Download PDF
Synlett 2009(18): 3032-3036  
DOI: 10.1055/s-0029-1218276
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Tandem Reaction of 2-Haloaniline Derivatives with Tetraalkylthiuram Disulfides: Selective Synthesis of 2-Aminobenzothiazoles

Sha-Sha Pi, Xing-Guo Zhang, Ri-Yuan Tang, Jin-Heng Li*
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China
Fax: +86(577)88368607; e-Mail: jhli@wzu.edu.cn;
Further Information

Publication History

Received 17 July 2009
Publication Date:
09 October 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

A simple and efficient protocol for the synthesis of 2-aminobenzothiazoles by copper-catalyzed tandem reaction has been developed. In the presence of CuBr and Cs2CO3, a variety of 2-haloanilines underwent the reaction with tetramethylthiuram di­sulfide (TMTD) efficiently to afford the corresponding 2-aminobenzothiazoles in moderate to excellent yields. The present process allows the construction of 2-aminobenzothiazoles from a wide range of 2-haloaniline derivatives, including 2-iodoanilines, 2-bromoanilines, and 2-chloroanilines.

Key words

copper - tandem reaction - 2-haloanilimine - tetraalkyl­thiuram disulfides - 2-aminobenzothiazoles

    References and Notes

  • For selected recent examples, see:
  • 1a Kok SHL. Gambari R. Chui CH. Yuen MCW. Lin E. Wong RSM. Lau FY. Cheng GYM. Lam WS. Chan SH. Lam KH. Cheng CH. Lai PBS. Yu MWY. Cheung F. Tang JCO. Chan ASC. Bioorg. Med. Chem.  2008,  16:  3626 
    Google Scholar
  • 1b Liu C. Lin J. Pitt S. Zhang RF. Sack JS. Kiefer SE. Kish K. Doweyko AM. Zhang H. Marathe PH. Trzaskos J. Mckinnon M. Dodd JH. Barrish JC. Schieven GL. Leftheris K. Bioorg. Med. Chem. Lett.  2008,  18:  1874 
    Google Scholar
  • 1c Henriksen G. Hauser AI. Westwell AD. Yousefi BH. Schwaiger M. Drzezga A. Wester H.-J. J. Med. Chem.  2007,  50:  1087 
    Google Scholar
  • 2 Suter H. Zutter H. Helv. Chim. Acta  1967,  50:  1084 
    CrossrefPubMedGoogle Scholar
  • 3a Hays SJ. Rice MJ. Ortwine DF. Johnson G. Schwartz RD. Boyd DK. Copeland LF. Vartanian MG. Boxer PA. J. Pharm. Sci.  1994,  83:  1425 
    Google Scholar
  • 3b Jimonet P. Audiau F. Barreau M. Blanchard JC. Boireau A. Bour Y. Coleno M.-A. Doble A. Doerflinger G. Huu CD. Donat M.-H. Duchesne JM. Ganil P. Gueremy C. Honore E. Just B. Kerphirique R. Gontier S. Hubert P. Laduron PM. Le Blevec J. Meunier M. Miquet JM. Nemecek C. Pasquet M. Piot O. Pratt J. Rataud J. Reibaud M. Stutzmann JM. Mignani S. J. Med. Chem.  1999,  42:  2828 
    Google Scholar
  • 3c He Y. Benz A. Fu T. Wang M. Covey DF. Zorumski CF. Mennick S. Neuropharmacology  2002,  42:  199 
    Google Scholar
  • 4 Shirke VG. Bobade AS. Bhamaria RP. Khadse BG. Sengupta SR. Indian Drugs  1990,  27:  350 
    Google Scholar
  • For aldehydes, see:
  • 5a Ranu BC. Jana R. Dey S. Chem. Lett.  2004,  33:  274 
    Google Scholar
  • 5b Itoh T. Nagata K. Ishikawa H. Ohsawa A. Heterocycles  2004,  63:  2769 
    Google Scholar
  • 5c Kawashita Y. Ueba C. Hayashi M. Tetrahedron Lett.  2006,  47:  4231 
    Google Scholar
  • 5d Li Y. Wang Y.-L. Wang J.-Y. Chem. Lett.  2006,  35:  460 
    Google Scholar
  • 5e Pratap UR. Mali JR. Jawale DV. Mane RA. Tetrahedron Lett.  2009,  50:  1352 
    Google Scholar
  • 5f Kumar A. Maurya RA. Ahmad P. J. Comb. Chem.  2009,  11 198 
    Google Scholar
  • For carboxylic acid, see:
  • 5g Hein DW. Alhein RJ. Leavitt JJ. J. Am. Chem. Soc.  1957,  79:  427 
    Google Scholar
  • 5h Ge F.-L. Wang Z.-X. Wan W. Lu W.-C. Hao J. Tetrahedron Lett.  2007,  48:  3251 
    Google Scholar
  • 6a Jordan AD. Luo C. Retiz AB. J. Org. Chem.  2003,  68:  8693 
    Google Scholar
  • 6b Mu X.-J. Zou J.-P. Zeng R.-S. Wu J.-C. Tetrahedron Lett.  2005,  46:  4345 
    Google Scholar
  • 6c Bose DS. Idrees M. J. Org. Chem.  2006,  71:  8261 
    Google Scholar
  • 6d Bose DS. Idrees M. Tetrahedron Lett.  2007,  48:  669 
    Google Scholar
  • 6e Bose DS. Idrees M. Srikanth B. Synthesis  2007,  819 
    Google Scholar
  • 6f Downer-Riley NK. Jackson YA. Tetrahedron  2008,  64:  7741 
    Google Scholar
  • 6g Inamoto K. Hasegawa C. Hiroya K. Doi T. Org. Lett.  2008,  10:  5147 
    Google Scholar
  • 6h Thiel OR. Bernard C. King T. Dilmeghani-Seran M. Bostick T. Larsen RD. Faul MM. J. Org. Chem.  2008,  73:  3508 
    Google Scholar
  • 6i Pande S. Saha A. Jana S. Sarkar S. Basu M. Pradhan M. Sinha AK. Saha S. Pal A. Pal T. Org. Lett.  2009,  11:  2792 
    Google Scholar
  • 7a Benedi C. Bravo F. Uriz P. Fernandez E. Claver C. Castillon S. Tetrahedron Lett.  2003,  44:  6073 
    Google Scholar
  • 7b Joyce LL. Evindar G. Batey RA. Chem. Commun.  2004,  446 
    Google Scholar
  • 7c Evindar G. Batey RA. J. Org. Chem.  2006,  71:  1802 
    Google Scholar
  • 7d Vera MD. Pelletier JC. J. Comb. Chem.  2007,  9:  569 
    Google Scholar
  • 7e Itoh T. Mase T. Org. Lett.  2007,  9:  3687 
    Google Scholar
  • 7f Ding Q. He X. Wu J. J. Comb. Chem.  2009,  11:  587 
    Google Scholar
  • 8a Grunwell JR. J. Org. Chem.  1970,  35:  1500 
    Google Scholar
  • 8b Priefer R. Lee YJ. Barrios F. Wosnick JH. Lebuis AM. Farrell PG. Harpp DN. Sun A. Wu S. Snyder JP. J. Am. Chem. Soc.  2002,  124:  5626 
    Google Scholar
  • 8c Krasovskiy A. Gavryushin A. Knochel P. Synlett  2005,  2691 
    Google Scholar
  • 8d Krasovskiy A. Gavryushin A. Knochel P. Synlett  2006,  792 
    Google Scholar
  • 8e Krasovskiy A. Malakhov V. Gavryushin A. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  6040 
    Google Scholar
  • 9a Tang R.-Y. Zhong P. Lin Q.-L. J. Fluor. Chem.  2006,  127:  948 
    Google Scholar
  • 9b Tang R.-Y. Zhong P. Lin Q.-L. Synthesis  2007,  85 
    Google Scholar
  • 9c Wang Z.-L. Tang R.-Y. Luo P.-S. Deng C.-L. Zhong P. Li J.-H. Tetrahedron  2008,  64:  10670 
    Google Scholar
  • 9d Luo P.-S. Yu M. Tang R.-Y. Zhong P. Li J.-H. Tetrahedron Lett.  2009,  50:  1066 
    Google Scholar
  • 9e Luo P.-S. Wang F. Li J.-H. Tang R.-Y. Zhong P. Synthesis  2009,  921 
    Google Scholar
10

