions
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A rapid and chemoselective method for the N-formylation of structurally diverse amines with formic acid using silica supported perchloric acid (HClO4-SiO2) at room temperature and under solvent-free conditions has been developed. The catalyst was found to be compatible with different functional groups and the formylation proceeded smoothly with amines bearing electron withdrawing as well as electron donating substituents.
- Ansari, Mohd. Imran,Hussain, Mohd. Kamil,Yadav, Nisha,Gupta, Puneet K.,Hajela
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- A remarkably simple N-formylation of anilines using polyethylene glycol
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N-Formylation of anilines has efficiently been carried out at room temperature in excellent yields by treatment with formic acid in polyethylene glycol (PEG-400). No additional solvent and catalyst are required.
- Das, Biswanath,Krishnaiah, Maddeboina,Balasubramanyam,Veeranjaneyulu, Boyapati,Nandan Kumar
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- TEMPO-Catalyzed Aerobic Oxidative Selenium Insertion Reaction: Synthesis of 3-Selenylindole Derivatives by Multicomponent Reaction of Isocyanides, Selenium Powder, Amines, and Indoles under Transition-Metal-Free Conditions
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A novel and efficient approach for the selenium functionalization of indoles was developed with selenium powder as the selenium source, catalyzed by 2,2,6,6-tetramethylpiperidinooxy (TEMPO) and employing O2 as the green oxidant. This protocol provides a practical route for the synthesis of 3-selenylindole derivatives and has the advantages of readily available starting materials, mild reaction conditions, and a wide scope of substrates. Electron spin-resonance (ESR) studies reveal that the approach involves the formation of nitrogen-centered radicals and selenium radicals via oxidation of in situ generated selenoates.
- Liu, Huan,Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
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Read Online
- Effective Synthesis of N-Arylformamide from α-Halo-N-arylacetamides
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A convenient synthetic method for N-arylformamide derivatives was successfully developed by reacting α-iodo-N-arylacetamides with formamide. This method was applicable to α-iodo-N-arylacetamide substrates bearing electron-donating or electron-withdrawing groups, N-(benzo[d][1,3]dioxol-5-yl)-2-iodoacetamide, 2-iodo-N-(pyridin-2-yl)acetamide, and 2-iodo-N-(naphthalen-4-yl)acetamide to give the corresponding N-arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.
- Chiang, Kun-Heng,Lu, Shi-Han,Yen, Wan-Ping,Uramaru, Naoto,Tseng, Wei-Siou,Chang, Te-Wei,Wong, Fung Fuh
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- One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles
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One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.
- Dong, Xiaosu,Wang, Zhaozhan,Duan, Yanan,Yang, Yong
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Read Online
- Novel 4-phenoxypyridine derivatives bearing imidazole-4-carboxamide and 1,2,4-triazole-3-carboxamide moieties: Design, synthesis and biological evaluation as potent antitumor agents
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Two series of novel 4-phenoxypyridine derivatives containing imidazole-4-carboxamide and 4-methyl-5-oxo-4,5-dihydro-1,2,4-triazole-3-carboxamide moieties were synthesized and evaluated for their in vitro inhibitory activities against c-Met kinase and anti
- Chen, Ye,Ding, Shi,Du, Siyuan,Hou, Yunlei,Li, Chunyan,Li, Zhen,Liu, Fang,Liu, Ju,Shen, Jiwei,Wang, Huan,Wei, Hao,Wu, Shuang
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- Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
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A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N-methylarylamines to N-arylformamides.
- Li, Dianjun,Wang, Shihaozhi,Yang, Jiale,Yang, Jinhui
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supporting information
p. 6768 - 6772
(2021/12/31)
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- Thermolysis-Induced Two- or Multicomponent Tandem Reactions Involving Isocyanides and Sulfenic-Acid-Generating Sulfoxides: Access to Diverse Sulfur-Containing Functional Scaffolds
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Direct reaction of isocyanides with some sulfenic-acid-generating sulfoxides led to the effective formation of the corresponding thiocarbamic acid S-esters in good to high yields. A multicomponent reaction involving isocyanide, sulfoxide, and a suitable nucleophile has also been developed, providing ready access to a diverse range of sulfur-containing compounds, including isothioureas, carbonimidothioic acid esters, and carboximidothioic acid esters.
