Transformation of 2-(Hydroxymethyl)-5-(aminomethyl)-furan into 6-Methyl-3-pyridinol.

Abstract

cf. C.A. 49, 10948g; 50, 3385e. 5-(Hydroxymethyl)furfural (12.8 g.) shaken 1 hr. at 65-75°/100 atm. with 30 ml. MeOH, 5 ml. liquid NH3, and 0.4 g. Raney Ni gave 72% 2-(hydroxymethyl)-5-(aminomethyl)furan (I), pale yellow liquid, b0.1 102-5°, n25D 1.5278 [HCl salt, m. 118-21° (cor.)], characterized after electrolytic methoxylation of its diacetate, m. 65-7° (Et2O), alk. hydrolysis of the product, and HCl treatment as 6-(hydroxymethyl)-3-pyridinol, light brown crystals, m. 123-5°, 74% yield. I refluxed 15 hrs. with N HCl gave 88% 6-methyl-3-pyridinol, light brown crystals, m. 168-70°; picrate, m. 205-8° (decompn.). [on SciFinder(R)]