6-Methoxy-2-oxo-1,2-dihydroquinoline-3,4-dicarbonitriles, A Red Compound Class with Solvent and pH Independent Green Fluorescence Maxima

摘要

The sodium p-toluenesulfinate mediated reaction of potassium cyanide with 4-chlorocarbostyrils 8, 16, 18, and 23 gave in all cases the highly fluorescent and stable 6-methoxy-2-oxoquinoline-3,4-dicarbonitrile 9 (λ_(exc) 460 nm and λ_(em) 545 nm). This is remarkable, because starting carbostyrils 8, 16, 18, and 23 had a chloro substituent, a nitro substituent, an acetylamino substituent, or a piperidinyl substituent in position 3. Hence, we observed not only a substitution of the 4-chloro and expected 3-chloro substituents by the cyanide nucleophile but also an exchange of a nitro substituent, an acetylamino substituent, and a piperidinyl substituent in position 3. The multistep insertion of substituents leading to 8, 16, 18, and 23 started from 4-hydroxy-6-methoxyquinolone 4, easily obtained from p-anisidine and malonic acid. Substitutions in position 3 gave 4-hydroxy-3-nitro and 3-chloro intermediates, which were converted to 3,4-dichlorocarbostyril 8 and 4-chloro-3-nitrocarbostyril 16. Reduction of the 3-nitro intermediate led to the 3-acetylamino analog and subsequent chlorination led to 3-acetylamino-4-chlorocarbostyril 18. 4-Chloro-3-piperidinylcarbostyril 23 was obtained from intermediate 3,3-dichloroquinolinedione by subsequent amination, reduction and chlorination. Further, 3-acetylamino-4-chlorocarbostyril 18 gave with lithium p-toluenesulfinate highly fluorescent 3-amino-6-methoxy-4-p-tolylsulfonylquinolone 19.