4-Chloropyridine → 4-(Diallylamino)pyridine

Participants

Reaction Steps

4-Diallylaminopyridine was prepared by the condensation of 4-chloropyridine with diallylamine, as described by Mathias and Cei (Macromolecules, 1987, 20, 2645). This product was hydrosilylated with diethoxymethylsilane in the presence of chloroplatinic acid, as described by Rubinsztajn, et al, (Macromolecules, 1990, 23, 4026) to yield 4-bis(3'-diethoxymethylsilylpropyl)aminopyridine. Finally, following a procedure similar to that described by Tundo and Venturello (J. Amer. Chem. Soc., 1979, 101, 6606), this product (14.1 gm, 0.032 mol) was added to a 500 ml round bottom flask, equipped with a magnetic stirrer and a distillation head, containing 250 ml of toluene and 39.8 gm activated silica (Davison Grade 22, 60-200 mesh, 60 Angstrom, 500 m2 /gram BET surface area, 0.75 cm3 /gram pore volume). The mixture was stirred and heated to distill off about 125 ml of a toluene and ethanol solution over a period of about 3 hours. The resulting silica bound dialkylaminopyridine was separated from the reaction mixture by filtration, washed with three 100 ml portions of methanol and then finally washed with 100 mls of diethyl ether. After drying in a vacuum oven at 45° C. for 18 hours, the product was found to contain 0.6 meq aminopyridine/gram.

Provenance & Evidence