PROMOTING EFFECT OF PYRIDINE BASES ON INDIRECT ELECTROCHEMICAL OXIDATION OF ALCOHOLS

Abstract

The effect of pyridine on the reaction of indirect electrochemical oxidation of alcohols to carbonyl compounds by the catalytic system of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl - iodine in a two-phase aqueous-organic medium: methylene chloride - an aqueous solution of sodium bicarbonate (pH 8.6) was studed. It was shown that the process of indirect electrochemical oxidation of alcohols is accelerated by 1.5–2 times in the presence of pyridine. The corresponding aldehydes and ketones are formed with a high yield (75-95%) after passing 2-2.2 F of electricity. Additionally, the effect of other pyridine bases (2,6-lutidine, 4-acetylpyridine, 2-methyl-5-ethylpyridine, collidine) on indirect electrochemical oxidation of alcohols was studied using the example of 1-octanol. The absence of significant differences in the promoting action of pyridine bases was established and it was shown that in all cases the octanol is obtained with a high yield and coulombic efficiency (90-95 %). A mechanism for the reaction of indirect electrochemical oxidation of alcohols with the participation of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl and pyridine bases is proposed. The promoting effect of pyridine (or other pyridine bases) consists in the formation of an intermediate complex between the base, oxoammonium cation and alcohol. The formation of the complex facilitates the rapid transfer of the proton from the alcohol to the pyridine base and the hydride ion to the oxoammonium cation with the formation of the corresponding carbonyl compound from the alcohol. The preparative methods for the electrochemical synthesis of carbonyl compounds from aliphatic, cyclic, aromatic, heterocyclic alcohols including synthesis of 2,5-diformylfuran from 5-hydroxymethylfurfuralin using the two-phases catalytic system of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl - potassium iodide in the presence of pyridine bases, are proposed.