Efficient one-pot access to poly(arylene ethynylene) homopolymers: use of the Bu3Sn - moiety as a recyclable carrier to introduce the ethynyl unit into the chain

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 38, Issue 14, 2000, Pages 2603-2621

  Giardina, Giorgio ^a   Rosi, Patrizia ^a   Ricci, Antonella ^a   Lo Sterzo, Claudio ^a  

^a SAPIENZA UNIVERSITY OF ROME   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CATALYSTS; DISTILLATION; HOMOPOLYMERIZATION; MIXTURES; PALLADIUM; PRECIPITATION (CHEMICAL);

HOMOPOLYMERS; ONE POT POLYMERIZATION; POLYARYLENE ETHYNYLENE; STILLE COUPLING;

AROMATIC POLYMERS;

EID: 0033685839     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0518(20000715)38:14<2603::AID-POLA100>3.0.CO;2-Y     Document Type: Article

References (56)

1. Handbook of Conducting Polymers; Skotheim, T. J.; Elsenbaumer, R. L.; Reynolds, J. R., Eds.; Marcel Dekker: New York, 1998.
2. Lo Sterzo, C. Synlett 1999, 1704.
3. Fradet, A. In Comprehensive Polymer Science, Second Supplement; Allen, G.; Aggarwal, S. L.; Russo, S., Eds.; Pergamon: Elmsford, 1996; Chapter 4.
4. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett 1975, 4467.
5. Dieck, H. A.; Heck, R. F. J Organomet Chem 1975, 93, 259.
6. Cassar, L. J Organomet Chem 1975, 93, 253.
7. Brandsma, L.; Vasilevsky, S. F.; Verkruijsse, H. D. Application of Transition Metal Catalysts in Organic Synthesis; Springer-Verlag: Heidelberg, Germany, 1999.
8. Kiehl, A; Mullen, K. In Catalysis in Precision Polymerization; Kobayashi, S., Ed.; Wiley: Chichester, England, 1997.
9. Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction; Wiley: New York, 1998.
10. Davies, A. G. Organotin Chemistry; VCH Verlagsgesellschaft: Weinheim, Germany, 1997.
11. (a) Neenan, T. X.; Whitesides, G. M. J Org Chem 1988, 53, 2489 and references therein;
12. (b) Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett 1993, 6403;
13. Nguyen, P.; Todd, S.; Van den Biggelaar, D.; Taylor, N. J.; Marder, T. B.; Wittmann, F.; Friend, R. H. Synlett 1994, 299;
14. Bleicher, L.; Cosford, N. D. P. Synlett 1995, 1115;
15. (e) Diederich, F.; Rubin, Y.; Chapman, O. L.; Goroff, N. S. Helv Chim Acta 1994, 77, 1441;
16. (f) Berris, B. C.; Hovakeemian, G. H.; Lai, Y-H.; Mestdagh, H.; Vollhardt, K. P. C. J Am Chem Soc 1985, 107, 5670:
17. (g) Giesa, R. Rev Macromol Chem Phys 1996, C36, 631.
18. Antonelli, E.; Rosi, P.; Lo Sterzo, C.; Viola, E. J Organomet Chem 1999, 578, 210.
19. (a) Szabo, L.; Cik, G.; Lesny, J. Synth Met 1996, 78, 149;
20. (b) Bauerle, P.; Pfau, F.; Schlupp, H.; Wurthner, F.; Gaudl, K.-U.; Caro, M. B.; Fischer, P. J Chem Soc Perkin Trans 2 1993, 489.
21. Kim, J.; McHugh, S. K.; Swager, T. M. Macromolecules 1999, 32, 1500.
22. Swager, T. M.; Gil, C. J.; Wrighton, M. S. J Phys Chem 1995, 99, 4886.
23. 3SnC≡CH is volatile enough to be lost under these conditions, thus obtaining wrong information on completion of Step 1.
24. Venkatesan, D.; Yoneda, M.; Ueda, M. React Funct Polym 1996, 30, 341.
25. Weder, C.; Wrighton, M. S. Macromolecules 1996, 29, 5157.
26. Both products are commercially available, however the cost (per mol) of bis(tributylstannyl)acetylene is almost twice that of tributyl(ethynyl)tin (Aldrich catalogue 1999-2000, 1 g size bottle).
27. Blank experiments have shown that in the absence of catalyst, even under forcing conditions, no reaction takes place and reagents are recovered unchanged.