- Wu, Shengfeng,Lei, Xiaofang,Fan, Erkang,Sun, Zhihua
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supporting information
p. 522 - 525
(2018/02/10)
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- Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
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A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
- Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
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p. 3907 - 3913
(2018/09/12)
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- Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
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The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
- Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
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p. 3615 - 3624
(2018/05/26)
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- Rh2(II)-Catalyzed Ring Expansion of Cyclobutanol-Substituted Aryl Azides to Access Medium-Sized N-Heterocycles
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A new reactivity pattern of Rh2(II)-N-arylnitrenes was discovered that facilitates the synthesis of medium-sized N-heterocycles from ortho-cyclobutanol-substituted aryl azides. The key ring-expansion step of the catalytic cycle is both chemosel
- Mazumdar, Wrickban,Jana, Navendu,Thurman, Bryant T.,Wink, Donald J.,Driver, Tom G.
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supporting information
p. 5031 - 5034
(2017/05/04)
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- Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
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A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
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supporting information
p. 1805 - 1809
(2017/02/05)
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- Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
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A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
- Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 7913 - 7919
(2017/08/14)
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- Microwave-Assisted Formylations of Weakly Basic Anilines with Methyl Formate Catalyzed by Calcium and Hydrogen Triflimides
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Catalytic amounts of calcium and hydrogen triflimides [Ca(NTf2)2, HNTf2] were found to be efficient for the solvent-free formylation of a variety of weakly basic anilines by using cheap and widely available methyl formate as the formylating agent under microwave irradiation. Initial investigations showed that in the case of calcium triflimide, Br?nsted acid catalysis was most likely operating. Remarkably, the corresponding calcium triflate and triflic acid were significantly less active.
- Tan, Eric,Ung, Sosthène,Corbet, Matthieu
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supporting information
p. 1836 - 1840
(2016/05/09)
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- Regiochemistry of nucleophilic substitution of pentachloropyridine with N and O bidentate nucleophiles
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Site reactivity of some enol-imines derived from N-aryl formamides with pentachloropyridine under basic conditions in dry CH3CN was investigated. The aromatic nucleophilic substitution of pentachloropyridine with enol-imines occurs at the 4-position of pyridine ring by both oxygen and nitrogen site of enol-imines. Nucleophilic attack by the oxygen of enol-imine gave corresponding oximino compounds as a mixture of E- and Z-isomers. In contrast, nucleophilic attack by the nitrogen of enol-imine gave the unexpected N,N-di-substituted aryl compounds. The structures of all the compounds were confirmed by IR, 1H NMR, 13C NMR and 19F NMR spectroscopy as well as elemental analysis and X-ray crystallography.
- Poorfreidoni, Alireza,Ranjbar-Karimi, Reza,Kia, Reza
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p. 4398 - 4406
(2015/06/16)
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- Synthesis of selenazolopyridine derivatives with capability to induce apoptosis in human breast carcinoma MCF-7 cells through scavenge of intracellular ROS
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A series of selenazolopyridine derivatives have been synthesized and characterized by X-ray diffraction, high resolution NMR and Mass spectrum. The in vitro anticancer activities of the synthetic compounds were screened against a panel of human cancer cell lines, human breast carcinoma MCF-7 cells, human liver carcinoma HepG2 cells and L02 normal cell line by MTT assay. By analyzing the structure-activity relationship among the synthetic compounds, it was found that 2-(phenylamino) selenazolo [5,4-b] pyridine, (PSeD, 7) had higher growth inhibitory effect on MCF-7 cells. The intracellular mechanism of cell death was evaluated by flow cytometric analysis and ROS assay, which revealed that PSeD could induce MCF-7 cells apoptosis by scavenging intracellular ROS. Taken together, we regard PSeD as an antioxidant which could inhibit cancer cell growth through induction of apoptosis.
- Zhou, Meiyun,Ji, Shengbin,Wu, Zhaojun,Li, Yiqun,Zheng, Wenjie,Zhou, Hua,Chen, Tianfeng
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- The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
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The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
- Desai, Salil Dileep,Kirsch, Lee E.
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p. 471 - 488
(2015/06/30)
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- FORMYLATION PROCESS FOR PREPARING AROMATIC FORMAMIDES
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The present invention mainly pertains to a catalytic process for preparing a formamide,comprising reacting a formic acid ester with an aromatic amine carrying at least one electron withdrawing group in the presence of a catalyst of fluorine-containing sulfonimide metal salt.
