- SEQUENCE OF REPLACEMENT OF HYDROGEN IN 2,6-DIMETHYLPYRIDINE BY LITHIUM OR HALOGEN
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It is shown that, according to the results of chromatographic mass spectrometry, the reaction of 2,6-dimethylpyridine with phenyllithium leads only to the monolithium derivative.The chlorination and bromination of 2,6-dimethylpyridine with various reagents were studied systematically.A method for the conversion of 2,6-bis(chloromethyl)pyridine to 2,6-bis(hydroxymethyl)pyridine is given.
- Karpman, Ya.S.,Azimov, V.A.,Anisimova, O.S.,Yakhontov, L.N.
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- IMPROVED PROCEDURES FOR PREPARATION OF 2-PYRIDONES AND 2-HYDROXYMETHYLPYRIDINES FROM PYRIDINE N-OXIDES
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2-Pyridones and 2-hydroxymethylpyridines were prepared from pyridine N-oxides by treatment with trifluoroacetic anhydride in dimethylformamide.The reaction proceeds at room temperature in satisfactory yields.
- Konno, Katsuhiro,Hashimoto, Kimiko,Shirahama, Haruhisa,Matsumoto, Takeshi
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- Creatinine recognition using designed synthetic receptors
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A series of neutral nonenzymatic receptors have been synthesized for the recognition of creatinine in a nondegrative way. The receptors contain different heterocyclic moieties for better interactions between host and guest. Among these, 1, 4, and 5 are fluorescent receptors for creatinine. From this study, it was found that the receptors 1 and 4 containing the naphthyridine moiety have higher binding affinity to the guest creatinine than receptors containing other heterocyclic moiety. Theoretical studies for the calculation of binding energy were carried out using discrete Fourier transform (DFT) for the hosts and their complexation with creatinine in both gas phase and acetonitrile medium.
- Jana, Subrata,Prajapati, Sunita,Suryavanshi, Kishor Kumar,Goswami, Shyamaprosad,Parida, Rakesh,Giri, Santanab
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- ANALOGS OF 2-PRALIDOXIME AS ANTIDOTES AGAINST ORGANOPHOSPHORUS NERVE AGENTS
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Provided herein are compounds useful in treating exposure to an organophosphorus compound, such as a nerve agent, pesticide, or, generally, an acetylcholinesterase inhibitor, such as sarin. Compositions, e.g. pharmaceutical compositions or dosage forms, comprising the compounds also are provided herein. Methods of treating a patient exposed to a nerve agent, pesticide, or, generally, an acetylcholinesterase inhibitor, e.g., an organophosphorus compound, such as sarin, also are provided.
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- Methyl Scanning and Revised Binding Mode of 2-Pralidoxime, an Antidote for Nerve Agent Poisoning
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Organophosphorus nerve agents (OPNAs) inhibit acetylcholinesterase (AChE) and, despite the Chemical Weapons Convention arms control treaty, continue to represent a threat to both military personnel and civilians. 2-Pralidoxime (2-PAM) is currently the only therapeutic countermeasure approved by the United States Food and Drug Administration for treating OPNA poisoning. However, 2-PAM is not centrally active due to its hydrophilicity and resulting poor blood-brain barrier permeability; hence, these deficiencies warrant the development of more hydrophobic analogs. Specifically, gaps exist in previously published structure activity relationship (SAR) studies for 2-PAM, thereby making it difficult to rationally design novel analogs that are concomitantly more permeable and more efficacious. In this study, we methodically performed a methyl scan on the core pyridinium of 2-PAM to identify ring positions that could tolerate both additional steric bulk and hydrophobicity. Subsequently, SAR-guided molecular docking was used to rationalize hydropathically feasible binding modes for 2-PAM and the reported derivatives. Overall, the data presented herein provide new insights that may facilitate the rational design of more efficacious 2-PAM analogs.
- Gambino, Adriana,Burnett, James C.,Koide, Kazunori
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p. 1893 - 1898
(2020/02/06)
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- Photochemical C-H Silylation and Hydroxymethylation of Pyridines and Related Structures: Synthetic Scope and Mechanisms
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Considering the synthetic relevance of heteroarenes in various areas ranging from organic synthesis to medicinal chemistry, developing practically simple methodologies to access functionalized heteroarenes is of a significant value. Described herein is an efficient approach for C-H silylation and hydroxymethylation of pyridines and related heterocycles by the combination of silanes or methanol with readily available N-methoxypyridinium ions with a low catalyst loading (2 mol %) under blue light irradiation. The synthetic importance of the developed reactions is demonstrated by the synthesis of biologically relevant compounds. Electron paramagnetic resonance spectroscopy, quantum yield measurements, and density-functional theory calculations allowed us to understand reaction mechanisms of both photocatalytic reactions.
