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Evidence for Heterolytic Cleavage of C-S Bonds in the Photolysis of 1,3,5-Trithianes

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Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
The homolytic/heterolytic nature of photolytic C-S bond cleavage was studied in 1,3,5-trithianes. The mechanism of photolysis was refined from previous studies. First, evidence was presented for the existence of a precursor of the biradical-like transient (I) which it self was identified in previous studies. Second, the nature of I was further clarified through methanol-scavenging experiments where the results could be interpreted as lending credibility to the notion that I has significant bipolar character. Kinetic and spectral analyses of transient absorptions, following laser excitation of the trithianes, showed that I was reacting with methanol. Complementary steady-state photolytic quantum yields supported this finding, and additional, but unidentified, stable products from irradiations in methanol were seen in the HPLC. The formation of these products was interpreted as likely arising from a nucleophilic attack of methanol at the carbocationic end of the bipolar structure of I.
Słowa kluczowe
Rocznik
Strony
883--892
Opis fizyczny
Bibliogr. 13 poz., rys.
Twórcy
autor
autor
autor
autor
autor
  • Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland phone: +48 61 8291327; fax: +48 61 8658008, marcinia@amu.edu.pl
Bibliografia
  • 1. Still I.W.J., in: Bernardi F., Csizmadia I.G., Mangini A., (Eds.), Organic Sulfur Chemistry. Theoretical and Experimental Advances, Elsevier, Amsterdam, 1985, p. 596.
  • 2. Reid S.T., in: Bryce-Smith D., (Eds.), Photochemistry, Burlington House, London, 1982-1988.
  • 3. Kropp P.J., Fryxell G.E., Tubergen M.W., Hager MW., Harris G.D., Jr., McDermott T.P., Jr. and Tornero-Velez R., J. Am. Chem. Soc., 113, 7300 (1991).
  • 4. Fleming S.A. and Jensen A.W, J. Org. Chem., 61, 7040 (1996).
  • 5. Vialaton D. and Richard C., J. Photochem. Photobiol. A: Chem., 136, 169 (2000).
  • 6. Janeba-Bartoszewicz E., Hug G.L., Kozubek H., Urjasz W. and Marciniak B., J. Photochem. Photobiol. A: Chem.,140, 133(2001).
  • 7. SugiyamaN., Yoshioka M., Aoyama H. and Nishio T., Chem. Comm., 1063 (1971).
  • 8. Nishio T., Yoshioka M., Aoyama H. and SugiyamaN., Bull. Chem. Soc. Jpn., 46, 2253 (1973).
  • 9. Janeba-Bartoszewicz E., Hug G.L., Andrzejewska E. and Marciniak B., J. Photochem. Photobiol. A:Chem., 177, 17 (2006).
  • 10. Douglas J.B. and Hydro W.R., J. Am. Chem. Soc., 73, 3507 (1951).
  • I1. Hawehi Z. El. and Hempel D., J. Prakt. Chem., 21, 286 (1963).
  • 12. Murov S.L., Carmichael 1. and Hug G.L., Handbook of Photochemistry, Marcel Dekker, New York,1993.
  • 13. Thomas M.D. and Hug G.L., Comput. Chem. (Oxford), 22,491 (1998).
Typ dokumentu
Bibliografia
Identyfikator YADDA
bwmeta1.element.baztech-article-BUJ6-0024-0100
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