Article

Photoreduction of oxoisoaporphines. Another example of a formal hydride-transfer mechanism.

Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Casilla 233, Santiago, Chile.
Photochemical and Photobiological Sciences (Impact Factor: 2.92). 03/2004; 3(2):194-9. DOI: 10.1039/b310696a
Source: PubMed

ABSTRACT Photoreduction of 5,6-dimethoxy-, 5-methoxy- and 2,3-dihydro-7H-dibenzo[de,h]quinolin-7-one (A) by tertiary amines in oxygen-free solutions generates long-lived semi-reduced metastable photoproducts, A-NH(-), via a stepwise electron-proton-electron transfer mechanism with a limit quantum yield of about 0.1 at high TEA concentrations. These metastable photoproducts revert thermally to the initial oxoisoaporphine nearly quantitatively in the presence or absence of oxygen. We present spectrophotometric, NMR and UV-vis data for the metastable photoproducts. The spectrophotometric results and PM3 and ZINDO/S calculations support the proposed mechanism for the photoreduction of the oxoisoaporphines.

0 Bookmarks
 · 
102 Views
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The aim of this study was to determine the electronic influence of substituent groups and annelated rings such as oxazole-oxazinone on the physicochemical and photoprotection, antioxidant capacity, toxicity and singlet oxygen photosensitization biological properties of isoquinoline alkaloid frameworks. Thus, oxoisoaporphine derivatives 1 - 5 and 3-azaoxoisoaporphine ( 6 ), some of them with phenolic structures, did not present any antioxidant capacity, possibly either by formation of keto-enol tautomerism species or the formation of unstable free radicals. Due to the singlet oxygen quantum yields (F<sub>D</sub>) near to unity, and greater photostability than phenalenone, oxoisoaporphines 4 - 6 may be considered as photosensitizers for singlet oxygen production and can be used as new universal study tools. The biological application as antibacterial agents is an important and possible tool in the study of compounds with low cytotoxicity and high reactivity in antineoplastic chemotherapy. On the other hand, when boldine and its annelated derivatives B1 - 4 are irradiated, a photoprotector effect is observed (SPF = 2.35), even after 30 minutes of irradiation. They also act as photoprotectors in cell fibroblast cultures. No hemolysis was detected for boldine hydrochloride and its salts without irradiation. In solutions irradiated before incubation (at concentrations over 200 ppm) photoproducts were toxic to the nauplii of Artemia salina.
    Molecules 01/2012; 17(9):10958-70. · 2.43 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Photoreduction of 7H-benzo[e]perimidin-7-one (3-AOIA, A1) and its 2-methyl derivative (2-Me-3-AOIA, A2) by non-H-donating amines (1,4-diazabicyclo[2.2.2]octane [DABCO]; 2,2,6,6-tetramethylpiperidine [TMP]), and a hydrogen-donating amine (triethylamine [TEA]), has been studied in deaerated neat acetonitrile solutions using laser flash photolysis (LFP) and steady-state photolysis. The triplet excited states of A1 and A2 were characterized by a strong absorption band with λmax = 440 nm and lifetimes of 20 and 27 μs respectively. In the presence of tertiary amines, both triplet excited states were quenched with rate constants close to the diffusional limit (kq ranged between 109 and 1010 M−1 s−1). The transient absorption spectra observed after quenching with DABCO and TMP were characterized by maxima located at 460 nm and broad shoulders in the range of 500–600 nm. These transient species are attributed to solvent-separated radical ion pairs and/or to isolated radical anions. In the presence of TEA, these transients undergo proton transfer, leading to the neutral hydrogenated radicals, protonated over the N1- and O-atoms. Transient absorption spectra of these transients were characterized by maxima located at 400 and 520 nm and 430 nm respectively. Additional support for these spectral assignments was provided by pulse radiolysis (PR) experiments in acetonitrile and 2-propanol solutions.
    Photochemistry and Photobiology 01/2013; 89(6):1417-1426. · 2.29 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Photoinduced electron transfer between N‐phenylglycine (NPG) and electronically excited triplets of 7‐substituted‐3‐methyl‐quinoxalin‐2‐ones in acetonitrile generate the respective ion radical pair, where by decarboxylation the phenyl‐amino‐alkyl radical, PhNHCH2•, is generated. This radical reacts with the 3‐methyl‐quinoxalin‐2‐ones ground states, leading to the product 2. Other, unexpected, 7‐substituted‐1,2,3,3a‐tetrahydro‐3a‐methyl‐2‐phenylimidazo[1,5‐a]quinoxalin‐4(5H)‐ones, annulation products, 3a–f, were generated; likely by the addition of two PhNHCH2• radicals, to positions 3 and 4 of the quinoxalin‐2‐ones. The reaction mechanism includes a photoinduced one electron transfer initiation step, propagation steps involving radical intermediates and NPG with radical chain termination steps that lead to the respective products 2a–f and 3a–f and NPG by‐products. The proposed mechanism accounts for the strong dependency found for the initial photoconsumption quantum yields on the electron‐withdrawing power of the substituent. Therefore, photolysis of common reactants widely used such as NPG and substituted quinoxalin‐2‐ones may provide a simple synthetic way to the unusual, unreported tetrahydro‐imidazoquinoxalinones 3a–f.
    Photochemistry and Photobiology 08/2013; · 2.29 Impact Factor