One-Pot, Regioselective Consecutive Multihalogenation of 2,2′-Bithiophene
Bo Ram Kim
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorEun Jung Kim
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorGi Hyeon Sung
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorJeum-Jong Kim
Advanced Solar Technology Research Department, Electronics and Telecommunications Research Institute, Daejeon 305-700, Korea
Search for more papers by this authorDong-Soo Shin
Department of Chemistry, Changwon National University, Changwon, GN 641-773, Korea, Fax: +82-55-2133439
Search for more papers by this authorSang-Gyeong Lee
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorYong-Jin Yoon
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorBo Ram Kim
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorEun Jung Kim
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorGi Hyeon Sung
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorJeum-Jong Kim
Advanced Solar Technology Research Department, Electronics and Telecommunications Research Institute, Daejeon 305-700, Korea
Search for more papers by this authorDong-Soo Shin
Department of Chemistry, Changwon National University, Changwon, GN 641-773, Korea, Fax: +82-55-2133439
Search for more papers by this authorSang-Gyeong Lee
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorYong-Jin Yoon
Department of Chemistry & Research Institute of Natural Sciences Department of Chemistry, Graduate School for Molecular Materials and Nanochemistry, Gyeongsang National University, Jinju Gyeognam 660-701, Korea, Fax: +82-55-7721489, http://nongae.gsnu.ac.kr/~yjyoon/
Search for more papers by this authorGraphical Abstract
The regioselective consecutive multihalogenation of 2,2′-bithiophene as a model compound was demonstrated by using lithium halides and lead tetraacetate in chloroform in one pot. This method offers new possibilities for the control of the regioselectivity and the multiplicity in the halogenation of electron-rich aromatic compounds.
Abstract
The one-pot regioselective consecutive multihalogenation of 2,2′-bithiophene (1) was demonstrated. Compound 1 was consecutively halogenated with lithium halides such as lithium bromide, chloride, and/or iodide in the presence of lead tetraacetate in chloroform at room temperature or under reflux conditions to give 5-bromo(or chloro)-5′-iodo(or chloro)-, 3-bromo(or chloro)-5,5′-dibromo(or dichloro, diiodo)-, 3,3′-dibromo-(or dichloro)-5,5′-diiodo(or dibromo, dichloro)-, and 3,3′,5-tribromo(or trichloro)-5′-iodo(or bromo)-2,2′-bithiophenes. Notably, this process offers a regioselective method for consecutive multihalogenation in one pot, and the yields and selectivity are also higher than those obtained in the step-by-step and concurrent halogenation methods.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| ejoc_201300379_sm_miscellaneous_information.pdf1 MB | miscellaneous_information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1 For selected examples, see:
- 1a J. J. Kim , D. H. Kweon , S. D. Cho , H. K. Kim , S. G. Lee , Y. J. Yoon , Synlett 2006 , 2 , 194 –200 .
- 1b
A. S. Dudnik
, N. Chernyak
, C. Huang
, V. Gevorgyan
, Angew. Chem.
2010
, 122
, 8911
; Angew. Chem. Int. Ed.
2010
, 49
, 8729
–8732
.
10.1002/ange.201004426 Google Scholar
- 1c G. K. S. Prakash, T. Mathew , D. Hoole , P. M. Esteves , Q. Wang , G. Rasul , G. A. Olah , J. Am. Chem. Soc. 2004 , 126 , 15770 –15776 .
- 1d X. Wan , Z. Ma , B. Li , K. Zhang , S. Cao , S. Zhang , Z. Shi , J. Am. Chem. Soc. 2006 , 128 , 7416 –7417 .
- 1e J. M. Murphy , X. Liao , J. F. Hartwig , J. Am. Chem. Soc. 2007 , 129 , 15434 –15435 .
- 1f M. L. Ho , A. B. Flynn , W. W. Ogilvie , J. Org. Chem. 2007 , 72 , 977 –983 .
- 1g D. Kalyani , A. R. Dick , W. Q. Anani , M. S. Sanford , Org. Lett. 2006 , 8 , 2523 –2526 .
- 1h G. Majetich , R. Hicks , S. Reister , J. Org. Chem. 1997 , 62 , 4321 –4326 .
- 2a E. M. Kosower , W. J. Cole , G. S. Wu , D. E. Cardy , G. Meister , J. Org. Chem. 1963 , 28 , 630 –633 .
