Halopyri dines

The rather classic catalyst palladium on activated carbon has been applied by Sun and Sowa et al. [183] and Heidenreich et al. [158] without additional ligands. This simple system was able to convert (mainly activated) aryl chlorides in mixtures of water and an organic solvent (DMA and NMP, respectively). Lysen et al. were able to convert aryl chlorides in pure water and without addition of any ligand [184,185]. Suzuki reactions using Pd/C in an aqueous medium were also reported by Arcadi et al. (in the presence of surfactants) [186] and the group of Leadbeater, who applied microwave techniques [187]. Microwave (as weU as ultrasound) conditions were also employed by Cravotto and Palmisano et al. [188] The substrate scope of Suzuki-type reactions in the presence of Pd/C was extended to halopyri-dines and haloquinoUnes by Tagata and Nishida [189]. 

P3o-idine-I-oxides are comparatively resistant to reduction because of resonance stabilization by the aromatic system. Typical reagents that have been used for the formation of pyridones and pyridinols are Raney Nickel in methanol, palladium-on-charcoal, phosphorous trichloride, or phosphorus oxychloride in ethyl acetate. The N-oxides of pyridoxine, pyridoxal, and pyridoxamine have been deoxygenated catalytically. 4-Alkoxy-3-halopyri-dine-1-oxides are A-deoxygenated by phosphorous trichloride in chloroform. 2-Amino-3-pyridinol can be prepared ffom2-nitro-3-pyridinol-l-oxide (X1I450) in acetic acid by treatment with iron and mercuric chloride and then with zinc. 2-Halo-3-pyridinols can be prepared from XII-450 by treatment with phosphorous trihalides in chlorofiMm ... 

Ammonodehalogenation, amino-pyridines from halopyri-dines, 46... 

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