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The deoxydative substitution reactions of nicotinamide and nicotinic acid N ‐oxides by 1‐adamantanethiol in acetic anhydride
Author(s) -
Prachayasittikul Supaluk,
Bauer Ludwig
Publication year - 1985
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570220332
Subject(s) - chemistry , acetic anhydride , acetic acid , nicotinamide , pummerer rearrangement , organic chemistry , nicotinic agonist , yield (engineering) , medicinal chemistry , oxide , sulfide , hydrochloric acid , catalysis , biochemistry , materials science , receptor , metallurgy , enzyme
The reaction of nicotinamide N ‐oxide with 1‐adamantanethiol in acetic anhydride yielded a mixture of 2‐and 6‐(1‐adamantylthio)nicotinamides (49%, in the ratio of 24:1) and 2‐, 5‐, and 6‐(1‐adamantylthio)nicotino‐nitriles (18%, in the ratio of 79:1:20). From a reaction of nicotinic acid N ‐oxide with 1‐adamantanethiol, there was isolated 2‐(1‐adamantylthio)nicotinic acid as the only sulfide in 23% yield. Carbonsulfur bond cleavage took place when 2‐(1‐adamantylthio)nicotinic acid, or the corresponding amide or nitrile, were boiled with concentrated hydrochloric acid to furnish 2‐mercaptonicotinic acid and 1‐chloroadamantane, quantitatively. The reaction of nicotinamide N ‐oxide alone in acetic anhydride at 135° formed N ‐acetyl‐2‐hydroxynicotinamide (61%), 2‐hydroxynicotinonitrile (0.5%) and N,N ‐diacetyl‐2‐acetoxynicotinamide (0.8%).