An efficient trifluoroacetic acid-mediated denitrogenative hydroxylation of 1,2,3-benzotriazin-4­(3H)-ones is described. This metal-free approach is compatible with a wide range of 1,2,3-benzotriazin-4­(3H)-ones, affording ortho-hydroxylated benzamides in good to high yields with a short reaction time. The reaction is believed to proceed via a benzene diazonium intermediate. The synthetic utility of the reaction was successfully demonstrated by the preparation of an antimicrobial drug, Riparin C, and benzoxazine-2,4­(3H)-diones in good yields.

Metal nanoparticles grafted within inert and porous wide-area supports are emerging as recyclable, sustainable catalysts for modern industry applications. Here, we bioengineered gold nanoparticle-based supported catalysts by utilizing the innate metal binding and reductive potential of eggshell as a sustainable strategy. Variable hand-recyclable wide-area three-dimensional catalysts between ∼80 ± 7 and 0.5 ± 0.1 cm2 are generated simply by controlling the size of the support. The catalyst possessed high-temperature stability (300 °C) and compatibility toward polar and nonpolar solvents, electrolytes, acids, and bases facilitating ultra-efficient catalysis of accordingly suspended substrates. Validation was done by large-volume (2.8 liters) dye detoxification, gram-scale hydrogenation of nitroarene, and the synthesis of propargylamine. Moreover, persistent recyclability, monitoring of reaction kinetics, and product intermediates are possible due to physical retrievability and interchangeability of the catalyst. Finally, the bionature of the support permits ∼76.9 ± 8% recovery of noble gold simply by immersing in a royal solution. Our naturally created, low-cost, scalable, hand-recyclable, and resilient supported mega-catalyst dwarfs most challenges for large-scale metal-based heterogeneous catalysis.

An efficient and straightforward approach to synthesize salicylanilide aryl and alkyl sulfonates from 1,2,3-benzotriazin-4(3H)-ones and organosulfonic acids is described. This protocol is operationally simple and scalable, exhibits a broad substrate scope with high functional group tolerance, and affords the desired products in good to high yield. Application of the reaction is also demonstrated by converting the desired product to synthetically useful salicylamides in high yields.