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Paragraph 0056-0058
(2016/04/26)
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- 1,4-AZABORINE COMPOUNDS AND METHODS OF SYNTHESIS
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A compound comprising a structure of formula A
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Page/Page column 57
(2014/01/17)
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- An eco-benign and highly efficient procedure for N-acylation catalyzed by heteropolyanion-based ionic liquids using carboxylic acid under solvent-free conditions
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An eco-benign and highly efficient route for N-acylation of amines has been developed by treating amines with corresponding carboxylic acids in the presence of 2 mol % of heteropolyanion-based ionic liquids as catalysts under solvent-free conditions. This practical reaction could tolerate a wide range of substrates. Thus, various N-acylation products including N-acyl α-amino acid derivatives were obtained in moderate to excellent yields at 70 C to 120 C. Moreover, recycling studies revealed that heteropolyanion-based ionic liquids were easily reusable for this N-acylation. This method provides a green and much improved protocol over the existing methods.
- Chen, Zhikai,Fu, Renzhong,Chai, Wen,Zheng, Hao,Sun, Lin,Lu, Qiang,Yuan, Rongxin
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p. 2237 - 2245
(2014/03/21)
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- Synthesis, structural characterization, and catalytic activity of flower like zno nanostructures
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Tageteserecta flower like zinc oxide nanostructures composed of hexagonal nanorods were synthesized via sonochemical method at room temperature. The synthesized nanomaterials exhibited wurtzite hexagonal phase structure with the single crystalline nature. The diameter of the individual nanorods that constitute the flower shaped zinc oxide structures is in the range of 120-160 nm. The sonication time effectively determined the morphological properties of the prepared materials. The catalytic activity of prepared zinc oxide nanostructures towards N-formylation reactions were evaluated without any surface modification and the nanostructures exhibited good reaction yield with the prompt recyclability behavior.
- Ramachandran,Gnana Kumar,Kim, Ae Rhan,Yoo, Dong Jin
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p. 1091 - 1097
(2014/05/06)
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- Highly efficient four-component synthesis of 4(3H)-quinazolinones: Palladium-catalyzed carbonylative coupling reactions
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Given the importance of quinazolinones and carbonylative transformations, a palladium-catalyzed fourcomponent carbonylative coupling system for the synthesis of diverse 4(3H)-quinazolinone in a concise and convergent fashion has been developed. Starting from 2-bromoanilines (1 mmol), trimethyl orthoformate (2 mmol), and amines (1.1 mmol), under 10 bar of CO, the desired products were isolated in good yields in the presence of Pd(OAc)2 (2 mol%), BuPAd2 (6 mol%) in 1,4-dioxane (2 mL) at 1008C, using N,Ndiisopropylethylamine (2 mmol) as the base. Notably, the process tolerates the presence of various reactive functional groups and is very selective for quinazolinones, and was used in the synthesis of the precursor to the bioactive dihydrorutaempine.
- He, Lin,Li, Haoquan,Neumann, Helfried,Beller, Matthias,Wu, Xiao-Feng
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p. 1420 - 1424
(2014/03/21)
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- Syntheses of 2-unsubstituted 1h-1,3-benzazaphospholes from n-formyl-2-bromoanilides
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The phosphonylation of 2-bromo-formylanilides 1 with triethyl phosphite in the presence of preformed Pd(0)(triethyl phosphite)n catalyst furnished 2-phosphono-formanilides 2 in good yields. Reduction with excess LiAlH4 provided mainl
- Ghalib, Mohammed,Niaz, Basit,Jones, Peter G.,Heinicke, Joachim W.
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p. 452 - 459
(2013/12/04)
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- Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
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A deep eutectic solvent was used as a dual catalyst and reaction medium for the efficient N-formylation of aromatic amines without hazardous organic solvent and catalyst. Treatment of aromatic amines with trimethyl orthoformate and formic acid in deep eutectic solvent at 70 °C gives the corresponding N-formyl derivatives in good to excellent yields. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and SnCl2, with 100% atom economy and making it applicable to industry and laboratory. Furthermore, heating the trimethyl orthoformate and aromatic primary amines in the deep eutectic solvent results in formation of the corresponding N,N'-diarylamidines in high yields.
- Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
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p. 768 - 773
(2012/10/30)
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- Photoinduced intramolecular cyclization of o -ethenylaryl isocyanides with organic disulfides mediated by diphenyl ditelluride
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Photoinduced reaction of o-ethenylaryl isocyanides with organic disulfides in the presence of diphenyl ditellurides affords the corresponding bisthiolated indole derivatives via a radical cyclization process. The cyclization can proceed at room temperature upon visible-light irradiation and exhibits good tolerance to functional groups. Several organic disulfides also can be employed for this cyclization, and the corresponding bisthiolated indole derivatives are obtained selectively. In addition, the photoinduced reaction of o-ethenylaryl isocyanides with bis(2-aminophenyl) disulfide affords tetracyclic compounds in one portion.
