Singlet- and triplet-state photodissociation of CO and CN bonds in aromatic acetones studied by 1H-CIDNP spectroscopy

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Abstract

The photolysis of (4-methoxyphenoxy)acetone (1a) and (N-methylanilino)acetone (1b) in fluid solution was investigated by photo 1H chemically induced dynamic nuclear polarization (CIDNP) spectroscopy. The primary step is a dissociation of the CO or CN bond to give acetonyl and 4-methoxyphenoxy or N-methylanilino radicals respectively. For 1a the dissociative state is the singlet state on direct excitation while by triplet state in a separate reaction channel, acetone is formed. On direct excitation, 1b decomposes via both the singlet and the triplet states to the same primary radical pair. At temperatures below 290 K the triplet reaction dominates. With increasing temperature the singlet reaction becomes favoured and thus an unusual inversion of the CIDNP polarization sign is observed. These quite unexpected observations suggest that the photochemistry of these acetone derivatives should not be classified as those of a typical carbonyl compound. Rather, they show strong resemblance to the photo-Claisen reaction of unsatured ethers or the photo-Fries rearrangement of phenyl esters and anilides.

References (45)

  • J.C. Netto-Ferreira et al.

    Tetrahedron Lett.

    (1989)
  • W.U. Palm et al.

    J. Photochem. Photobiol. A: Chem.

    (1990)
  • M. Läufer et al.

    J. Magn. Reson.

    (1984)
  • P.J. Wagner

    Tetrahedron Lett.

    (1967)
  • J.-K. Vollenweider et al.

    Chem. Phys.

    (1988)
  • H. Zuckermann et al.

    Chem. Phys. Lett.

    (1988)
  • J.C. Scaiano et al.

    J. Photochem.

    (1986)
  • H. Kobsa

    J. Org. Chem.

    (1962)
  • J.W. Meyer et al.

    J. Am. Chem. Soc.

    (1972)
  • C.E. Kalmus et al.

    J. Am. Chem. Soc.

    (1974)
  • H. Shizuka et al.

    Bull. Chem. Soc. Jpn.

    (1969)
  • H. Shizuka

    Bull. Chem. Soc. Jpn.

    (1969)
  • H. Shizuka

    Bull. Chem. Soc. Jpn.

    (1969)
  • J.T. Pinhey et al.

    Aust. J. Chem.

    (1968)
  • F.A. Carroll et al.

    J. Am. Chem. Soc.

    (1972)
  • K. Schaffner

    Pure Appl. Chem.

    (1967)
  • J.C. Netto-Ferreira et al.

    J. Org. Chem.

    (1990)
  • H.E. Zimmerman

    Top. Curr. Chem.

    (1982)
  • W.U. Palm et al.

    Ber. Bunsenges. Phys. Chem.

    (1992)
  • P.J. Wagner

    Top. Curr. Chem.

    (1976)
  • N.J. Turro
    (1978)
  • W. Adam et al.

    J. Org. Chem.

    (1973)
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