Chemie freier cyclischer vicinaler Tricarbonyl‐Verbindungen (‘1,2,3‐Trione’). Teil 3

Abstract

Abstract Chemistry of Free Cyclic Vicinal Tricarbonyl Compounds (‘1,2,3‐Triones’). Part 3. Polar and Redox Reactions of 1,2,3‐Triones with Enamines of Different Types – News on Oxonol Dyes, Radicals, and Biradicals The central CO groups of cyclic 1,2,3‐triones possess outstanding electrophilic (electron‐pair‐accepting) as well as oxidizing (one‐electron‐accepting) properties. Thus, 1,2,3‐triones are chemically related to 1,2‐ and 1,4‐benzoquinones. Whereas polar reactions with carbanion‐like (electron rich) species give rise to nucleophilic addition reactions to CO groups under exclusive C,C‐bond formation, SET (single‐electron transfer) or redox reactions effect a partial ‘ carbonyl Umpolung ’ via ketyl intermediates (C,C‐ and/or C,O‐bond formation). Here, we report on numerous reactions between electron‐rich, more‐ or less‐polar enamines with 5,5‐dimethylcyclohexane‐1,2,3‐trione ( 9a ) and 1 H ‐indene‐1,2,3‐trione ( 9b ). Various new derivatives of basic oxonol dyes were formed, including the first oxonol dye incorporating a 1,3‐dioxocyclohexyl moiety. A novel stable radical, 50 / 50′ , was obtained from 9b and 11a via addition, hydrolysis, and treatment with conc. H 2 SO 4 . Radical 50 / 50′ represents a vinylogous ‘monodehydroreductone’ and is, thus, related to monodehydroascorbic acid ( 143 ), to Russell 's radical cation ( 144 ), to indigo ( 141 / 141′ ), and to quinhydrone.