- An atom economical method for the direct synthesis of quinoline derivatives from substituted o-nitrotoluenes
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A highly efficient one-pot procedure for the preparation of substituted quinolines from substituted o-nitrotoluenes with electron-withdrawing groups and olefins (acrylic esters and acrylonitriles) using a cesium catalyst has been developed. A plausible [2+4] cycloaddition mechanism is proposed. This method uses nitroaromatic compounds as the starting materials to give quinoline derivatives in good to high yields under mild conditions with no transition metal catalysis. It provides an atom economical pathway for the synthesis of quinoline derivatives which could be used in industrial processes.
- Liu, Guiyan,Yi, Maocong,Liu, Lu,Wang, Jingjing,Wang, Jianhui
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p. 2911 - 2914
(2015/02/19)
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- An NMR study on a pseudo-intramolecular transacylation reaction of an α-aryl-β-keto ester
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The pseudo-intramolecular transacylation reaction efficiently proceeds like an intramolecular reaction, even though it is actually an intermolecular reaction. We have obtained valuable insights by monitoring the reaction by 1H NMR spectroscopy.
- Hirai, Sho,Asahara, Haruyasu,Hirao, Shotaro,Sawayama, Jun,Sugimoto, Ryuichi,Saigo, Kazuhiko,Nishiwaki, Nagatoshi
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p. 4889 - 4892
(2014/01/23)
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- Transition-metal-free formal sonogashira coupling and α-carbonyl arylation reactions
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Transition-metal-free formal Sonogashira coupling and α-carbonyl arylation reactions have been developed. These transformations are based on the nucleophilic aromatic substitution (SNAr) of β-carbonyl sulfones to electron-deficient aryl fluorides, producing a key intermediate that, depending on the reaction conditions, gives the aromatic alkynes or α-aryl carbonyl compounds. The development of these reactions is presented and, based on investigations under basic and acidic conditions, mechanisms have been proposed. To develop the formal disclosed that expands the reaction concept. The scope of these reactions is demonstrated for the synthesis of Sonogashira and α-carbonyl arylated products from a range of electron-deficient aryl fluorides with a variety of functional groups and aryl-, heteroaryl-, alkyl-, and alkoxy-substituted sulfone nucleophiles. These transition-metal-free reactions complement the metal-catalyzed versions in terms of substitution patterns, simplicity, and reaction conditions.
- Prueger, Birgit,Hofmeister, Gretchen E.,Jacobsen, Christian Borch,Alberg, David G.,Nielsen, Martin,Jorgensen, Karl Anker
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supporting information; experimental part
p. 3783 - 3790
(2010/07/13)
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- Indazoles, benzothiazoles, benzoisothiazoles, benzisoxazoles, pyrazolopyridines, isothiazolopyridines, and preparation and uses thereof
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The present invention relates generally to the field of ligands for nicotinic acetylcholine receptors (nACh receptors), activation of nACh receptors, and the treatment of disease conditions associated with defective or malfunctioning nicotinic acetylcholine receptors, especially of the brain. Further, this invention relates to novel compounds (e.g., indazoles and benzothiazoles), which act as ligands for the α7 nACh receptor subtype, methods of preparing such compounds, compositions containing such compounds, and methods of use thereof.
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Page/Page column 72
(2010/11/26)
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- Six membered amino-amide derivatives an angiogenisis inhibitors
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The present invention relates to six membered amino-amide derivatives, processes for their preparation, pharmaceutical compositions containing them as active ingredient, methods for the treatment of disease states associated with angiogenesis and/or increased vascular permeability, to their use as medicaments and to their use in the manufacture of medicaments for use in the production of antiangiogenic and/or vascular permeability reducing effects in warm-blooded animals such as humans.
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- Decomposition of alkene adducts of thianthrene cation radical in nitrile solvents. Formation of alkyl-2-oxazolines and a new class of four-component products: 5-[(1-alkoxyalkylidene) ammonio]alkylthianthrenium diperchlorates
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The monoadducts (4a-d) of thianthrene cation radical perchlorate (1a) and isobutene, 2-methyl-butene, 2-methyl-2-butene, and 2-methylpentene decompose spontaneously in acetonitrile (MeCN) solution, with the formation of thianthrene (Th). Decomposition of 4a (1,2-(5,10-thianthreniumdiyl)-2-methylpropane diperchlorate) and 4a', the corresponding dihexafluorophosphate, was studied in depth and extensively with 1H and 13C NMR spectroscopy. Decomposition of 4a was found to involve the solvent itself as well as water in the solvent, remaining from incomplete drying, and gave, apart from Th, successively, the perchlorate salts of 2,4,4-trimethyl-2-oxazoline (6) and 2-amino-2-methylpropyl acetate (7). These salts, 6-HCIO4 and 7-HCIO4, respectively, were prepared and used in understanding the reactions of 4a as well as the relationships among 6, 7, and 2-(acetylamino)-2-methyl propanol (8) in acidified MeCN solution. Decompositions of 4a-d in MeCN and other nitriles (RCN) containing an added alcohol (ROH) led to new products, 5-[(1-alkoxyalkylidene)ammonio]alkylthianthrenium diperchlorates (5a-u). These compounds were identified with 1H and 13C NMR spectroscopy and, in part, with X-ray crystallography and elemental analysis. The mechanisms of formation of 5-7 are discussed.
