Download PDF
Synlett 2011(18): 2750-2756  
DOI: 10.1055/s-0031-1289541
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Mild and Efficient Synthesis of Aryl Sulfones from Aryl Chlorides and Sulfinic Acid Salts Using Microwave Heating

Yan-qin Yuan, Sheng-rong Guo*
Department of Chemistry, Lishui University, 323000 Zhejiang, P. R. of China
e-Mail: guosr9609@lsu.edu.cn;
Further Information

Publication History

Received 3 August 2011
Publication Date:
19 October 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

The CuCl-catalyzed coupling of aryl chlorides and sulfinic acid salts provides a simple and extremely efficient route to unsymmetrical aryl sulfones in high to excellent yields under microwave irradiation within 3-30 minutes.

Key words

aryl chloride - microwave - sulfone - sulfinic acid salts - quinoline - CuCl

    References and Notes

  • 1 Simpkins NS. Sulfones in Organic Synthesis   Pergamon Press; Oxford: 1993. 
    Google Scholar
  • 2a Yoshino T. inventors; JP  2001260544.  ; Chem. Abstr. 2001, 135, 264604
  • 2b Otzen T. Wempe EG. Kunz B. Bartels R. Lehwark-Yvetot G. Hänsel W. Schaper K.-J. Seydel JK. J. Med. Chem.  2004,  47:  240 
    Google Scholar
  • 3a Sun Z.-Y. Botros E. Su A.-D. Kim Y. Wang E. Baturay NZ. Kwon C.-H. J. Med. Chem.  2000,  43:  4160 
    Google Scholar
  • 3b Faucher A.-M. White PW. Brochu C. Grand-Maitre C. Rancourt J. Fazal G. J. Med. Chem.  2004,  47:  18 
    Google Scholar
  • 4 Takahashi T, and Yoshino T. inventors; JP  2001260544.  ; Chem. Abstr. 2001, 135, 264604
  • 5 Prasit P. Wang Z. Brideau C. Chan C.-C. Charleston S. Cromlish W. Ethier D. Evans JF. Ford-Hutchinson AW. Gauthier JY. Gordon R. Guay J. Gresser M. Kargman S. Kennedy B. Leblanc Y. Léger S. Mancini J. ONeill GP. Ouellet M. Percival MD. Perrier H. Riendeau D. Rodger I. Tagari P. Thérien M. Vickers P. Wong E. Xu L.-J. Young RN. Zamboni R. Bioorg. Med. Chem. Lett.  1999,  9:  1773 
    Google Scholar
  • 6 Sturino CF. Lachance N. Boyd M. Berthelette C. Labelle M. Li L. Roy B. Scheigetz J. Tsou N. Aubin Y. BatemanK P. Chauret N. Day SH. Levesque J.-F. Seto C. Silva JH. Trimble LA. Carriere M.-C. Denis D. Greig G. Kargman S. Lamontagne S. Mathieu M.-C. Sawyer N. Slipetz D. Abraham WM. Jones T. McAuliffe M. Piechuta H. Nicoll-Griffith DA. Wang Z. Zamboni R. Young RN. J. Med. Chem.  2007,  50:  794 
    Google Scholar
  • 7 Schank K. In The Chemistry of Sulfones and Sulfoxides   Patai S. Rappoport Z. Stirling CJM. Wiley; New York: 1988.  Chap. 7.
    Google Scholar
  • 8a Gilman H. Beaver NJ. Meyers CH. J. Am. Chem. Soc.  1925,  47:  2047 
    Google Scholar
  • 8b Baarshers WH. Can. J. Chem.  1976,  54:  3056 
    Google Scholar
  • 9a Truce WE. Klinger TC. Brand WW. In Organic Chemistry of Sulfur   Plenum Press; New York: 1977. 
    Google Scholar
  • 9b Graybill BM. J. Org. Chem.  1967,  32:  2931 
    Google Scholar
  • 10a Suzuki H. Abe H. Tetrahedron Lett.  1995,  36:  6239 
    Google Scholar
  • 10b Baskin JM. Wang Z. Org. Lett.  2002,  4:  4423 
    Google Scholar
  • 10c Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Org. Lett.  2002,  4:  4719 
    Google Scholar
  • 10d Zhu W. Ma D. J. Org. Chem.  2005,  70:  2696 
    Google Scholar
  • 10e Bian M. Xu F. Ma C. Synthesis  2007,  2951 
    Google Scholar
  • 11a Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Synlett  2003,  361 
    Google Scholar
  • 11b Cacchi S. Fabrizi G. Goggiamani A. Parisi LM. Bernini R. J. Org. Chem.  2004,  69:  5608 
    Google Scholar
  • 12a Bandgar BP. Bettigeri SV. Phopase J. Org. Lett.  2004,  6:  2105 
    Google Scholar
  • 12b Dubbaka SR. Vogel P. Chem. Eur. J.  2005,  11:  2633 
    Google Scholar
  • 12c Anirban K. Iliyas AS. Luo WF. Kaiser HM. Beller M. Tse MK. Org. Lett.  2007,  9:  3405 
    Google Scholar
  • 12d Bandgar BP. Bettigeri SV. Phopase J. Org. Lett.  2004,  6:  2105 
    Google Scholar
  • 13a Roberts BA. Strauss CR. Acc. Chem. Res.  2005,  38:  653 
    Google Scholar
  • 13b Arvela RK. Leadbeater NE. J. Org. Chem.  2003,  68:  9122 
    Google Scholar
  • 14 Sauer DR. Kalvin D. Phelan KM. Org. Lett.  2003,  5:  4721 
    Google Scholar
  • 15 Lei S. Wang M. Fan C.-A. Zhang F.-M. Tu Y.-Q. Org. Lett.  2003,  5:  3515 
    Google Scholar
  • 16 Kwong FY. Buchwald SL. Org. Lett.  2003,  5:  793 
    Google Scholar
  • 17 Zou J. Li F. Tao FG. Chin. Chem. Lett.  2009,  20:  17 
    Google Scholar
  • 18a Zhang H. Cai Q. Ma D. J. Org. Chem.  2005,  70:  5164 
    Google Scholar
  • 18b Paine AJ. J. Am. Chem. Soc.  1987,  109:  1496 
    Google Scholar
  • 18c Chow WS. Chan TH. Tetrahedron Lett.  2009,  50:  1286 
    Google Scholar
19