- 2b L. C. King , G. K. Ostrum , J. Org. Chem. 1964 , 29 , 3459 –3461 .
- 3 E. W. Warnhoff , D. G. Martin , W. S. Johnson (Eds.), Org. Synth., Coll. Vol. IV, John Wiley & Sons, New York, 1963 , p. 162.
- 4 K. M. Brummond , K. D. Gesenberg , Tetrahedron Lett. 1999 , 40 , 2231 –2234 .
- 5 J. C. Lee , J. Y. Park , S. Y. Yoon , Y. H. Bae , S. J. Lee , Tetrahedron Lett. 2004 , 45 , 191 –193 .
- 6
T. Schlama
, K. Gabriel
, V. Gouverneur
, C. Mioskowski
, Angew. Chem.
1997
, 109
, 2440
; Angew. Chem. Int. Ed. Engl.
1997
, 36
, 2342
–2344
.
10.1002/ange.19971092117 Google Scholar
- 7 D. Yang , Y.-L. Yan , B. Lui , J. Org. Chem. 2002 , 67 , 7429 –7431 .
- 8 H. Poisel , U. Schmidt , Angew. Chem. 1976 , 88 , 295 ; Angew. Chem. Int. Ed. Engl. 1976 , 15 , 294 –295 .
- 9 B. Daoust , J. Lessard , Tetrahedron 1999 , 55 , 3495 –3514 .
- 10
B. Miosses
, R. Danion-Bougot
, D. Danion
, Synthesis
1994
, 1171
–1174
.
10.1055/s-1994-25666 Google Scholar
- 11 S. P. L. de Souza , J. F. M. da Silva , M. C. S. de Matts , Synth. Commun. 2003 , 33 , 935 –939 .
- 12 O. V. Larionov , S. I. Kozhushkov , A. de Meijere , Synthesis 2003 , 1916 –1919 .
- 13 Y. D. Park , J. J. Kim , S. G. Lee , J. R. Farlck , Y. J. Yoon , Synthesis 2005 , 1136 –1140 .
- 14 M. Marigo , N. Kumaragurubaran , K. A. Jorgensen , Chem. Eur. J. 2004 , 10 , 2133 –2137 .
- 15 R. S. Drago , D. A. Wenz , R. L. Carlson , J. Am. Chem. Soc. 1962 , 84 , 1106 –1109 .
- 16 C. Bachand , H. Driguez , J. M. Paton , D. Touchard , J. Lessard , J. Org. Chem. 1974 , 39 , 3136 –3138 .
- 17 M. Curini , F. Epifano , M. C. Marcotullio , O. Rosati , A. Tsadjout , Synlett 2000 , 813 –814 .
- 18 L. D. Luca , G. Giacomelli , G. Nieddu , Synlett 2005 , 223 –226 .
- 19 For selected examples, see:
- 19a K. R. J. Thomas, Y.-C. Hus , J. T. Lin , K.-M. Lee , K.-C. Ho , C.-H. Lai , Y.-M. Cheng , P.-T. Chou , Chem. Mater. 2008 , 20 , 1830 –1840 .
- 19b R. Yamada , H. Kumazawa , T. Noutoshi , S. Tanaka , H. Tada , Nano Lett. 2008 , 8 , 1237 –1240 .
- 19c Z.-Y. Yang , H.-M. Zhang , G.-B. Pan , L.-J. Wan , ACS Nano 2008 , 2 , 743 –749 .
- 19d F. Nishiyama , K. Ogawa , S. Tanaka , T. Yokoyama , J. Phys. Chem. B 2008 , 112 , 5272 –5275 .
- 19e J. M. Hancock , A. P. Gifford , R. D. Champion , S. A. Jenekhe , Macromolecules 2008 , 41 , 3588 –3597 .
- 19f R. O. Steen , L. J. Nurkkala , S. J. Angus-Dunne , C. X. Schmitt , E. C. Constable , M. J. Riley , P. V. Bernhardt , S. J. Dunne , Eur. J. Inorg. Chem. 2008 , 1784 –1794 .
- 19g O. A. Gus'kova , P. G. Khalatur , P. Bäuerle , A. R. Khokhlov , Chem. Phys. Lett. 2008 , 461 , 64 –70 .
- 19h Y. A. Getmanenko , R. J. Twieg , J. Org. Chem. 2008 , 73 , 830 –839 .
