- Tri- and difluoromethoxylated N-based heterocycles ? Synthesis and insecticidal activity of novel F3CO- and F2HCO-analogues of Imidacloprid and Thiacloprid
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The preparation of F3CO- and F2HCO-analogues of Imidacloprid and Thiacloprid and the evaluation of their biological activity have been performed. For this purpose, a first synthetic approach allowed the preparation of a desired F3CO-containing key intermediate. To allow a facile access to the second F2HCO-containing key intermediate, the difluoromethylation of hydroxylated N-based heterocycles has been developed using difluoromethyl triflate (a liquid non-ODS reagent) under air in aqueous conditions and with very short reaction time. The broad diversity of compatible heterocycles includes a large series of substituted hydroxy-pyridines, but also ?pyrazoles, ?pyrazine, ?pyridazine, and ?quinolines. The couplings of both key intermediates with the required 4,5-dihydro-N-nitro-1H-imidazol-2-amine and [N(Z)]-N-2-thiazolidinylidene-cyanamide were successfully achieved using literature conditions. This work enables the preparation of valuable building blocks, which could lead to the discovery of new bioactive entities.
- Landelle, Gregory,Schmitt, Etienne,Panossian, Armen,Vors, Jean-Pierre,Pazenok, Sergiy,Jeschke, Peter,Gutbrod, Oliver,Leroux, Frédéric R.
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p. 155 - 165
(2017/09/07)
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- Decarboxylative Trifluoromethylating Reagent [Cu(O2CCF3)(phen)] and Difluorocarbene Precursor [Cu(phen)2][O2CCF2Cl]
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This article describes the new economic decarboxylative trifluoromethylating reagent [Cu(phen)(O2CCF3)] (1; phen=1,10-phenanthroline) and the efficient difluorocarbene precursor [Cu(phen)2][O2CCF2Cl] (2). Treatment of copper tert-butoxide with phen and subsequent addition of trifluoroacetic acid or chlorodifluoroacetic acid afforded air-stable complexes 1 and 2, respectively, which were characterized by X-ray crystallography. The copper(I) ion in 1 is coordinated by a bidentate phen ligand, a monodentate trifluoroacetate group, and a molecule of CH3CN in a distorted tetrahedral coordination geometry. The molecular structure of 2 adopts an ionic form that consists of a [Cu(phen)2]+ cation and a chlorodifluoroacetate anion. Complex 1 reacted with a variety of aryl and heteroaryl halides to form trifluoromethyl (hetero)arenes in good yields. The corresponding Hammett plot exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest-to-excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper-mediated formation of difluorocarbene and subsequent concerted addition of difluorocarbene to the phenol to form a three-center transition state.
- Lin, Xiaoxi,Hou, Chuanqi,Li, Haohong,Weng, Zhiqiang
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supporting information
p. 2075 - 2084
(2016/02/12)
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- Use of fluoroform as a source of difluorocarbene in the synthesis of N-CF2H heterocycles and difluoromethoxypyridines
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Fluoroform is used as a source of difluorocarbene to convert various N-, O-, and C-nucleophiles to their difluoromethylated derivatives. Imidazole, benzimidazole, benztriazole, hydroxypyridines, and their derivatives underwent reaction at moderate temperatures and atmospheric pressure, using potassium hydroxide as base in a two-phase (water/acetonitrile) process to provide moderate to good yields of the respective products. Nitrophenols required addition of a co-solvent (methanol) to obtain good yields of products.
- Thomoson, Charles S.,Wang, Linhua,Dolbier, William R.
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- Novel Heterocyclic Compounds and Uses Thereof
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New substituted heterocyclic compounds, compositions containing them, and methods of using them for the inhibition of Raf kinase activity are provided. The new compounds and compositions may be used either alone or in combination with at least one additional agent for the treatment of a Raf kinase mediated disorder, such as cancer.
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Paragraph 0414
(2013/08/28)
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- CHEMICAL COMPOUNDS
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PC71695A Abstract Chemical Compounds The invention relates to sulfonamide derivatives, to their use in medicine, to 5 compositions containing them, to processes for their preparation and to intermediates used in such processes. More particularly the invention relates to a new sulfonamide Nav1.7 inhibitors of formula (I):10 X NH O S O O R1 R2 R5 R4 R3 Het1 (I) or a pharmaceutically acceptable salt thereof, wherein X, Het1, R1, R2, R3, R4 and R5 are as defined in the description. 15 Nav 1.7 inhibitors are potentially useful in the treatment of a wide range of disorders, particularly pain.
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Page/Page column 107
(2012/02/02)
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- NOVEL HETEROCYCLIC COMPOUNDS AND USES THEROF
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New substituted heterocyclic compounds, compositions containing them, and methods of using them for the inhibition of Raf kinase activity are provided. The new compounds and compositions may be used either alone or in combination with at least one additional agent for the treatment of a Raf kinase mediated disorder, such as cancer.
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Page/Page column 125
(2009/10/22)
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