Typical Procedure
Aryl halides (1.0 mmol), CuCl (10% mol), quinoline (10% mol), and sulfinic acid salts added to NMP (1.5 mL) MW 250 W at 140 ˚C for the indicated time. The reaction was found not to be sensitive to air and moisture; hence there
was no need for an inert atmosphere. With the use of a microwave power of 250 W, the reaction mixture was ramped from r.t. to 140-150 ˚C over 30 s, and then held
at this temperature for another 3-30 min until complete consumption of starting material (GC monitoring). After being cooled to rt, the resulting mixture was mixed with
an ample amount of ice water, extracted with EtOAc. The resulting solution was washed with H2O and concentrated
to yield the product, which was purified by silica gel chromatography to give the 1-methyl-4-(4-nitrophenyl-sulfonyl)benzene in 90% yield. ¹H NMR (300 MHz, CDCl3): δ = 8.27 (d, J = 7.0 Hz, 2 H), 8.05 (d, J = 7.0 Hz, 2 H), 7.78 (d, J = 8.2 Hz, 1 H), 7.28 (d, J = 8.0 Hz, 2 H), 2.35 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 150.1, 147.8, 145.3, 137.0, 130.3, 128.8, 128.1, 124.4, 21.6. The identity and purity of other products was confirmed by ¹H NMR and ¹³C NMR spectroscopic analysis.