- Rammal, Fatima,Gao, Di,Boujnah, Sondes,Hussein, Aqeel A.,Lalevée, Jacques,Gaumont, Annie-Claude,Morlet-Savary, Fabrice,Lakhdar, Sami
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p. 13710 - 13717
(2020/11/30)
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- Palladium aminopyridine complexes catalyzed selective benzylic C-H oxidations with peracetic acid
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Four palladium(ii) complexes with tripodal ligands of the tpa family (tpa = tris(2-pyridylmethyl)amine) have been synthesized and X-ray characterized. These complexes efficiently catalyze benzylic C-H oxidation of various substrates with peracetic acid, affording the corresponding ketones in high yields (up to 100%), at 1 mol% catalyst loadings. Complex [(tpa)Pd(OAc)](PF6) with the least sterically demanding ligand tpa demonstrates the highest substrate conversions and ketone selectivities. Preliminary mechanistic data provide evidence in favor of metal complex-mediated rate-limiting benzylic C-H bond cleavage by an electron-deficient oxidant.
- Bryliakov, Konstantin P.,Lubov, Dmitry P.,Lyakin, Oleg Yu.,Rybalova, Tatyana V.,Samsonenko, Denis G.,Talsi, Evgenii P.
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supporting information
p. 11150 - 11156
(2020/09/02)
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- Methanol as hydrogen source: Transfer hydrogenation of aromatic aldehydes with a rhodacycle
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A cyclometalated rhodium complex has been shown to perform highly selective and efficient reduction of aldehydes, deriving the hydrogen from methanol. With methanol as both the solvent and hydrogen donor under mild conditions and an open atmosphere, a wide range of aromatic aldehydes were reduced to the corresponding alcohols, without affecting other functional groups.
- Aboo, Ahmed H.,Bennett, Elliot L.,Deeprose, Mark,Robertson, Craig M.,Iggo, Jonathan A.,Xiao, Jianliang
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supporting information
p. 11805 - 11808
(2018/11/10)
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- A 6 - methyl - 2 - pyridyl methanol preparation method
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The invention discloses a preparation method of 6-methyl-2-pyridyl methanol and belongs to the field of organic chemical synthesis, solving the problems of poor selectivity, abundant byproducts, low yield and environment pollution in the prior art. The preparation method of 6-methyl-2-pyridyl methanol comprises the following steps: carrying out high-selectivity oxidization on 2,6-dimethyl pyridine based on 2,6-dimethyl pyridine and glacial acetic acid which serve as raw materials in the presence of tungsten oxide and hydrogen peroxide which serve as catalysts, introducing an acetyl group into an alpha position of a pyridine ring, then carrying out alpha-carbon electronic transfer rearrangement to generate 6-methyl-2-pyridyl ethyl formate, subsequently carrying out hydrolysis to generate 6-methyl-2-pyridyl methanol, then carrying out extraction and distillation to obtain high-purity 6-methyl-2-pyridyl methanol. The preparation method of 6-methyl-2-pyridyl methanol can fully accord with the synthesis requirements of medical manufacturing enterprises, has the advantages of high selectivity, few byproducts, high product yield and low production cost, is mild in reaction conditions and is suitable for industrial production.
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- Effect of substituent in pyridine-2-carbaldehydes on their heterocyclization to 1,2,4-triazines and 1,2,4-triazine 4-oxides
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A series of substituted pyridine-2-carbaldehydes were brought into heterocyclization with isonitrosoacetophenone hydrazones, followed by aromatization by the action of oxidants or by dehydration in boiling acetic acid. As a result, substituted 3-(pyridin-2-yl)-1,2,4-triazines or 3-(pyridin-2-yl)-1,2,4-triazine 4-oxides were formed. 6-Formylpyridine-2-carbonitrile failed to undergo heterocyclization, 6-methylpyridine-2-carbaldehyde and methyl 6-formylpyridine-3-carboxylate can be converted to both 1,2,4-triazine and 1,2,4-triazine 4-oxide derivative, and only 1,2,4-triazine 4 oxides were obtained from 6-bromopyridine-2-carbaldehyde and 6-formyl-3-phenylpyridine-2-carbonitrile. Convenient procedures were proposed for the synthesis of some initial pyridinecarbaldehydes.
- Krinochkin,Kopchuk,Chepchugov,Kovalev,Zyryanov,Rusinov,Chupakhin
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p. 963 - 970
(2017/09/07)
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- METHOD FOR PRODUCING ORGANIC COMPOUND
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PROBLEM TO BE SOLVED: To provide a method of subjecting a compound having on one carbon atom a carbon atom constituting a carbon-carbon double bond and a functional group such as a hydroxyl group to a reductive reaction condition and producing an organic compound having the functional group substituted with a hydrogen atom. SOLUTION: There is provided a method for producing a compound represented by a formula (50) from a raw material compound represented by a formula (10). The method includes a step of irradiating a reaction system with light, the reaction system comprising the raw material compound, a hydrogen source compound, and a catalyst having a palladium component supported by a carrier containing titanium oxide. (R11 to R15 are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a cyclic structure or a derivative group thereof, or a heteroatom-containing group having 1 to 20 carbon atoms which may have a cyclic structure or a derivative group thereof; and R16 is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or an acyl group having 1 to 20 carbon atoms which may have a cyclic structure, or -CH(CH2OH)2).) COPYRIGHT: (C)2015,JPO&INPIT
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Paragraph 0084-0087; 0097; 0129; 0133; 0138
(2018/10/16)
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- Iridium-catalyzed direct dehydroxylation of alcohols
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Iridium-catalyzed direct dehydroxylation of alcohols with hydrazine was developed through a combination of the oxidation of alcohols and the Wolff-Kishner reduction. This protocol is simple to perform and highly efficient for a series of primary, benzylic and allylic alcohols. Iridium-catalyzed direct dehydroxylation of alcohols with hydrazine is developed through a combination of the oxidation of alcohols and Wolff-Kishner reduction. This protocol is simple to perform and highly efficient for a series of primary alcohols, especially benzylic and allylic ones. Copyright
- Huang, Jian-Lin,Dai, Xi-Jie,Li, Chao-Jun
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supporting information
p. 6496 - 6500
(2013/11/06)
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- Total synthesis of (±)-monomorine
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An efficient, two-operation synthesis of the trail ant pheromone (±)-monomorine is reported. The synthesis features an aqueous Claisen-Schmidt condensation followed by the stereocontrolled installation of the three resident stereocenters in a single operation.
