8-Aminoquinoline (AQ) is a widely used bidentate auxiliary in metal-catalyzed directed C−H functionalization reactions. Herein, we report an efficient and chemoselective method to convert various N-quinolyl carboxamides to primary amides with the treatment of a stoichiometric amount of 2-iodoxybenzoic acid oxidant or the combination of a catalytic amount of 2-iodobenzoic acid and Oxone co-oxidant in mixed solvents of H 2 O and HFIP. Its unique compatibility with the Phth-protected α-amino acid (αAA) substrates enhances the overall synthetic utility of the AQ-directed palladium-catalyzed C−H functionalization strategy for synthesis of complex αAAs.Recently, we demonstrated that reactions of N-aryl carboxamides featuring relatively electron-rich arenes with IBX in hexafluoro-2-propanol (HFIP) and water at room temperature undergo C(aryl)−N cleavage to give primary amides in good yield and selectivity. 8 Notably, the mechanism of the C(aryl)−
The solubility of florfenicol form A in eight pure organic solvents (propionic acid, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-methyl-1-propanol, 3-methyl-1-butanol, and 2-ethyl-1-hexanol) and three binary solvents (dimethyl sulfoxide + ethanol, dimethyl sulfoxide + 1-propanol, and dimethyl sulfoxide + 1-butanol) was measured by a laser dynamic method at temperature from 283.15 to 323.15 K. The experimental results show that the mole fraction solubility of florfenicol in the pure solvents decreased according to the following order: ethanolThe experimental results show that the mole fraction solubility of florfenicol form A in the binary solvents increased with the increase of temperature and dimethyl sulfoxide mass fraction. The experimental solubility data were well correlated with the four thermodynamic models: modified Apelblat equation, λh equation, NRTL model equation, and Wilson model equation. The modified Apelblat model equation was regarded as the best one to fit the experimental values in the pure solvents.
A highly selective, IBX-promoted reaction has been developed for the oxidative cleavage of inert C(aryl)-N bonds on secondary amides while leaving the C(carbonyl)-N bond unchanged. This metal-free reaction proceeds under mild conditions (HFIP/HO, 25 °C), providing facile access to various useful primary amides, some of which would be otherwise unattainable using conventional aminolysis and hydrolysis approaches.
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