28. 1H NMR integral of the aromatic signals for the mixtures of the three products 1a-e, 2a-e, and 3a-e obtained after Step1 of Scheme 4, the overall iodine/acetylenic moieties ratio averaged the ratios 105/95 (a), 105/95 (b), 110/90 (c), 103/97 (d), 98/102 (e), respectively. We believe that, within experimental error, these values are very close to the 1/1 expected ratio.
29. If the thiophene mixtures 1-3d and 1-3e were treated with LDA under the same conditions used for the alkoxybenzene mixtures 1-3a-c (-20°C), even with the use of a large excess of the base, the alkyne intermediates were not completely transformed, and formation of thiophene oligomers was observed. Preliminary MS and NMR data suggest the formation of dimers and trimers of type I and II. matrix presented
30. 1H NMR may be attributed to loss of compounds during work up and chromatographic separation (see Experimental).
31. Chen, T.-A.; Wu, X.; Rieke, R. D. J Am Chem Soc 1995, 117, 233.
32. The most intense resonances have been arbitrarily attributed to the HT linkages (a and b-marks) on the basis of their lesser sterical constraint with respect to HH linkages.
33. 13C NMR signals of the parent compounds 1b and 5b.
34. The much lower signal-to-noise ratio of spectrum b) over a) is due to the less solubility of this material in comparison with that obtained after 12 h reaction.
35. In some cases the Stille cross-coupling of alkynylstannanes and vinyl iodides degenerate towards homocoupling of the tin alkynes [ref. 30(e)]. We believe that in our conditions this side reaction is unlikely to occur.
36. 13C NMR data, we believe that in our cases the use of this technique to estimate polymer chain length is quite reliable.
37. (a) Bao, Z.; Chan, W. K.; Yu, L. J Am Chem Soc 1995, 117, 12426;
38. (b) Yu, L.; Bao, Z.; Cai, R. Angew Chem Int Ed Eng 1993, 32, 1345;
39. Giesa, R.; Schulz, R. C. Makromol Chem 1990, 191, 857;
40. Bochmann, M.; Kelly, K. J Chem Soc Chem Commun 1989, 532;
41. (e) Wright, M. E.; Forsch, M. J.; Buckley, C.; Cochran, B. B. J Am Chem Soc1997, 119, 8393.
42. (a) Tour, J. M. Chem Rev 1996, 96, 537;
43. (b) Wautelet, P.; Moroni, M.; Oswald, L.; Le Moigne, J.; Pham, A.; Bigot, J. Y.; Luzzati, S. Macromolecules 1996, 29, 446;
44. ten Hoeve, W.; Wynberg, H.; Havinga, E. E.; Meijer, E. W. J Am Chem Soc 1991, 113, 5887.
45. 3SnI is sold by Aldrich at 90% purity. The material we recovered by vacuum distillation showed a higher purity than the commercial sample.
46. (a) Renaldo, A. F.; Labadie, J. W.; Stille, J. K. Org Synth 1989, 67, 86;
47. (b) Bottaro, J. C.; Hanson, R. N.; Seitz, D. E. J Org Chem 1981, 46, 5221.
48. Warner, B. P.; Buchwald, S. L. J Org Chem 1994, 59, 5822.
49. (a) The Pd-catalyzed TMSA-diiodide coupling/TMS deprotection/Pd-catalyzed terminal acetylene-diiodide coupling sequence, is the most generally used procedure for the formation of polylarylene ethynylene) polymers. The overall yield obtained in the formation of 10 with this procedure is consistent with that as generally found by a number of authors [ref. 11 (g) and references therein, 30(c), 35(b,c)];
50. (b) Yamamoto, T.; Takagi, M.; Kizu, K.; Maruyama, T.; Kubota, K.; Kanbara, H.; Kurihara, T.; Kaino, T. J Chem Soc Chem Commun 1993, 797, and references therein;
51. Moroni, M.; Le Moigne, J.; Pham, T. A.; Bigot, J.-Y. Macromolecules 1997, 30, 1964.
52. (a) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice; Oxford University Press: New York, 1998; pp 29-55;
53. (b) Maleczka, R. E.; Gallagher, W. P.; Terstiege, I. J Am Chem Soc 2000, 122, 384.
54. (a) Trost, B. M. Science 1991, 254, 1471;
55. (b) Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; Ruter, G. J Am Chem Soc 1997, 119, 698;
56. Trost, B. M.; Krische, M. J. Synlett 1998, 1.