Chemiluminogenic Features of 10-Methyl-9-(phenoxycarbonyl)acridinium Trifluoromethanesulfonates Alkyl Substituted at the Benzene Ring in Aqueous Media

• Published in: Journal of organic chemistry 2011-02, Vol.76 (4), p.1072-1085
• Main Authors: Krzymiński, Karol, Ożóg, Agnieszka, Malecha, Piotr, Roshal, Alexander D, Wróblewska, Agnieszka, Zadykowicz, Beata, Błażejowski, Jerzy
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Kinetics and mechanisms; Noncondensed benzenic compounds; Organic chemistry; Preparations and properties; Reactivity and mechanisms
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo1020882

10-Methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulfonates bearing alkyl substituents at the benzene ring were synthesized, purified, and identified. In the reaction with OOH− in basic aqueous media, the cations of the compounds investigated were converted to electronically excited 10-methyl-9-acridinone, whose relaxation was accompanied by chemiluminescence (CL). The kinetic constants of CL decay, relative efficiencies of light emission, chemiluminescence quantum yields, and resistance toward alkaline hydrolysis were determined experimentally under various conditions. The mechanism of CL generation is considered on the basis of thermodynamic and kinetic parameters of the reaction steps predicted at the DFT level of theory. The chemiluminescence efficiency is the result of competition of the electrophilic center at C(9) between nucleophilic substitution by OOH− or OH− and the ability of the intermediates thus formed to decompose to electronically excited 10-methyl-9-acridinone. Identification of stable and intermediate reaction products corroborated the suggested reaction scheme. The results obtained, particularly the dependency of the “usefulness” parameter, which takes into account the CL quantum yield and the susceptibility to hydrolysis, on the cavity volume of the entity removed during oxidation, form a convenient framework within which to rationally design chemiluminescent 10-methyl-9-(phenoxycarbonyl)acridinium cations.