Premium
Meerwein arylation of methyleneglutaronitrile with anthraquinone diazonium hydrogensulfate. Synthesis of an enolizable benzanthrone lactone
Author(s) -
Sutter P.,
Weis C. D.
Publication year - 1987
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.5570240115
Subject(s) - chemistry , anthraquinone , hydrazone , lactone , derivative (finance) , organic chemistry , nitrile , catalysis , medicinal chemistry , economics , financial economics
The Meerwein reaction of 1‐anthraquinone diazonium hydrogensulfate with 2‐methyleneglutaronitrile in methanol yielded predominantly 3‐hydroxy‐4‐(1‐anthraquinone)‐1,3‐butanedicarbonitrile ( 5 ), while the corresponding 2‐methyleneglutaric acid diethyl ester furnished a derivative of 1‐(anthraquinone)butanolide 10. Catalytic dehydrocyanation of 5 was effected with Dowex‐50 to furnish 3‐oxo‐4‐(anthraquinone)butanecarbo‐nitrile ( 6 ). Both nitriles 5,6 gave in a double cyclization reaction a benzanthrone lactone 12 from which a crystalline derivative of the enol form was isolated, the structure of which was elucidated by 1 H‐ and 13 C‐nmr spectra. The methylene group of the lactone ring underwent coupling reactions with aromatic diazonium salts to form hydrazone derivatives.