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Synthesis 2009(24): 4167-4174  
DOI: 10.1055/s-0029-1217059
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

The Synthesis of 2-Cyano-cyanothioformanilides from 2-(4-Chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitriles Using DBU

Sophia S. Michaelidou, Panayiotis A. Koutentis*
Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus
Fax: +357(22)892809; e-Mail: koutenti@ucy.ac.cy;
Further Information

Publication History

Received 30 June 2009
Publication Date:
19 October 2009 (online)

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Abstract

A series of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitriles were prepared from the reaction of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) and the corresponding anthranilonitriles. Reaction of the 1,2,3-dithiazolimines with DBU (3 equiv) at -5 ˚C gave the corresponding 2-cyano-cyanothioformanilides in near quantitative yields. Treatment of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitrile with DBU (4 equiv) at -5 to +20 ˚C gave 2-isothiocyanatobenzonitrile in 96% yield. The latter compound was also formed directly from 2-cyano-cyanothioformanilide on treatment with DBU (1 equiv) in 95% yield. A tentative mechanism for the DBU-mediated dithiazole to cyanothioformanilide transformation is proposed and all compounds were fully characterized.

Key words

Appel salt - DBU - Cyanothioformanilide - isothiocyanate

    References

  • 1 Olin JF. inventors; US Patent  3287102. 
  • 2a El-Sharief AMSh. Ammar YA. Mohamed YA. El-Gaby MSA. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  148:  117 
    Google Scholar
  • 2b Elagamey AA. El-Taweel FMA. El-Enein RANA. Phosphorus, Sulfur Silicon Relat. Elem.  2006,  181:  2155 
    Google Scholar
  • 3a Singer MS. inventors; US Patent  3655689. 
  • 3b Huang L. Graves MD. J. Heterocycl. Chem.  1987,  24:  1781 
    Google Scholar
  • 3c El-Sharief AMSh. Ammar YA. Zahran MA. Sabet HKh. Phosphorus, Sulfur Silicon Relat. Elem.  2004,  179:  267 
    Google Scholar
  • 3d Ketcham R. Schumann E. J. Org. Chem.  1980,  45:  3748 
    Google Scholar
  • 3e Kinzel P, and Wilhelm M. inventors; Ger Offen.  3000130. 
  • 3f Kinzel P. inventors; Ger Offen.  3437853. 
  • 3g Ammar YA. El-Sharief AMSh. Ali MM. Mohamed YA. Mohamed ShI. Phosphorus, Sulfur Silicon Relat. Elem.  2000,  166:  173 
    Google Scholar
  • 3h El-Sharief AMSh. Ammar YA. Mohamed YA. Ali MM. El-Gaby MSA. Ali AS. Phosphorus, Sulfur Silicon Relat. Elem.  2001,  173:  39 
    Google Scholar
  • 3i El-Sharief AMSh. Ammar YA. El-Gaby MSA. Zahran MA. Khames AA. Afinidad  2003,  60:  47 
    Google Scholar
  • 3j El-Gaby MSA. El-Sharief AMSh. Atalla AA. El-Adasy AAAM. J. Chin. Chem. Soc. (Taipei)  2004,  51:  327 
    Google Scholar
  • 3k Kobayashi-Matsunaga Y. Ishii T. Hamaguchi T. Osada H. Sato M. Lett. Drug Des. Discovery  2005,  2:  224 
    Google Scholar
  • 4a Ketcham R. Synthesis  1980,  11:  869 
    Google Scholar
  • 4b El-Sharief AMSh. Ammar YA. Mohamed YA. El-Gaby MSA. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  148:  215 
    Google Scholar
  • 4c El-Sharief AMSh. Ammar YA. Zahran MA. Sabet HKh. J. Chem. Res., Synop.  2003,  162 
    Google Scholar
  • 5 Mahran AM. Hassan NA. Arch. Pharm. Res.  2006,  29:  46 
    CrossrefGoogle Scholar
  • 6a Deck LM. Papadopoulos EP. Smith KA. J. Heterocycl. Chem.  2003,  40:  885 
    Google Scholar
  • 6b El-Sharief AMS. Ammar YA. Mohamed YA. El-Gaby MSA. Heteroat. Chem.  2002,  13:  291 
    Google Scholar
  • 6c Besson T. Rees CW. J. Chem. Soc., Perkin Trans. 1  1996,  2857 
    Google Scholar