- Mitamura, Takenori,Iwata, Kimiyo,Ogawa, Akiya
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experimental part
p. 3880 - 3887
(2011/07/09)
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- Facile N-formylation of amines using Lewis acids as novel catalysts
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Alky, aryl, and heteroaryl amines were found to react efficiently with formic acid under Lewis acid catalysis giving N-formyl derivatives in high yields. A study of ZnCl2-catalyzed N-formylation of a variety of amines using formic acid as formylating agent is described.
- Chandra Shekhar,Ravi Kumar,Sathaiah,Luke Paul,Sridhar, Madabhushi,Shanthan Rao
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experimental part
p. 7099 - 7101
(2010/03/03)
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- ortho-Lithiophenyl isocyanide: A versatile precursor for 3H-quinazolin-4-ones and 3H-quinazolin-4-thiones
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(Chemical Equation Presented) ortho-Lithiophenyl isocyanide has been generated from ortho-bromophenyl isocyanide and successfully employed toward the synthesis of 2-substituted phenyl Isocyanides as well as 2,3-disubstituted 3H-quinazoline-4-ones and 3H-q
- Lygin, Alexander V.,De Meijere, Armin
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supporting information; experimental part
p. 389 - 392
(2009/09/05)
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- New carboxylic acid amides of the pyrrole series: Synthetic routes and biological aspects
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Complex II inhibitors play an important role in agrochemical fungicide research and have been known for more than 40 years. With the introduction of ortho-substituted heterocyclic amides, a breakthrough in activity level and spectrum within this class was achieved. In the meantime all major agrochemical companies have entered this field. In this paper, a special complex II subclass, the pyrrole carboxamides, will be introduced in more detail and the synthesis of selected compounds as well as a short biological SAR analysis of the pyrrole subclass will be discussed.
- Walter, Harald
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scheme or table
p. 351 - 362
(2009/01/31)
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- CRYSTAL AND SALT OF 1-CYCLOPROPYLMETHYL-4-Y2-(3,3,5,5)-TETRAMETHYLCYCLOHEXYL)PHENYL¨PIPERAZINE
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Salts and crystals of 1-cyclopropylmethyl-4-[2-(3,3,5,5-tetramethylcyclohexyl)phenyl]piperazine have excellent cell adhesion inhibitory action and cell infiltration inhibitory action, and are useful as therapeutic or prophylactic agents for various inflam
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- ZnO as a new catalyst for N-formylation of amines under solvent-free conditions
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The treatment of amines with formic acid in the presence of ZnO under solvent-free conditions brings about highly and efficient N-formylation to give the corresponding formamides in excellent yields. The N-formylation reaction not only involves mild conditions, simple operation, and high yields but also high chemoselectivity.
- Hosseini-Sarvari, Mona,Sharghi, Hashem
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p. 6652 - 6654
(2007/10/03)
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- CRYSTAL AND SALT OF 1-CYCLOPROPYLMETHYL-4-[2-(3,3,5,5)-TETRAMETHYLCYCLOHEXYL)PHENYL]PIPERAZINE
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A crystal and salt of 1-cyclopropylmethyl-4-[2-(3,3,5,5)-tetramethylcyclohexyl)phenyl]piperazine have excellent cellular adhesion inhibiting potency and cellular infiltration inhibiting potency. Therefore, these crystal and salt are useful as a preventive
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(2008/06/13)
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- INTERMEDIATE IN PRODUCTION OF [2-(3,3,5,5-TETRAMETHYLCYCLOHEXYL)PHENYL]PIPERAZINE COMPOUND
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A compound represented by the general formula below or a salt thereof is a useful intermediate in the production of a [2-(3,3,5,5-tetramethylcyclohexyl)phenyl]piperazine compound that has excellent cell adhesion inhibitory effect and cell invasion inhibitory effect and therefore is useful as a therapeutic or prophylactic agent for various inflammatory diseases and autoimmune diseases induced by the adhesion and invasion of leukocytes, such as inflammatory bowel diseases (particularly ulcerative colitis or Crohn's disease), irritable bowel syndrome, rheumatoid arthritis, psoriasis, multiple sclerosis, asthma and atopic dermatitis. [Chemical formulae] wherein R1 and R2 independently represent a hydrogen atom or an amino-protecting group for an amino group, or R1 and R2 may together form a pyrrole ring which may have a substituent.
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Page/Page column 24
(2008/06/13)
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