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Quinone methides in the photodehydration of 2-hydroxy-3-(hydroxymethyl)anthracenes

Basarić, Nikola; Škalamera, Đani; Mlinarić-Majerski, Kata; Wan, Peter
Quinone methides in the photodehydration of 2-hydroxy-3-(hydroxymethyl)anthracenes // ICP 2013
Leuven, Belgija, 2013. str. 220-220 (predavanje, međunarodna recenzija, sažetak, znanstveni)

Quinone methides in the photodehydration of 2-hydroxy-3-(hydroxymethyl)anthracenes

Basarić, Nikola ; Škalamera, Đani ; Mlinarić-Majerski, Kata ; Wan, Peter

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

ICP 2013 / - Leuven, Belgija, 2013, 220-220

ICP 2013 / International Conference in Photochemistry

Mjesto i datum
Leuven, Belgija, 21-26.07.2013

Vrsta sudjelovanja

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
Anthrols; Anthracene derivatives; Photodehydration; Quinone methides

Quinone methides (QMs) are important intermediates in the photochemistry of phenols. Interest in their chemistry was initiated by the discovery of their biological activity ; they are potent DNA alkylating and cross-linking agents. The most common photoreaction for the formation of QMs is photodehydration of hydroxymethyl-substituted phenols.[1] Further, Popik et al. have reported on photodehydration of 2-naphthol derivatives giving rise to QMs. The suggested photochemical reaction mechanism involved ESIPT in 1 as a primary step, followed by the formation of benzoxete 2 and ring-opening to QM 3 (Eq. 1) [2]. Later, we investigated a series of 2-hydroxy-2-adamantyl derivatives of naphthols wherein photodehydration and formation of QMs was also documented. However, benzoxete derivatives were not detected. In addition, we conducted an antiproliferative investigation of the photogenerated QMs and found that the adamantyl derivative of 2-naphthol gives QMs with the selective activity on MCF-7 carcinoma cells.[3] Herein, we report the photodehydration of a series of anthrols. Although anthracene derivatives are important QM precursors in some clinical anticancer drugs, the photodehydration reaction of anthrols has not been reported. The photodehydration reaction in the anthrol series is envisaged to be of particular importance in the potential development of novel anticancer treatments based on the photogeneration of QMs as a potential DNA-alkylating species. We investigated the photodehydration reaction mechanism in the anthracene series by preparative irradiations, fluorescence measurements, and laser flash photolysis (LFP). For example, the LFP measurements for anthrol 4 in trifluoroethanol (TFE) gave rise to the transient spectra that was assigned to QM 5. Contrary to the results of Popik in the naphthalene series, no evidence was found for formation of a benzoxete. QM 5 decays by protonation giving cation 6 that subsequently reacts with nucleophiles giving stable adducts 7 (Eq. 2).

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Projekt / tema
098-0982933-2911 - Kavezasti spojevi: ugradbene jedinice u molekularnim sustavima (Kata Majerski, )

Institut "Ruđer Bošković", Zagreb