  • 7a Kattak I. Ketcham R. Schaumann E. Adiwidjaja G. J. Org. Chem.  1985,  50:  3431 
    Google Scholar
  • 7b El-Sharief AMSh. Hussein AM. Atalla AA. El-Gaby MSA. Hassan AA. Phosphorus, Sulfur Silicon Relat. Elem.  2000,  160:  141 
    Google Scholar
  • 7c El-Sharief AMSh. Hussein AM. El-Gaby MSA. Atalla AA. Ahmed AA. Phosphorus, Sulfur Silicon Relat. Elem.  2001,  170:  47 
    Google Scholar
  • 7d El-Sharief AMSh. Mahmoud FF. Taha NM. Ahmed EM. Phosphorus, Sulfur Silicon Relat. Elem.  2005,  180:  573 
    Google Scholar
  • 7e El-Sharief AMSh. El-Gaby MSA. Atalla AA. El-Adasy A.-BAAM. Afinidad  2003,  60:  475 
    Google Scholar
  • 7f El-Sharief AMS. El-Gaby MSA. Atalla AA. El-Adasy A.-BAAM. Heteroat. Chem.  2005,  16:  218 
    Google Scholar
  • 7g El-Sharief AMS. Al-Amri AM. Al-Raqa SY. J. Sulfur Chem.  2006,  27:  245 
    Google Scholar
  • 8a Friedrich K. Zamkanei M. Tetrahedron Lett.  1977,  18:  2139 
    Google Scholar
  • 8b Friedrich K. Zamkanei M. Chem. Ber.  1979,  112:  1867 
    Google Scholar
  • 8c Friedrich JD. J. Org. Chem.  1987,  52:  2442 
    Google Scholar
  • 9 Friedrich K. Zamkanei M. Chem. Ber.  1979,  112:  1916 
    CrossrefGoogle Scholar
  • 10 Friedrich K. Zamkanei M. Chem. Ber.  1979,  112:  1873 
    CrossrefGoogle Scholar
  • 11 Grabenko AD. Danchenko MN. Pel’kis PS. J. Org. Chem. USSR (Engl. Transl.)  1972,  8:  532 
    Google Scholar
  • 12 El-Gaby MSA. Ammar YA. El-Sharief AMSh. Zahran MA. Khames AA. Heteroat. Chem.  2002,  13:  611 
    CrossrefGoogle Scholar
  • 13a Gonda J. Kristian P. Coll. Czech. Chem. Commun.  1988,  53:  1761 
    Google Scholar
  • 13b Walter W. Hell P.-M. Liebigs Ann.  1969,  727:  22 
    Google Scholar
  • 13c Walter W. Bode K.-D. Liebigs Ann.  1966,  698:  131 
    Google Scholar
  • 13d Reissert A. Brüggemann K. Chem. Ber.  1924,  57:  981 
    Google Scholar
  • 14 Kantlehner W. Haug E. Isak H. Schulz W. Hippich S. Baur R. Hagen H. Chem. Ber.  1982,  115:  1721 
    CrossrefGoogle Scholar
  • 15 Reissert A. Chem. Ber.  1904,  37:  3708 
    Google Scholar
  • 16 Besson T. Rees CW. J. Chem. Soc., Perkin Trans. 1  1995,  1659 
    CrossrefGoogle Scholar
  • 17 Lee H. Kim K. Bull. Korean Chem. Soc.  1992,  13:  107 
    Google Scholar
  • 18 English RF. Rakitin OA. Rees CW. Vlasova OG. J. Chem. Soc., Perkin Trans. 1  1997,  201 
    CrossrefGoogle Scholar
  • 19 Chang Y.-G. Kim K. Heterocycles  1999,  51:  2653 
    CrossrefGoogle Scholar
  • 20 Lee H.-S. Chang Y.-G. Kim K. J. Heterocycl. Chem.  1998,  35:  659 
    CrossrefGoogle Scholar
  • 21 Mohanta PK. Kim K. Tetrahedron Lett.  2002,  43:  3993 
    CrossrefGoogle Scholar
  • 22 Pereira M.-F. Thiéry V. Besson T. Tetrahedron  2007,  63:  847 
    CrossrefGoogle Scholar
  • 23 Lee H.-S. Kim K. Tetrahedron Lett.  1996,  37:  869 
    CrossrefGoogle Scholar
  • 24a Besson T. Emayan K. Rees CW. J. Chem. Soc., Chem. Commun.  1995,  1419 
    Google Scholar
  • 24b Besson T. Emayan K. Rees CW. J. Chem. Soc., Perkin Trans. 1  1995,  2097 
    Google Scholar
  • 24c Cottenceau G. Besson T. Gautier V. Rees CW. Pons A.-M. Bioorg. Med. Chem. Lett.  1996,  6:  529 
    Google Scholar
  • 24d Besson T. Rees CW. Cottenceau G. Pons A.-M. Bioorg. Med. Chem. Lett.  1996,  6:  2343 
    Google Scholar
  • 24e Le V.-D. Rees CW. Sivadasan S. Tetrahedron Lett.  2000,  41:  9407 
    Google Scholar
  • 24f Besson T. Guillard J. Rees CW. J. Chem. Soc., Perkin Trans. 1  2000,  563 
    Google Scholar
  • 24g Le V.-D. Rees CW. Sivadasan S. J. Chem. Soc., Perkin Trans. 1  2002,  1543 
    Google Scholar
  • 24h Besson T. Guillard J. Rees CW. Thiéry V. J. Chem. Soc., Perkin Trans. 1  1998,  889 