- 19i S. Zrig , G. Koeckelberghs , T. Verbiest , B. Andrioletti , E. Rose , A. Persoons , I. Asselberghs , K. Clays , J. Org. Chem. 2007 , 72 , 5855 –5858 .
- 19j J. Hassan , C. Gozzi , E. Schulz , M. Lemaire , J. Organomet. Chem. 2003 , 687 , 280 –283 .
- 19k H. Usta , G. Lu , A. Facchetti , T. J. Marks , J. Am. Chem. Soc. 2006 , 128 , 9034 –9035 .
- 19l M. Takahashi , K. Masui , H. Sekiguchi , N. Kobayashi , A. Mori , M. Funahashi , N. Tamaoki , J. Am. Chem. Soc. 2006 , 128 , 10930 –10933 .
- 19m M. Funahashi , J.-I. Hanna , Adv. Mater. 2005 , 17 , 594 –598 .
- 19n R. Chen , X. Yang , H. Tian , X. Waang , A. Hagfeldt , L. Sun , Chem. Mater. 2007 , 19 , 4007 –4015 .
- 19o
A. Facchetti
, M.-H. Yoon
, C. L. Stern
, T. L. Katz
, Angew. Chem.
2003
, 115
, 4030
; Angew. Chem. Int. Ed.
2003
, 42
, 3900
–3903
.
10.1002/ange.200351253 Google Scholar
- 19p R. D. McCullough , Adv. Mater. 1998 , 10 , 93 –116 .
- 19q J. M. Tour , Chem. Rev. 1996 , 96 , 537 –554 .
- 19r J. Roncali , Chem. Rev. 1992 , 92 , 711 –738 .
- 20a
A. Krasovskiy
, A. Tishkov
, V. del Amo
, H. Mayr
, P. Knochel
, Angew. Chem.
2006
, 118
, 5132
; Angew. Chem. Int. Ed.
2006
, 45
, 5010
–5014
.
10.1002/ange.200600772 Google Scholar
- 20b K. Masui , H. Ikegami , A. Mori , J. Am. Chem. Soc. 2004 , 126 , 5074 –5075 .
- 20c K. Kobayashi , A. Sugie , M. Takahashi , K. Masui , A. Mori , Org. Lett. 2005 , 7 , 5083 –5085 .
- 21
- 21a P. Bäuerle , F. Würthner , G. Götz , F. Effenberger , Synthesis 1993 , 1099 –1103 .
- 21b V. G. Nenajdenko , I. L. Barazenenok , E. S. Balenkova , J. Org. Chem. 1998 , 63 , 6132 –6136 .
- 21c R. M. Kellogg , A. P. Schaap , H. Wynberg , J. Org. Chem. 1969 , 34 , 343 –346 .
- 22 T. Okamoto , T. Kakinami , H. Fujimoto , S. Kajigaeshi , Bull. Chem. Soc. Jpn. 1991 , 64 , 2566 –2568 .
- 23 T. Sone , K. Sakai , K. Kuroda , Bull. Chem. Soc. Jpn. 1970 , 43 , 1411 –1415 .
- 24 K. J. Jung , S. B. Kang , J. E. Won , S. E. Park , K. H. Park , J. K. Park , S. G. Lee , Y. J. Yoon , Synlett 2009 , 490 –494 .
- 25 P. B. D. de la Mare (Ed.), Electrophilic Halogenation, Cambridge University Press, Cambridge, UK, 1976 , p. 101.
- 26 Metal halides used were KI, LiI, NaI, CuI, KBr, LiBr, ZnBr2, CuBr2, HfCl4, AlCl3, LiCl, CuCl, ZnCl2, FeCl3, and NaCl. Also, the solvents used were benzene, chloroform, ethyl acetate, diethyl ether, n-hexane, dichloromethane, acetonitrile, and tetrahydrofuran.
- 27 J. A. Joule , K. Mills , G. F. Smith (Eds.), Heterocyclic Chemistry, 3rd ed., Chapman & Hall, London, 1996 , pp. 225–228.
- 28 Q. Meng , J. Gao , R. Li , L. Jiang , C. Wang , H. Zhao , C. Liu , H. Li , W. Hu , J. Mater. Chem. 2009 , 19 , 1477 –1482 .
- 29 Y. J. Yoon , I. S. Koo , J. K. Park , Bull. Chem. Soc. Jpn. 2011 , 84 , 172 –180 .
Citing Literature
