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Studies on Tertiary Amine Oxides. LXXXI. Formation of 1-Isoquinolinio-methylides by the reaction of Isoquinoline 2-Oxide with Cyanoacetic Acid and Benzoylacetonitrile in the Presence of Acetic Anhydride
Funakoshi, Kazuhisa,Inada, Haruaki,Hamana, Masatomo
, p. 4731 - 4739 (2007/10/02)
Isoquinoline 2-oxide (1) reacts with cyanoacetic acid in the presence of Ac2O to afford various types of 1-substituted isoquinolines (2, 4, 6, and 7) and N-ylides (3 and 5a) depending upon the reaction conditions and processing procedures (Table I).The reaction in Ac2O gives initially α-acetoxycarbonyl-1-isoquinolineacetonitrile (2) and 2-isoquinolinio-acetoxycarbonylcyanomethylide (3), and that in Ac2O-dimethylformamide yields only 3.Products 2 and 3 are readily convertible into α-acetyl-1-isoquinolineacetonitrile (4) and 2-isoquinolinio-acetylcyanomethylide (5a), respectively, by processing involving heating.The reaction in ethanol gives ethyl α-cyano-1-isoquinolineacetate (6) and di(1-isoquinolyl)acetonitrile (7).The reaction of 1 with benzoylacetonitrile affords both the corresponding 1-substituted isoquinoline (10) and N-ylide (11).Reactions with ethyl benzoylacetate and, methyl and ethyl acetoacetates produce 1-substituted isoquinolines (12 and 14a, b) and 4-acetoxyisoquinoline (13), no ylide being formed.Keywords - isoquinoline 2-oxide; nucleophilic reaction; decarboxylative acyl migration; α-acetoxycarbonyl-1-isoquinolineacetonitrile; α-acetyl-1-isoquinolineacetonitrile; ethyl α-cyano-1-isoquinolineacetate; α-benzoyl-1-isoquinolineacetonitrile; 2-isoquinolinio-acetoxycarbonylcyanomethylide; 2-isoquinolinio-acetylcyanomethylide; 2-isoquinolinio-benzoylcyanomethylide.
