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Synthesis 2009(15): 2616-2626  
DOI: 10.1055/s-0029-1217399
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Aryl Ring Migration Reaction in the Synthesis of 2,4-Diaryl-4H-3,1-benzothiazines

Alexander V. Butin*a, Fatima A. Tsiunchika, Vladimir T. Abaevb, Andrey V. Gutnovc, Dmitry A. Cheshkovd
a Research Institute of Heterocyclic Compounds Chemistry, Kuban State Technological University, Moskovskaya st. 2, Krasnodar 350072, Russian Federation
Fax: +7(861)2596592.; e-Mail: alexander_butin@mail.ru; e-Mail: av_butin@yahoo.com.;
b North-Ossetian State University, Vatutina St. 46, Vladikavkaz 362025, Russian Federation
c ChiroBlock GmbH, Andresenstr. 1a, 06766 Wolfen, Germany
d State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds, Entuziastov Shosse 38, Moscow 111123, Russian Federation
Further Information

Publication History

Received 2 April 2009
Publication Date:
22 June 2009 (online)

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Abstract

A new rearrangement of 1-(diarylmethyl)-2-isothiocyanatobenzenes into 2,4-diaryl-4H-3,1-benzothiazine derivatives is described. Treatment of the starting compounds with aluminum trichloride under Friedel-Crafts conditions leads to migration of an aryl substituent by an electrophilic ipso-substitution mechanism, followed by cyclization to form a 3,1-benzothiazine ring. The expected intramolecular thiocarbamoylation reaction also takes place, and 5,11-dihydro-6H-dibenzo[b,e]azepine-5-thiones are isolated as byproducts. Factors influencing the mechanism and selectivity of the reaction are discussed. The corresponding 1-(arylmethyl)-2-isothiocyanatobenzene derivatives were also synthesized, and their behavior under Friedel-Crafts reaction conditions was investigated to confirm the crucial role of the stability of the intermediate benzhydryl/benzyl cations in determining the course of the reaction.

Key words

1-(diarylmethyl)-2-isothiocyanatobenzenes - Friedel-Crafts - rearrangement - aryl migration - 3,1-benzothiazines

