Effective C-N bond formation on the 1-methyl-2-quinolone skeleton

Abstract

Electron-deficient 1-methyl-3,6,8-trinitro-2-quinolone is highly reactive, and readily reacted with two equivalents of primary amines at room temperature to afford ammonium salts of 4-alkylamino-3,4-dihydro-1-methyl-3,6,8-trinitro-2-quinolones.4-Alkylamino-6,8-dinitro-1-methyl-2-quinolones were also prepared when the reaction was conducted at elevated temperature.

A direct and vicinal functionalization of the 1-methyl-2-quinolone framework: 4-alkoxylation and 3-chlorination

“…20 However, no direct amination method for the MeQone framework has been reported, except for our report. 11 Hence, this imidation is a useful method for the direct aminochlorination of the MeQone framework.…”

“…We have shown that 1-methyl-3,6,8-trinitro-2-quinolone (TNQ) is highly reactive among MeQones to form either a C-C or a C-N bond at the 4-position regioselectively or to undergo a cycloaddition reaction readily. [8][9][10][11] Inspired by these results, we envisioned that a direct C-O bond formation at the 4-position of MeQone would be possible by the treatment of 3-nitrated MeQones including TNQ with an alkoxide ion. In this case, it is necessary to trap the anionic adduct intermediate by an electrophile because a heteronucleophile is easily eliminated even though it adds to TNQ.…”