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

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.

photochemistry - electron transfer - alkylations - cycloadditions - rearrangements

References and Notes

<A NAME="RC02701SS-1">1</A> March J. Advanced Organic Chemistry   Wiley Interscience; New York: 1992.  p.534 

For some recent examples see:

<A NAME="RC02701SS-2A">2a</A> Mangion D. Arnold DR. Can. J. Chem.  1999,  77:  1655 

<A NAME="RC02701SS-2B">2b</A> Mangion D. Arnold DR. Cameron TS. Robertson KN. J. Chem. Soc., Perkin Trans. 2  2001,  48 

<A NAME="RC02701SS-2C">2c</A> Mangion D. Kendall J. Arnold DR. Org. Lett.  2001,  3:  45 

For reviews on the synthetic aspects of electron transfer photochemistry see:

<A NAME="RC02701SS-3A">3a</A> Mattes SL. Farid S. In Organic Photochemistry   Vol. 6:  Padwa A. Marcel Dekker; New York: 1983.  p.238 

<A NAME="RC02701SS-3B">3b</A> Muller F. Mattay J. Chem. Rev.  1993,  93:  99 

<A NAME="RC02701SS-3C">3c</A> Pandey G. Top. Curr. Chem.  1993,  168:  175 

<A NAME="RC02701SS-3D">3d</A> Mizuno K. Otsuji Y. Top. Curr. Chem.  1994,  169:  301 

<A NAME="RC02701SS-3E">3e</A> Hintz S. Heidbreder A. Mattay J. Top. Curr. Chem.  1996,  177:  77 

<A NAME="RC02701SS-4A">4a</A> Ohashi M. Tanaka Y. Yamada S. J. Chem. Soc., Chem. Commun.  1976,  800 

<A NAME="RC02701SS-4B">4b</A> Ohashi M. Tanaka Y. Yamada S. Tetrahedron Lett.  1977,  3629 

<A NAME="RC02701SS-5A">5a</A> Bowman RM. Chamberlain TR. Huang CW. McCullough JJ. J. Am. Chem. Soc.  1970,  92:  4106 

<A NAME="RC02701SS-5B">5b</A> Bowman RM. Chamberlain TR. Huang CW. McCullough JJ. J. Am. Chem. Soc.  1974,  96:  692 

<A NAME="RC02701SS-6">6</A> McCullough JJ. Huang CW. Can. J. Chem.  1969,  47:  757 

<A NAME="RC02701SS-7">7</A>

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.

<A NAME="RC02701SS-8">8</A> Miyamoto T. Mori T. Odaira Y. J. Chem. Soc., Chem. Commun.  1970,  1598 

<A NAME="RC02701SS-9">9</A>

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: [phone] or e-mail: [e-mail])

<A NAME="RC02701SS-10">10</A> Zweig A. Maurer AH. Roberts BG. J. Org. Chem.  1967,  32:  1322 

<A NAME="RC02701SS-11">11</A> Rehm D. Weller A. Isr. J. Chem.  1970,  8:  259 

<A NAME="RC02701SS-12">12</A>

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.

<A NAME="RC02701SS-13">13</A> House HO. Huber LE. Umen MJ. J. Am. Chem. Soc.  1972,  94:  8471 

<A NAME="RC02701SS-14A">14a</A> Lewis FD. Kojima M. J. Am. Chem. Soc.  1988,  110:  8664 

<A NAME="RC02701SS-14B">14b</A> Bauld NL. Tetrahedron  1989,  45:  5307 

<A NAME="RC02701SS-14C">14c</A> Johnston LJ. Schepp NP. Adv. Electron Transfer Chem.  1996,  5:  41 

<A NAME="RC02701SS-15">15</A> Barltrop JA. Carless HAJ. J. Am. Chem. Soc.  1972,  94:  1951 

<A NAME="RC02701SS-16">16</A> Karplus M. J. Am. Chem. Soc.  1963,  85:  2870 

<A NAME="RC02701SS-17">17</A> Breitmaier E. Structure Elucidation by NMR in Organic Chemistry   Wiley Interscience; New York: 1993.  p.43 

<A NAME="RC02701SS-18">18</A> Friebolin H. Basic One- and Two-Dimensional NMR Spectroscopy   VCH; New York: 1993.  p.91 

<A NAME="RC02701SS-19">19</A> Akhtar IA. McCullough JJ. J. Org. Chem.  1981,  46:  1447 

<A NAME="RC02701SS-20">20</A> Still WC. Kahn M. Mitra A. J. Org. Chem.  1978,  43:  2923 

<A NAME="RC02701SS-21">21</A>

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

<A NAME="RC02701SS-22">22</A>

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