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Pregled bibliografske jedinice broj: 579062

Sterically Congested Adamantylnaphthalene Quinone Methides


Veljković, Jelena; Uzelac, Lidija; Molčanov, Krešimir; Mlinarić-Majerski, Kata; Kralj, Marijeta; Wan, Peter; Basarić, Nikola
Sterically Congested Adamantylnaphthalene Quinone Methides // Journal of organic chemistry, 77 (2012), 10; 4596-4610 doi:10.1021/jo3002479 (međunarodna recenzija, članak, znanstveni)


Naslov
Sterically Congested Adamantylnaphthalene Quinone Methides

Autori
Veljković, Jelena ; Uzelac, Lidija ; Molčanov, Krešimir ; Mlinarić-Majerski, Kata ; Kralj, Marijeta ; Wan, Peter ; Basarić, Nikola

Izvornik
Journal of organic chemistry (0022-3263) 77 (2012), 10; 4596-4610

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Adamantanes ; antiproliferative activity ; laser flash photolysis ; naphthols ; photodehydroxylation ; proton transfer ; quinone methides

Sažetak
Five new (2-adamantyl)naphthol derivatives (5-9, quinone methide precursors, QMP) were synthesized and their photochemical reactivity investigated by preparative photolyses, fluorescence spectroscopy and laser flash photolysis (LFP). Excitation of QMP 5 to S1 leads to efficient excited state intramolecular proton transfer (ESIPT) coupled with dehydration, giving quinone methide QM5 which was characterized by LFP (in CH3CN-H2O, λmax = 370 nm, τ =0.19 ms). On irradiation of QMP 5 in CH3OH-H2O (4:1), the quantum yield of methanolysis is Φ = 0.70. Excitation of naphthols QMP 6-8 to S1 in CH3CN leads to photoionization and formation of naphthoxyl radicals. In a protic solvent QMP 6-8 undergo solvent-assisted PT giving QM6 or zwitterion QM8 that react with nucleophiles delivering adducts, but with a significantly lower quantum efficiency. QMP 9 in a protic solvent undergoes two competitive processes, photosolvolysis via QM9 and solvent-assisted PT to carbon atom of the naphthalene giving zwitterion. QM9 has been characterized by LFP (in CH3CN-H2O, λmax > 600 nm, τ =0.9 ms). In addition to photogenerated QMs, two stable naphthalene QMs QM10 and QM11 were synthesized thermally and characterized by X-ray crystallography. QM10 and QM11 do not react with H2O but undergo acid-catalyzed fragmentation or rearrangement. Antiproliferative activity of 5-9 was investigated on three human cancer cell lines. Exposure of MCF-7 cells treated with 5 to 300 nm irradiation leads to enhanced antiproliferative effect, in accordance with the activity being due to the formation of QM5.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Temeljne medicinske znanosti



POVEZANOST RADA


Projekt / tema
098-0982933-2911 - Kavezasti spojevi: ugradbene jedinice u molekularnim sustavima (Kata Majerski, )
HRZZ-UIP-02.05/25 - Fotokemija policikličkih molekula: od istraživanja mehanizma reakcije do novih lijekova i medicinskih primjena (Nikola Basarić, )

Ustanove
Institut "Ruđer Bošković", Zagreb

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


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