A Facile and Practical Solvent-Free One-Pot Synthesis of (Z)-4-Methylene-3-selenaquinoline Derivatives from o-Ethynylanilines and Isoselenocyanates [¹]

Abstract

Heating of o-ethynylanilines with isoselenocyanates directly resulted in the 6-exo-dig mode ring-closure reaction of the adducts to give the (Z)-2-imino-4-methylene-3-selenaquinolines in moderate to good yields. Based on this convenient, solvent-free, catalyst-free method, several 3-selenaquinoline derivatives (3,1-benzoselenazines) were easily obtained in one pot. Successful application of the microwave-assisted synthesis of these compounds was also investigated.

o-ethynyaniline - isoselenocyanate - 3-selenaquinoline - 6-exo mode cyclization - microwave

References

<A NAME="RF07110SS-1">1</A> This paper constitutes Part 31 in the series ‘Studies on Tellurium-Containing Heterocycles’, For Part 30, see: Sashida H. Kaname M. Nakayama A. Suzuki H. Minoura M. Tetrahedron  2010,  66:  5149 

<A NAME="RF07110SS-2A">2a</A> Selenium in Biology and Medicine   Wengel A. Springer; Berlin: 1989. 

<A NAME="RF07110SS-2B">2b</A> Burk RF. Selenium in Biology and Human Health   Springer; New York: 1994. 

<A NAME="RF07110SS-2C">2c</A> Xu Y. Kool ET. J. Am. Chem. Soc.  2000,  122:  9040 

<A NAME="RF07110SS-2D">2d</A> Mugesh G. du Mont W.-W. Sies H. Chem. Rev.  2001,  101:  2125 

<A NAME="RF07110SS-2E">2e</A> Soriano-Garcia M. Curr. Med. Chem.  2004,  11:  1657 

<A NAME="RF07110SS-3">3</A> Koketsu M. Ishihara H. Curr. Org. Chem.  2003,  7:  175 

<A NAME="RF07110SS-4A">4a</A> Koketsu M. Tanaka Y. Hiramatsu S. Ishihara H. Heterocycles  2001,  55:  1181 

<A NAME="RF07110SS-4B">4b</A> Koketsu M. Senda T. Hiramatsu S. Ishihara H. J. Chem. Soc., Perkin Trans. 1  1999,  453 

<A NAME="RF07110SS-4C">4c</A> Koketsu M. Hiramatsu S. Ishihara H. Chem. Lett.  1999,  485 

<A NAME="RF07110SS-4D">4d</A> Bochu C. Couture A. Grandelaudon P. J. Org. Chem.  1988,  53:  4852 

<A NAME="RF07110SS-4E">4e</A> Dubreuil D. Pradere JP. Giraudeau N. Goli M. Tonnard F. Tetrahedron Lett.  1995,  36:  237 

<A NAME="RF07110SS-4F">4f</A> Sekiguchi M. Ogawa A. Fujiwara S. Ryu I. Kambe N. Sonoda N. Chem. Lett.  1990,  913 

<A NAME="RF07110SS-4G">4g</A> Shimada K. Akikawa K. Fujita T. Aoyagi S. Takikawa Y. Kabuto C. Chem. Lett.  1997,  701 

<A NAME="RF07110SS-5A">5a</A> Takahashi M. Watanabe S. Kasai T. Heterocycles  1980,  14:  1921 

<A NAME="RF07110SS-5B">5b</A> Liebscher J. Hartmann H. Tetrahedron Lett.  1976,  17:  2005 

<A NAME="RF07110SS-6">6</A> Yokoyama M. Kumada K. Hatanaka H. Shiraishi T. Bull. Chem. Soc. Jpn.  1986,  48:  1613 

<A NAME="RF07110SS-7A">7a</A> Simchen G. Angew. Chem., Int. Ed. Engl.  1968,  7:  464 

<A NAME="RF07110SS-7B">7b</A> Simchen G. Wenzelburger J. Chem. Ber.  1970,  103:  413 

<A NAME="RF07110SS-7C">7c</A> Simchen G. Entenmann G. Angew. Chem., Int. Ed. Engl.  1973,  12:  119 

