Photochemical Formation of Anthracene Quinone Methide Derivatives

• Published in: Journal of organic chemistry Vol. 82; no. 12; pp. 6006 - 6021
• Main Authors: Škalamera, Đani, Mlinarić-Majerski, Kata, Martin Kleiner, Irena, Kralj, Marijeta, Oake, Jessy, Wan, Peter, Bohne, Cornelia, Basarić, Nikola
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 16.06.2017; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; DNA ALKYLATION; LASER FLASH-PHOTOLYSIS; SEQUENCE-SPECIFIC ALKYLATION; NAPHTHOQUINONE METHIDES; PROTON-EXCHANGE REACTION; RATE CONSTANTS; CROSS-LINKING; HYDRATED ELECTRONS; PHOTODEHYDRATION REACTIONS; PHENOXYL RADICALS
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.6b02735

Anthrols 2–7 were synthesized and their photochemical reactivity investigated by irradiations in aq CH3OH. Upon excitation with visible light (λ > 400 nm) in methanolic solutions, they undergo photodehydration or photodeamination and deliver methyl ethers, most probably via quinone methides (QMs), with methanolysis quantum efficiencies ΦR = 0.02–0.3. Photophysical properties of 2–7 were determined by steady-state fluorescence and time-correlated single photon counting. Generally, anthrols 2–7 are highly fluorescent in aprotic solvents (ΦF = 0.5–0.9), whereas in aqueous solutions the fluorescence is quenched due to excited-state proton transfer (ESPT) to solvent. The exception is amine 4 that undergoes excited-state intramolecular proton transfer (ESIPT) in neat CH3CN where photodeamination is probably coupled to ESIPT. Photodehydration may take place via ESIPT (or ESPT) that is coupled to dehydration or via a hitherto undisclosed pathway that involves photoionization and deprotonation of radical cation, followed by homolytic cleavage of the alcohol OH group from the phenoxyl radical. QMs were detected by laser flash photolysis and their reactivity with nucleophiles investigated. Biological investigation of 2–5 on human cancer cell lines showed enhancement of antiproliferative effect upon exposure of cells to irradiation by visible light, probably due to formation of electrophilic species such as QMs.