Hostname: page-component-7479d7b7d-t6hkb Total loading time: 0 Render date: 2024-07-12T06:19:53.133Z Has data issue: false hasContentIssue false
  • English
  • Français

Synthesis of 3,4-Disubstituted Poly(thiophene)s via Substitution of Poly(3-alkylthiophene)

Published online by Cambridge University Press:  21 March 2011

Yuning Li ,
George Vamvounis  and
Steven Holdcroft
Yuning Li
Affiliation:
Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada
George Vamvounis
Affiliation:
Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada
Get access

Abstract

The electrophilic substitution of regioregular poly(3-hexylthiophene) (P3HT) at the 4- position was investigated to produce structurally well defined 3,4-disubstituted poly(thiophene)s. When P3HT was treated with N-bromosuccinimide (NBS) in chloroform at 25 to 50 °C, the 4-hydrogen atom in P3HT is completely substituted by bromine, as indicated by the 1H NMR, 13C NMR and elemental analysis. Similarly, the chlorinated product was obtained using N- chlorosuccinimide (NCS) at room temperature. However, only 85% of the 4-hydrogen atoms were replaced by chlorine and ∼15% of the α-hydrogen atoms on the hexyl side chain were chlorinated. P3HT readily reacts with fuming nitric acid in chloroform at 0 °C to generate a nitrated product with almost 100% substitution at the 4-position. Our preliminary study on the futher functionalizaton of these polymers was conducted on the brominated product. Our results showed that the bromine atom in this polymer could be further substituted with other groups.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 665: Symposium C – Electronic, Optical and Optoelectronic Polymers and Oligomers , 2001 , C5.25
Copyright
Copyright © Materials Research Society 2001

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1. (a) Patil, A. O., Heeger, A. J., and Wudl, F., Chem. Rev. 88, 183 (1988). (b) J. Roncali, J. Chem. Rev. 92, 711 (1992). (c) R. D. McCullough and P. C. Ewbank, In Handbook of Conducting Polymers, 2nd ed., ed. T. A. Skotheim, R. L. Elsenbaumer, and J. R. Reynolds (Marcel Dekker, 1998) p.225. (d) G. Schopf and G. Koβmehl, Adv. Polym. Sci. 129, 4 (1997). (e) A. Kraft, A. C. Grimsdale, and A. B. Holmes, Angew. Chem. Int. Ed. 37, 402 (1998).Google Scholar
2. Sugimoto, R., TakedaH, S.. Gu, B., and Yoshino, K., Chemistry Express 1, 635 (1986).Google Scholar
3. Chen, T. and Rieke, R. D., J. Am. Chem. Soc. 114, 10087 (1992).Google Scholar
4. McCullough, R. D., Low, R. D., Jayaraman, M., and Anderson, D. L., J. Org. Chem. 58, 904 (1993).Google Scholar
5. (a) Waltman, R. J., Diaz, A. F., and Bargon, J., J. Electrochem. Soc. 131, 1452 (1984). (b) M. Pomerantz, H. Yang, and Y. Cheng, Macromolecules 28, 5706 (1995).Google Scholar
6. (a) Macromolecular Reactions, ed. Platé, N. A., Litmanovich, A. D., and Noah, O. V. (John Wiley & Sons, 1995).Google Scholar
7. (a) Yue, J. and Epstein, A. J., J. Am. Chem. Soc. 112, 2800 (1990). (b) J. Yue, Z. H. Wang, K. R. Cromack, A. J. Epstein, and A. G. MacDiarmid, J. Am. Chem. Soc. 113, 2665 (1991). (c) Z. Qi, N. G. Rees, and P. Pickup, Chem. Mater. 8, 701 (1996).Google Scholar
8. McCullough, R. D., Tristram-Nagle, S., Williams, S. P., Lowe, R. D., and Jayaraman, M., J. Am. Chem. Soc. 115, 4910 (1993).Google Scholar
9. Li, Y., Vamvounis, G., and Holdcroft, S., Macromolecules 34, 141 (2001).Google Scholar
10. Li, Y., Vamvounis, G., Yu, J., and Holdcroft, S., Macromolecules 34, 3130 (2001).Google Scholar
11. Reinecke, M. G. and Pedaja, P., In The Chemistry of Heterocyclic Compounds, Thiophene and Its Derivatives Part 2; ed. Gronowitz, S. (John Wiley and Sons, Inc, 1986) Vol. 44, p 221.Google Scholar
12. Miyaura, N. and Suzuki, A., Chem. Rev. 95, 2457 (1995).Google Scholar
13. Stille, J. K., Angew. Chem. Int. Ed. Engl. 25, 508 (1986).Google Scholar
14. (a) Heck, R. F., Org. React. 27, 345 (1981). (b) I. P. Beletskaya and A. V. Cheprakov, Chem. Rev. 100, 3009 (2000).Google Scholar
15. Bao, Z., Chan, W. K., and Yu, L., J. Am. Chem. Soc. 117, 12426 (1995).Google Scholar