General Procedure for the Copper-Catalyzed Tandem Reaction of 2-Haloanilimine Derivatives with Tetraalkylthiuram Disulfides A flame-dried Schlenk tube with a magnetic stirring bar was charged with 2-haloanilimine derivative 1 (0.2 mmol), tetraalkylthiuram disulfide (0.15 mmol), CuBr (1.4 mg, 0.01 mmol), Cs2CO3 (196 mg, 0.6 mmol), and DMSO (1 mL). The reaction mixture was stirred at 80 ˚C for the indicated time (Tables  [¹] and  [²] ) until complete consumption of starting material as monitored by TLC and GC-MS analysis. After the reaction was finished, the mixture was poured into EtOAc, washed with brine (3 × 10 mL), and extracted with EtOAc. The combined organic layers were dried over anhyd Na2SO4 and evaporated under vacuum. The residue was purified by flash column chromatography (hexane-EtOAc) to afford the desired product.
N , N -Dimethy-6-(trifluoromethyl)benzo[ d ]thiazol-2-amine (4)
Mp 98.5-101.1 ˚C(uncorrected). ¹H NMR (300 MHz, CDCl3): δ = 7.84 (s, 1 H), 7.58 (d, J = 8.5 Hz, 1 H), 7.52 (d, J = 8.5 Hz, 1 H), 3.22 (s, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 170.3, 155.8, 131.2, 124.6 (q, J C-F = 269.9 Hz, 1 C), 123.4, 122.8 (d, J C-F = 32.2 Hz, 1 C), 122.1, 118.0, 40.2. ¹9F NMR (283 MHz, CDCl3): δ = -60.79. IR (KBr): 2913, 1616, 1573, 1337, 1145, 1099 cm-¹. LRMS (EI, 70 eV): m/z (%) = 246 (93) [M+], 217 (100). ESI-HRMS: m/z calcd for C10H10F3N2S+ [M + H]+: 247.0511; found: 247.0503.