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DOI: 10.1055/s-2001-15071
The Photochemistry of Acrylonitrile with Methoxylated Naphthalenes: Introducing the Photochemical Electrophile-Olefin Combination, Aromatic Substitution (Photo-EOCAS) Reaction
Publication History
Publication Date:
24 September 2004 (online)
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Abstract
The photochemical reactions of acrylonitrile (1) with 1,5-dimethoxynaphthalene (2), 1-methoxynaphthalene (3) and 1,4-dimethoxynaphthalene (4) in various solvents have been investigated. In polar solvents (methanol and acetontrile), an electron transfer pathway leads to the formation of aromatic substitution (with 2 and 3) and addition products (with 4). In benzene, an exciplex-mediated [2π + 2π] cycloaddition occurs. The cycloadducts formed undergo a further photoinduced rearrangement via a [2σ + 2σ] cycloreversion followed by an intramolecular [4π + 2π] cycloaddition.
Key words
photochemistry - electron transfer - alkylations - cycloadditions - rearrangements
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References and Notes
Half-wave excited state oxidation potential, E ox* = E ox - E 0,0, where E ox is the half-wave oxidation potential of the ground state and E 0,0 is the excited state energy. Values obtained from Ref 3a.
9Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 162031-162034 (compunds 6, 7, 16 and 12, respectively).Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.ac.uk)
12It has been estimated [11] that a PET process will proceed at a diffusion-controlled rate when the free energy is less than -20 kJ mol-1.
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