<A NAME="RF07110SS-8">8</A> Garud DR. Koketsu M. Ishihara H. Molecules  2007,  12:  504 

<A NAME="RF07110SS-9">9</A> Toyada Y. Garuda DR. Koketsu M. Heterocycles  2009,  78:  449 

<A NAME="RF07110SS-10">10</A> Garud DR. Toyoda Y. Koketsu M. Tetrahedron Lett.  2009,  50:  3035 

<A NAME="RF07110SS-11">11</A> Sommen GL. Linden A. Heimgartner H. Tetrahedron Lett.  2005,  46:  6723 

<A NAME="RF07110SS-12">12</A> Koketsu M. Sakai T. Kiyokuni T. Garuda DR. Ando H. Ishihara H. Heterocycles  2006,  68:  1604 

<A NAME="RF07110SS-13">13</A> Sommen GL. Linden A. Heimgartner H. Tetrahedron  2006,  62:  3344 

<A NAME="RF07110SS-14">14</A> Ye S. Ding Q. Wang Z. Zhou H. Wu J. Org. Biomol. Chem.  2008,  6:  4406 

<A NAME="RF07110SS-15">15</A> Ding Q. Wu J. J. Comb. Chem.  2008,  10:  541 

<A NAME="RF07110SS-16A">16a</A> Sashida H. Rev. Heteroat. Chem.  2000,  22:  59 

<A NAME="RF07110SS-16B">16b</A> Sashida H. J. Synth. Org. Chem. Jpn.  2001,  59:  355 

<A NAME="RF07110SS-17">17</A> Sashida H. Nakayama A. Kaname M. Synthesis  2008,  3229 

<A NAME="RF07110SS-18">18</A> Martins MAP. Frizzo CP. Moreira DN. Buriol L. Machado P. Chem. Rev.  2009,  109:  4140 

<A NAME="RF07110SS-19A">19a</A> Lidström P. Tierney J. Wathey B. Westman J. Tetrahedron  2001,  57:  9225 

<A NAME="RF07110SS-19B">19b</A> Xu Y. Guo Q.-X. Heterocycles  2004,  63:  903 

<A NAME="RF07110SS-19C">19c</A> Jindal R. Bajaj S. Curr. Org. Chem.  2008,  12:  836 

<A NAME="RF07110SS-19D">19d</A> Hugel HM. Molecules  2009,  14:  4936 

<A NAME="RF07110SS-20">20</A>

Single crystals of 3Dd were obtained from solns of CHCl₃ after slow evaporation of the solvent at r.t. Diffraction data were collected on a Bruker Apex-II CCD. The structure analysis is based on 2629 observed reflections with I > 2.00σ(I) and 217 variable parameters; colorless prisms, C₂₁H₁₆N₂Se, FW = 375.32, 233 K, monoclinic, space group P2₁/n, a = 10.3882(7) Å, b = 8.3928(5) Å, c = 19.432(1) Å, β = 91.164(1)˚, V = 1693.9(2) Å^³, Z = 4, R = 0.0288, R _w  = 0.0759, GOF = 1.037. The supplementary crystallographic data for 3Dd (CCDC-773220) can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/products/csd/request/request.php4.

<A NAME="RF07110SS-21">21</A> Shi C. Zhang Q. Wang K. J. Org. Chem.  1999,  64:  925 

<A NAME="RF07110SS-22">22</A> Koradin C. Dohle W. Rodrigues A. Schmid B. Knochel P. Tetrahedron  2003,  59:  157 

<A NAME="RF07110SS-23">23</A> Woodgate PD. Sutherland H. J. Organomet. Chem.  2001,  629:  131 

<A NAME="RF07110SS-24">24</A> Villemin D. Goussu D. Heterocycles  1989,  29:  1255 

<A NAME="RF07110SS-25">25</A> Sonoda N. Yamamoto G. Tsutsumi S. Bull Chem. Soc. Jpn.  1972,  45:  2937 

<A NAME="RF07110SS-26">26</A> Fernändes-Bolaños JG. López . Ulgar V. Maya I. Fuentes J. Tetrahedron Lett.  2004,  45:  4081