    References

  • 1 Kim MY, Shin HT, Lee CW, Kim JW, Kim SH, Choi Y, and Son MH. inventors; US  5171851.  ; Chem. Abstr. 1992, 118, 213099
  • 2 Rieu J.-P, Patoiseau J.-F, John GW, Legrand B, and Valentin J.-P. inventors; WO  9705134. (a) ; Chem. Abstr. 1997, 126, 225308
  • 2 Rieu J.-P, Patoiseau J.-F, John G, Legrand B, and Verscheure Y. inventors; WO  0043391. (b) ; Chem. Abstr. 2000, 133, 135319
  • 2 Tamada S, Fujioka T, Ogawa H, Teramoto S, and Kondo K. inventors; JP  1061469. (c) ; Chem. Abstr. 1989, 112, 118837
  • 3 Ogawa H. Tamada S. Fujioka T. Teramoto S. Kondo K. Yamashita S. Yabuuchi Y. Tominaga M. Nakagawa K. Chem. Pharm. Bull.  1988,  36:  2401 
    CrossrefPubMedGoogle Scholar
  • 4 Gauthier JA, and Asselin AA. inventors; CA  1210396.  ; Chem. Abstr. 1986, 106, 176409
  • 5 Jones GH. Venuti MC. Alvarez R. Bruno JJ. Berks AH. Prince A. J. Med. Chem.  1987,  30:  295 
    CrossrefPubMedGoogle Scholar
  • 6 Takasaki T, Sato K, and Abe T. inventors; JP  183282.  ; Chem. Abstr. 2003, 139, 85163
  • 7 Tsubata K, Shimaoka T, Nishida T, Takagi K, Baba K, and Tajima S. inventors; WO  9854163.  ; Chem. Abstr. 1998, 130, 38384
  • 8 Petrie C, Orme MW, Baindur N, Robbins KG, Harris SM, Kontoyianni M, Hurley LH, Kerwin SM, and Mundy GR. inventors; WO  9751308.  ; Chem. Abstr. 1997, 127, 17703
  • 9 Neumann U. Gütschow M. Bioorg. Chem.  1995,  23:  72 
    CrossrefGoogle Scholar
  • 10a Shridhar DR. Rao KS. Bhopale KK. Tripathi HN. Sai GST. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1981,  20:  471 
    Google Scholar
  • 10b Pelosi SS. inventors; US  4002620.  ; Chem. Abstr. 1977, 86, 140074
  • 11 Ishige S, Usui H, and Saeki K. inventors; DE  2704724.  ; Chem. Abstr. 1977, 87, 144134
  • 12a Dondoni A. Battaglia A. Giorgianni P. Gilli G. Sacerdoti M. J. Chem. Soc., Chem. Commun.  1977,  43 
    Google Scholar
  • 12b Dondoni A. Battaglia A. Giorgianni P. J. Org. Chem.  1980,  45:  3766 
    Google Scholar
  • 12c Dondoni A. Battaglia A. Giorgianni P. J. Org. Chem.  1982,  47:  3998 
    Google Scholar
  • 12d Carisi P. Mazzanti G. Zani P. Barbaro G. Battaglia A. Giorgianni P. J. Chem. Soc., Perkin Trans. 1  1987,  2647 
    Google Scholar
  • 13 Gromachevskaya EV. Kosulina TP. Kulnevich VG. Chem. Heterocycl. Compd. (Engl. Transl.)  1993,  29:  460;  Khim. Geterotsikl. Soedin.  1993,  537 
    CrossrefGoogle Scholar
  • 14 Gauthier J. Duceppe JS. J. Heterocycl. Chem.  1984,  21:  1081 
    CrossrefGoogle Scholar
  • 15 Sorkin E. Hinden W. Helv. Chim. Acta.  1949,  32:  63 
    CrossrefPubMedGoogle Scholar
  • 16 El-Desoky SI. Kandeel EM. Abd-el-Rahman AH. Schmidt RR. J. Heterocycl. Chem.  1999,  36:  153 
    CrossrefGoogle Scholar
  • 17a Beilenson B. Hamer FM. Rathbone RJ. J. Chem. Soc.  1945,  222 
    Google Scholar
  • 17b Lednicer D. Emmert DE. J. Heterocycl. Chem.  1971,  8:  903 
    Google Scholar
  • 18 Hari A. Miller BL. Org. Lett.  2000,  2:  3667 
    CrossrefPubMedGoogle Scholar
  • 19 Tarraga A. Molina P. Lopez JL. Tetrahedron Lett.  2000,  41:  4895 
    CrossrefGoogle Scholar
  • 20 Gonda J. Kristian P. Collect. Czech. Chem. Commun.  1986,  51:  2802 
    CrossrefGoogle Scholar
  • 21 Gonda J. Kristian P. Collect. Czech. Chem. Commun.  1986,  51:  2810 
    CrossrefGoogle Scholar
  • 22a Nishio T. Sekiguchi H. Heterocycles  2002,  58:  203 
    Google Scholar
  • 22b Nishio T. J. Org. Chem.  1997,  62:  1106 
    Google Scholar
  • 23 Lee H. Kim K. Heteroat. Chem.  1993,  4:  263 
    CrossrefGoogle Scholar
  • 24 Besson T. Guillaumet G. Lamazzi C. Rees CW. Synlett  1997,  704 
    Article in Thieme ConnectGoogle Scholar
  • 25 Besson T. Guillaumet G. Lamazzi C. Rees CW. Thiery V. J. Chem. Soc., Perkin Trans. 1  1998,  4057 
    CrossrefGoogle Scholar
  • 26a Dean WD. Papadopoulos EP. J. Heterocycl. Chem.  1982,  19:  1117 
    Google Scholar
  • 26b Looney-Dean V. Lindamood BS. Papadopoulos EP. Synthesis  1984,  68 
    Google Scholar
  • 26c Deck LM. Turner SD. Deck JA. Papadopoulos EP. J. Heterocycl. Chem.  2001,  38:  343 
    Google Scholar
  • 27a Butin AV. Abaev VT. Stroganova TA. Gutnov AV. Molecules  1997,  2:  62 
    Google Scholar
  • 27b Abaev VT. Tsiunchik FA. Gutnov AV. Butin AV. J. Heterocycl. Chem.  2008,  45:  475 
    Google Scholar
  • 28a Jones G. McKinley WH. J. Chem. Soc., Perkin Trans. 1  1979,  599 
    Google Scholar
  • 28b Schneider CS. Pook KH. J. Chem. Soc., Perkin Trans. 1  1986,  877 
    Google Scholar
  • 28c Abaev VT. Gutnov AV. Butin AV. Zavodnik VE. Tetrahedron  2000,  56:  8933 
    Google Scholar
  • 28d Butin AV. Tsiunchik FA. Abaev VT. Zavodnik VE. Synlett  2008,  1145 
    Google Scholar
  • 29 Abaev VT. Tsiunchik FA. Gutnov AV. Butin AV. Tetrahedron Lett.  2006,  47:  4029 
    CrossrefGoogle Scholar
  • 30a Gittos MW. Robinson MR. Verge JP. Davies RV. Iddon B. Suschitzky H. J. Chem. Soc., Perkin Trans. 1  1976,  33 
    Google Scholar
  • 30b Davies RV. Iddon B. Paterson TMcC. Pickering MW. Suschitzky H. Gittos M. J. Chem. Soc., Perkin Trans. 1  1976,  138 
    Google Scholar
  • 30c Davies RV. Iddon B. Suschitzky H. Pickering MW. Gallagher PT. Gittos MW. Robinson MD. J. Chem. Soc., Perkin Trans. 1  1977,  2357 
    Google Scholar
  • 30d Molina P. Alcantara J. Lopez-Leonardo C. Tetrahedron  1996,  52:  5833 
    Google Scholar
  • 30e Duceppe JS. Gauthier J. J. Heterocycl. Chem.  1984,  21:  1685 
    Google Scholar
  • 31 Tolstay TP. Vanchikov AN. Vinnik EV. Asulyan LD. Chem. Heterocycl. Compd. (Engl. Transl.)  1999,  35:  978;  Khim. Geterotsikl. Soedin.  1999,  1112 
    CrossrefGoogle Scholar
  • 32 Weissman SA. Zewge D. Tetrahedron  2005,  61:  7833 
    CrossrefGoogle Scholar
  • 33 Butin AV. Smirnov SK. Stroganova TA. Bender W. Krapivin GD. Tetrahedron  2007,  63:  474 
    CrossrefGoogle Scholar