- Le, Tri Q.,Oliver III, Robert M.,Arcari, Joel T.,Mitton-Fry, Mark J.
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p. 5660 - 5662
(2012/11/07)
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- Substituted triazolo-pyridazine derivatives as ligands for GABA receptors
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Substituted triazolo-pyridazine derivative compounds represented by wherein the variables are disclosed herein are selective ligands for GABA-A receptors, particularly for the α2 and/or α3 subunits.
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- 2--1H-thienoimidazoles. A Novel Class of Gastric H+/K+-ATPase Inhibitors
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2-thienoimidazoles were synthesized and investigated as potential inhibitors of gastric H+/K+-ATPase.The isomers of the two possible thienoimidazole series were found to be potent inhibitors of gastric acid secretion in vitro and in vivo.Structure-activity relationships indicate that especially lipophilic alkoxy, benzyloxy, and phenoxy substituents with additional electron-demanding properties in the 4-position of the pyridine moiety combined with an unsubstituted thienoimidazole lead to highly active compounds with a favorable chemical stability.Various substitution patterns in the thienoimidazole moiety result in lower biological activity.The heptafluorobutyloxy derivative saviprazole (HOE 731, 5d) was selected for further development and is currently undergoing clinical evaluation.Comprehensive pharmacological studies indicate a pharmacodynamic profile different to omeprazole, the first H+/K+-ATPase blocker introduced on the market.
- Weidmann, Klaus,Herling, Andreas W.,Lang, Hans-Jochen,Scheunemann, Karl-Heinz,Rippel, Robert,et al.
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p. 438 - 450
(2007/10/02)
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- AN IMPROVED METHOD FOR THE MONO-HYDROXYMETHYLATION OF PYRIDINES. A MODIFICATION OF THE MINISCI PROCEDURE
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The reaction of N-methoxy-derivatives of pyridines in methanol with ammonium persulphate gives improved yields of mono-hydroxymethylated products.In contrast to the original Minisci procedure the reaction requires only catalytic amounts of ammonium persulphate.Evidence is presented which establishes that the reaction does not proceed via an intramolecular pathway.
- Katz, R B,Mistry, J,Mitchell, M B
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p. 317 - 326
(2007/10/02)
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- 6-(SUBSTITUTED)METHYLENE-PENICILLANIC AND 6-(SUBSTITUTED)HYDROXYMETHYL-PENICILLANIC ACIDS AND DERIVATIVES THEREOF
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Beta-lactamase inhibiting compounds of the formula: or a pharmaceutically acceptable acid addition or carboxylate salt thereof; where n is zero, 1 or 2; X.3 is H or Br, R1 is H, the residue of certain carboxy-protecting groups or the residue of an ester group readily hydrolyzable in vivo; one of R12 and R13 is H and the other is vinyl, certain aryl, alkylthio, alkylsulfonyl or certain heterocyclyl, aminomethyl, thiocarboxamido or amidino groups; one or R2 and R3 is H and the other is as disclosed for the other of R12 and R13, or is Cl or CH2 OH, and R18 is H or certain acyl groups; intermediates useful in their production, methods for their preparation and use, and pharmaceutical compositions containing them
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- Triazolopyridines. Part 6. Ring Opening Reactions of Triazolopyridines
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The triazole ring in 1,2,3-triazolo-pyridines and -quinolines, and in 1,2,3-triazoloisoquinolines can be opened with loss of nitrogen.The reagents described are bromine, aqueous sulphuric acid, glacial acetic acid, and selenium dioxide; the products from the triazolopyridines are dibromomethyl, hydroxymethyl, acetoxymethyl, and acyl derivatives of pyridine.The generality of the reactions is discussed.The first reported reaction in which the six-membered ring of a 1,2,3-triazolopyridine is opened, by hydride reduction, gives a triazolylbutadiene.
- Jones, Gurnos,Mouat, Deborah J.,Tonkinson, Daryl J.
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p. 2719 - 2724
(2007/10/02)
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