PDF herunterladen
Synthesis 2008(17): 2701-2706  
DOI: 10.1055/s-2008-1067214
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Novel Approach to Pyrrolo[2,1-b][1,3]benzothiazines

Anton V. Tverdokhlebov*a, Alexander P. Andrushkoa, Andrey A. Tolmacheva,b, Svitlana V. Shishkinac, Oleg V. Shishkinc
a Enamine Ltd., Alexandra Matrosova Street 23, 01103 Kiev, Ukraine
Fax: +380(44)5373253; e-Mail: atver@univ.kiev.ua;
b Kiev National Taras Shevchenko University, Volodimirska Street 62, 01033 Kiev, Ukraine
c STC ‘Institute for Single Crystals’, NAS of Ukraine, 60 Lenina Avenue, 61001 Khar’kiv, Ukraine
Weitere Informationen

Publikationsverlauf

Received 7 April 2008
Publikationsdatum:
06. August 2008 (online)

   Lizenzen und Reprints Alle Artikel dieser Rubrik
Preview

Abstract

Alkylation of (3,4-dihydro-4-oxo-2H-1,3-benzothiazin-2-ylidene)acetic acid ethyl ester and (3,4-dihydro-4-oxo-2H-1,3-benzothiazin-2-ylidene)acetonitrile with phenacyl chlorides in the presence of potassium carbonate was shown to occur at the nitrogen atom yielding the corresponding N-phenacyl derivatives. The latter, upon treatment with DMF˙POCl3 complex, were converted into 1-aroyl-9-oxo-9H-pyrrolo[2,1-b][1,3]benzothiazine-3-carboxylic acid ethyl esters and -3-carbonitriles. The structure of the obtained pyrrolobenzothiazine derivatives was confirmed unambiguously by X-ray crystallographic study. Reaction of these pyrrolo[2,1-b][1,3]benzothiazines with aliphatic primary amines resulted in the thiazine ring cleavage and formation of 2-[(5-aroyl-3-cyano(or ethoxycarbonyl)-1H-pyrrol-2-yl)thio]-N-alkylbenzamides.

Key words

alkylations - cleavage - cyclizations - heterocycles - pyrroles

    References

  • 1 Boehme H. Boeing H. Arch. Pharm. (Weinheim, Ger.)  1961,  294:  556 
    CrossrefSuche in Google Scholar
  • 2a Hucher N. Daich A. Netchitailo P. Decroix B. Tetrahedron Lett.  1999,  40:  3363 
    Suche in Google Scholar
  • 2b Hucher N. Decroix B. Daich A. J. Org. Chem.  2001,  66:  4695 
    Suche in Google Scholar
  • 2c Hucher N. Pesquet A. Netchitailo P. Daich A. Eur. J. Org. Chem.  2005,  2758 
  • 2d Rothe M. Steinberger R. Tetrahedron Lett.  1970,  649 
  • 2e Rothe M. Steinberger R. Tetrahedron Lett.  1970,  2467 
  • 3a Garofalo A. Campiani G. Nacci V. Fiorini I. Heterocycles  1992,  34:  51 
    Suche in Google Scholar
  • 3b Tafel KA. Bates DK. J. Org. Chem.  1992,  57:  3676 
    Suche in Google Scholar
  • 3c Bates DK. Tafel KA. J. Org. Chem.  1994,  59:  8076 
    Suche in Google Scholar
  • 4a Duncia JV. Santella JB. Higley CA. Pitts WJ. Wityak J. Frietze WE. Rankin FW. Sun J.-H. Earl RA. Tabaka AC. Teleha CA. Blom KF. Favata MF. Manos EJ. Daulerio AJ. Stradley DA. Horiuchi K. Copeland RA. Scherle PA. Trzaskos JM. Magolda RL. Trainor GL. Wexler RR. Hobbs FW. Olson RE. Bioorg. Med. Chem. Lett.  1998,  8:  2839 
    Suche in Google Scholar
  • 4b Beveridge S. Harris RLN. Aust. J. Chem.  1971,  24:  1229 
    Suche in Google Scholar
  • 5 Beckwith ALJ. Boate DR. J. Org. Chem.  1988,  53:  4339 
    Suche in Google Scholar
  • 6a Tverdokhlebov AV. Andrushko AP. Tolmachev AA. Synthesis  2006,  1433 
  • 6b Tverdokhlebov AV. Andrushko AP. Tolmachev AA. Kostyuk AN. Chernega AN. Rusanov EB. Monatsh. Chem.  2005,  136:  1781 
    Suche in Google Scholar
  • 6c Tverdokhlebov AV. Resnyanska EV. Tolmachev AA. Andrushko AP. Synthesis  2003,  2632 
  • 7 Satzinger G. Liebigs Ann. Chem.  1978,  473 
  • 8 Zefirov NS. Palyulin VA. Dashevskaya EE. J. Phys. Org. Chem.  1990,  3:  147 
    CrossrefSuche in Google Scholar
  • 9 Burgi H.-B. Dunitz JD. Structure Correlation   Vol. 2:  VCH; Weinheim: 1994.  p.741 
    Suche in Google Scholar
  • 10a Tverdokhlebov AV. Andrushko AP. Resnyanska EV. Tolmachev AA. Synthesis  2004,  2317 
  • 10b Guillaumel J. Leonce S. Pierre A. Renard P. Pfeiffer B. Arimondo PB. Monneret C. Eur. J. Med. Chem.  2006,  41:  379 
    Suche in Google Scholar
  • 10c Flitsch W. Niehoff A. Liebigs Ann. Chem.  1989,  239 
  • 10d Black DStC. Bowyer MC. Catalano MM. Ivory AJ. Keller PA. Kumar N. Nugent SJ. Tetrahedron  1994,  50:  10497 
    Suche in Google Scholar
  • 10e Haynes HF. Nelson ER. Price JR. Aust. J. Sci. Res.  1952,  A5:  563 
    Suche in Google Scholar
  • 10f Fabris F. Sopkova de Oliveira Santos J. Fouchet-Jolivet S. Rault S. Tetrahedron Lett.  2001,  42:  5183 
    Suche in Google Scholar
  • 11a Kamal A. Sandbhor M. Ahmed K. Adil SF. Ahaik AA. Tetrahedron: Asymmetry  2003,  14:  3861 
    Suche in Google Scholar
  • 11b Rao VS. Gupta SVSAK. Gupta CNVHB. Synth. Commun.  2000,  30:  2763 
    Suche in Google Scholar
  • 12 Sheldrick GM. SHELXTL PLUS. PC Version. A System of Computer Programs for the Determination of Crystal Structure from X-ray Diffraction Data. Rev. 5.1   University of Göttingen; Göttingen: 1998. 
13

Full crystallographic parameters have been deposited at Cambridge Crystallographic Data Center under reference number CCDC 681250. Copies of the data may be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223 33603 or e-mail: deposit@ccdc.cam.ac.uk).