Photooxidation of acyclovir with thermally generated triplet excited ketones. A comparison with type I and II photosensitizers.
The antiviral drug acyclovir (Ac, 1) was treated with triplet excited ketones, which have been generated in thermal decomposition of 3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane (HTMD), in the dark. Three major oxidation products were detected by means of spectroscopic measurements. The products were (2-hydroxyethoxy) methyl spiroiminodihydantoin (2), (2-hydroxyethoxy) methyl (amino)-2-imino-1,2-dihydroimidazole-5-one (3), and 2,2-diamino-4-[(2-hydroxyethoxy) methyl) amino)-5-[2H]-oxazolone (4). Equal amounts of type I and type II photooxidation products were found, as could be established by comparison with predominant type I (riboflavin) and type II (rose bengal) photosensitizers. The concentration and time profiles for the HTMD-induced oxidation of Ac were also determined. The participation of singlet oxygen in HTMD-induced oxidation was confirmed by the substantial D(2)O effect in the formation of spiroiminodihydantoin (2).
Iqbal
Jawaid
J
Department of Chemistry, Organic Chemistry Section, Aligarh Muslim University, India. jawaid.iqbl0@lycos.com
Husain
Adil
A
Gupta
Anamika
A
D000212:Acyclovir / Q000737:chemistry*; D000998:Antiviral Agents / Q000737:chemistry*; D003624:Darkness; D004305:Dose-Response Relationship, Drug; D006151:Guanosine / Q000031:analogs & derivatives / Q000737:chemistry; D006574:Heterocyclic Compounds, 2-Ring / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry / Q000633:toxicity*; D010084:Oxidation-Reduction / Q000187:drug effects*; D010777:Photochemistry; D017319:Photosensitizing Agents / Q000737:chemistry*; D012256:Riboflavin / Q000737:chemistry; D012395:Rose Bengal / Q000737:chemistry; D013141:Spiro Compounds / Q000737:chemistry; D013696:Temperature; D013997:Time Factors
D000998:Antiviral Agents; D006574:Heterocyclic Compounds, 2-Ring; D007659:Ketones; D017319:Photosensitizing Agents; D013141:Spiro Compounds; C408822:spiroiminodihydantoin; D006151:Guanosine; D012395:Rose Bengal; C511091:3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane; D012256:Riboflavin; D000212:Acyclovir