    Google Scholar
  • 25 Besson T. Guillard J. Rees CW. Thérisod M. J. Chem. Soc., Chem. Commun.  1997,  881 
    Google Scholar
  • 26 Christoforou IC. Koutentis PA. Michaelidou SS. ARKIVOC  2006,  (vii):  207 
    Google Scholar
  • 27 Oediger H. Möller F. Eiter K. Synthesis  1972,  591 
    Article in Thieme ConnectGoogle Scholar
  • 28 Cowley AH. Acc. Chem. Res.  1984,  17:  386 
    CrossrefGoogle Scholar
  • 29a Fujii M. Ozaki K. Sekine M. Hata T. Tetrahedron  1987,  43:  3395 
    Google Scholar
  • 29b Reed R. Réau R. Dahan F. Bertrand G. Angew. Chem. Int. Ed.  1993,  32:  399 
    Google Scholar
  • 29c Lesnikowski ZJ. Zabawska D. Jaworska-Maslanka MM. Schinazi RF. Stec WJ. New J. Chem.  1994,  18:  1197 
    Google Scholar
  • 29d Dyer P. Guerret O. Dahan F. Baceiredo A. Bertrand G. J. Chem. Soc., Chem. Commun.  1995,  2339 
    Google Scholar
  • 29e Bouhadir G. Reed RW. Réau R. Bertrand G. Heteroat. Chem.  1995,  6:  371 
    Google Scholar
  • 29f Karsch HH. Rupprich T. Heckle M. Chem. Ber.  1995,  128:  959 
    Google Scholar
  • 29g Merckling FA. Rüedi P. Tetrahedron Lett.  1996,  37:  2217 
    Google Scholar
  • 29h Kers A. Stawiński J. Dembkowski L. Kraszewski A. Tetrahedron  1997,  53:  12691 
    Google Scholar
  • 29i Kers A. Kers I. Bollmark M. Stawinski J. Acta Chem. Scand.  1998,  52:  1405 
    Google Scholar
  • 29j Kers A. Kers I. Stawinski J. J. Chem. Soc., Perkin Trans. 2  1999,  2071 
    Google Scholar
  • 29k Blättner M. Nieger M. Ruban A. Schoeller WW. Niecke E. Angew. Chem. Int. Ed.  2000,  39:  2768 
    Google Scholar
  • 29l Ionkin AS. Marshall WJ. Heteroat. Chem.  2003,  14:  197 
    Google Scholar
  • 29m Dąbkowski W. Tworowska I. Kazimierczak Ł. Michalski J. Pol. J. Chem.  2005,  79:  467 
    Google Scholar
  • 30a Richter R. Chem. Ber.  1968,  101:  3002 
    Google Scholar
  • 30b House HO. DeTar MB. VanDerveer D. J. Org. Chem.  1979,  44:  3793 
    Google Scholar
  • 30c McCoy LL. Mal D. J. Org. Chem.  1981,  46:  1016 
    Google Scholar
  • 30d Alder RW. Sessions RB. Tetrahedron Lett.  1982,  23:  1121 
    Google Scholar
  • 30e Juneja TR. Garg DK. Schäfer W. Tetrahedron  1982,  38:  551 
    Google Scholar
  • 30f Forlani L. Sintoni M. Todesco PE. J. Chem. Res., Synop.  1986,  344 
    Google Scholar
  • 30g Collina G. Forlani L. J. Phys. Org. Chem.  1988,  1:  351 
    Google Scholar
  • 30h Forlani L. Cimarelli C. J. Phys. Org. Chem.  1989,  2:  653 
    Google Scholar
  • 30i Reid JG. Runge JMR. Tetrahedron Lett.  1990,  31:  1093 
    Google Scholar
  • 30j Reisch J. Iding M. von Bassewitz I. Monatsh. Chem.  1993,  124:  1225 
    Google Scholar
  • 30k Schenk WA. Urban P. Dombrowski E. Chem. Ber.  1993,  126:  679 
    Google Scholar
  • 30l Chambers RD. Roche AJ. Batsanov AS. Howard JAK. J. Chem. Soc., Chem. Commun.  1994,  2055 
    Google Scholar
  • 30m Lammers H. Cohen-Fernandes P. Habraken CL. Tetrahedron  1994,  50:  865 
    Google Scholar
  • 30n Ma L. Dolphin D. Tetrahedron  1996,  52:  849 
    Google Scholar
  • 30o Johnson MG. Foglesong RJ. Tetrahedron Lett.  1997,  38:  7003 
    Google Scholar
  • 30p Lönnqvist J.-ES. Jalander LF. J. Chem. Res., Miniprint  1999,  0430 
    Google Scholar
  • 31 Sekine M. Kume A. Hata T. Tetrahedron Lett.  1981,  22:  3617 
    CrossrefGoogle Scholar
  • 32a Bard RR. Strauss MJ. J. Am. Chem. Soc.  1975,  97:  3789 
    Google Scholar
  • 32b Miller J. Miyata Y. Sakazaki E. de Santos TW. J. Chem. Res., Synop.  1986,  396 
    Google Scholar
  • 33a Appel R. Janssen H. Siray M. Knoch F. Chem. Ber.  1985,  118:  1632 
    Google Scholar
  • 33b Koutentis PA. Molecules  2005,  10:  346 
    Google Scholar