Synthesis 2001(8): 1215-1222
DOI: 10.1055/s-2001-15071
PAPER
© Georg Thieme Verlag Stuttgart · New York

The Photochemistry of Acrylonitrile with Methoxylated Naphthalenes: Introducing the Photochemical Electrophile-Olefin Combination, Aromatic Substitution (Photo-EOCAS) Reaction

Dino Mangion, Matt Frizzle, Donald R. Arnold*, T. Stanley Cameron
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3
Fax: +1(902)4941310; e-Mail: arnold@ac.dal.ca;
Further Information

Publication History

Received 12 March 2001
Publication Date:
24 September 2004 (online)

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.

7

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.

9

Crystallographic 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)

12

It 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.

21

Molecular Structure Corporation, teXsan for Windows, Single Crystal Structure Analysis Software, Version 1.06, 1997-1998.

22

Sheldrick, G. M. SHELX-97, Program for Crystal Structure Determinations; 1997.