Nitration of methyl salicylate was performed by ferric nitrate in refluxing ethyl acetate solution. A coordination-mediated radical nitration process was proposed based on the results of electronic absorption spectra, cyclic voltammetry and electrospray ionization mass spectra. It was the coordination of methyl salicylate with ferric nitrate that promoted the splitting of NO bonds of nitrate group in ferric nitrate and resulted in the formation of nitro radicals, oxygen radicals and complex radicals. The nitro radicals reacted with methyl salicylate or its complexes with iron to give a series of nitration products and Fe(II) ions. Meanwhile, oxygen radicals hydrolyzed to hydroxide which precipitated free ferric ions to isolate solid ferric oxides.
One-pot synthesis of azide-substituted dihydropyrazoles in isopropanol was performed using chalcones, hydrazine hydrate, and acyl chloride at 0℃, and its subsequent Staudinger-aza-Wittig-dehydroaromatization reactions with methyldiphenylphosphine were also investigated for further application in the construction of pyrazolo[1,5-c]quinazolines.
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