- Shine, Henry J.,Zhao, Bing-Jun,Marx, John N.,Ould-Ely, Teyeb,Whitmire, Kenton H.
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p. 9255 - 9261
(2007/10/03)
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- Reactions of Nitroarenes with Secondary and Tertiary Carbanions Bearing Both a Leaving Group and Electron-Withdrawing Group: An Approach to Dihydronaphth[2,1-c]isoxazole N-oxides and Dihydroisoxazolo[4,3-f]quinoline N-oxides
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2-Nitronaphthalene (1) and 6-nitroquinoline (2) underwent direct cyclocondensation with secondary and tertiary carbanions derived from a methylene and methine group bearing both a leaving group and electron-withdrawing group (e.g., methyl chloroacetate, ethyl chloroacetate, chloroacetonitrile, methyl 2-chloropropionate, ethyl 2-chloropropionate and 2-chloropropionitrile) in the sodium hydride/N,N-dimethylformamide system at low temperature, giving the corresponding dihydronaphth[2,1-c]isoxazole N-oxides 3 and dihydroisoxazolo[4,3-f]quinoline N-oxides 4. On the other hand, nitroarenes 1 and 2 reacted with secondary carbanions in the sodium hydride/tetrahydrofuran system to yield the corresponding conventional vicarious nucleophilic substitution (VNS) products 5 and 6.
- Maruoka, Hiroshi,Tomioka, Yukihiko
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p. 1051 - 1057
(2007/10/03)
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- Transacylation of α-Aryl-β-keto Esters
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The acyl group of an α-aryl-β-keto ester was readily transferred to N-, O-, and S-nucleophiles. The transacylation from arylated diethyl 3-oxoglutarate to amines led to unsymmetrical malonic acid amide esters in high yields. The present reaction proceeded under mild conditions without formation of detectable byproducts. Only simple experimental manipulations were required. This reaction was also found to be sensitive to steric factors, which enabled the chemoselective monoacylation of diamines and amino alcohols without any modifications such as protection.
- Nishiwaki, Nagatoshi,Nishida, Daisei,Ohnishi, Tetsuya,Hidaka, Fumie,Shimizu, Satoru,Tamura, Mina,Hori, Kazushige,Tohda, Yasuo,Ariga, Masahiro
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p. 8650 - 8656
(2007/10/03)
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- Direct coupling of carbon nucleophiles with m-dinitrobenzene: A novel fluoride promoted nucleophilic aromatic photosubstitution for hydrogen
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Useful yields are achieved in the C-arylation of ketones, nitriles and esters through direct hydrogen nucleophilic aromatic photosubstitution of m-dinitrobenzene, promoted by fluoride anion.
- Cervera, Maria,Marquet, Jordi
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p. 7591 - 7594
(2007/10/03)
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- Synthesis of 2-(2,6-dinitrophenyl)malonates, -acetates and acetonitrile by copper-mediated vicarious nucleophilic substitution
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A regioselective, vicarious nucleophilic substitution of 1,3- dinitrobenzene with α-bromo- and iodocarbanions proceeds in the presence of copper(1) tert-butoxide and pyridine giving 2,6-dinitrophenylmalonates, 2,6- dinitrophenylacetates or 2,6-dinitrophenylacetonitrile as the only isomers from bromomalonate esters, bromoacetate esters, iodoacetate esters or iodoacetonitrile, respectively. Without copper(I) tert-butoxide, the 4- substituted isomer is the only product. We believe that the reaction proceeds via a σ-adduct of 1,3-dinitrobenzene and halocarbanion from which hydrogen and halogen are eliminated. This elimination is dependent upon the concentration of copper(I) tert-butoxide.
- Haglund,Nilsson
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p. 242 - 243
(2007/10/02)
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- Substituted indolinones useful as herbicidal agents
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Substituted indolinone compounds which are effective in the control of undesirable plant species are described. Also described are a method for the herbicidal use of the compounds and a method for their preparation.
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