A straightforward modular approach to NLO-active β-amino vinyl nitrothiophenes

Organic Letters

Volumn 2, Issue 16, 2000, Pages 2419-2422

  Müllier, Thomas J J ^a,b   Robert, Jan P ^a,b   Schmälzlin, Elmar ^a,c   Bräuchte, Christoph ^a,c   Meerholz, Klaus ^a,c  

^a UNIVERSITY OF MUNICH   (Germany)

^b Organic Chemistry (Haus F)   (Germany)

^c Physical Chemistry (Haus E)   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0037908128     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006048z     Document Type: Article

References (43)

1. For recent reviews on NLO materials, see: (a) Long, N. J. Angew. Chem., Int. Ed. Engl. 1995, 34, 6.
2. (b) Marder, S. R.; Perry, J. W. Adv. Mater. 1993, 5, 804.
3. (c) Nie, W. Adv. Mater. 1993, 5, 520.
4. (d) Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94, 195.
5. (e) Marks, T. J.; Ratner, M. A. Angew. Chem., Int. Ed. Engl. 1995, 34, 155.
6. (f) Wolff, J. J.; Wortmann, R. Adv. Phys. Org. Chem. 1999, 32, 121.
7. (a) Jen, A. K.-J.; Varanasi, P. R.; Wong, K. Y.; Drost, K. J. J. Chem. Soc., Chem. Commun. 1993, 90.
8. (b) Wong, M. S.; Meier, U.; Pan, F.; Gramlich, V.; Bosshard, C.; Günter, P. Adv. Mater. 1996, 8, 416.
9. (c) Boldt, P.; Bourhill, G.; Bräuchle, C.; Jim, Y.; Kammler, R.; Müller, C.; Rase, J.; Wichern, J. J. Chem. Soc., Chem. Commun. 1996, 793.
10. (a) Effenberger, F.; Würthner, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 719.
11. (b) Würthner, F.; Effenberger, F.; Wortmann, R.; Krämer, P. Chem. Phys. 1993, 173, 305.
12. (c) Bedworth, P. V.; Cai, Y.; Jen, A.; Marder, S. R. J. Org. Chem. 1996, 61, 2242.
13. (a) Végh, D.; Kovác, J.; Dandárová, M.; Ivanco, L. Collect. Czech. Chem. Commun. 1980, 45, 155.
14. (b) Végh, D.; Kovác, J.; Dandárová, M. Tetrahedron Lett. 1980, 21, 969.
15. (c) Kravchenko, V. V.; Popov, A. F.; Kotenko, A. A. J. Org. Chem. USSR (Engl. Transl.) 1988, 1332.
16. (d) Kravchenko, V. V.; Popov, A. F.; Kotenko, A. A.; Végh, D. J. Org. Chem. USSR (Engl. Transl.) 1991, 27, 134.
17. Papanastassiou, Z. B.; Bruni, R. J.; White, E. J. Med. Chem. 1967, 10, 701.
18. Jäger, V.; Viehe, H. G. In Alkine, Di- und Polyine, Allene, Kumulene; Houben-Weyl, Eds.; George Thieme Verlag: Stuttgart. 1977; Vol. 5/2a, p 713.
19. Prepared by Sonogashira coupling of 2-bromo-5-nitrothiophene and (trimethylsilyl)acetylene in a refluxing mixture of THF and triethylamine in 85% yield and subsequent desilylation with 2 N aqueous NaOH in methanol in 92% yield.
20. The same reaction was reported late last year independent from our group: Wu, I.-Y.; Lin, J. T.; Li, C-S.; Wang, W.-C.; Huang, T. H.; Wen, Y. S.; Chow, T.; Tsai, C. Tetrahedron 1999, 55, 13973.
21. Typical procedure (3a): To a magnetically stirred solution of 200 mg (1.30 mmol) of 2-ethynyl-5-nitrothiophene (1) in 5 mL of THF under nitrogen was added 1.7 g (24 mmol) of pyrrolidine (2a) dropwise at room temperature. After 5 min of stirring, the reaction mixture was filtered through a short pad of Celite, the solvents were evaporated in vacuo, and the residue was dried under high vacuum to give 290 mg (99%) of analytically pure 3a us violet microcrystals.
22. All compounds have been characterized spectroscopically and have the correct elemental analysis or HRMS.
23. Winterfeldt, E.; Preuss, H. Chem. Ber. 1966, 99, 450.
24. Huisgen, R.; Herbig, K.; Siegl, A.; Huber, H. Chem. Ber. 1966, 99, 2526.
25. Fabian, J.; Wagner, H. U. wPSIN. PPP-π-SCF-Singulett-CI, Version 1997, 11.
26. Schmälzlin, E.; Meerholz, K.; Stadler, S.; Bräuchle, C.; Patzelt, H.; Oesterhelt, D.; Chem. Phys. Lett. 1997, 280, 551.
27. Oudar, J. L.; Chemla, D. S. J. Chem. Phys. 1977, 66, 2664.
28. (a)Effenberger, F.; Würthner, F.; Steybe, F. J. Org. Chem. 1995, 60, 2082.
29. (b) Varanasi, P. R.; Jen, A. K.-Y.; Chandrasekhar, J.; Namboothiri, I. N. N.; Rathna, A. J. Am. Chem. Soc 1996, 118, 12443.
30. Reichardt, C. Angew. Chem., Int. Ed. Engl. 1979, 18, 98.
31. Clays, K.; Persoons, A. Phys. Rev. Lett. 1991, 66, 2980.
32. (a) Stadler, S.; Dietrich, R.; Bourhill, G.; Bräuchle, C. Opt. Lett. 1996, 21, 251.
33. (b) Lequan, M.; Branger, C.; Simon, J.; Thami, T.; Chauchard, E.; Persoons, A. Chem. Phys. Lett. 1994, 229, 101.
34. Lambert, C.; Nöll, G.; Schmälzlin, E.; Meerholz, K.; Bräuchle, C. Chem. Eur. J. 1998, 4, 2129.
35. Quantum CAChe 3.0 Program, Oxford Molecular Group, 1997.
36. Meerholz, K.; Kippelen, B.; Peyghambarian, N. In Electrical and Optical Polymer Systems: Wise, D. L., Wnek, G. E., Trantolo, D. J., Gresser, J. D., Cooper, T. M., Eds.; World Scientific Plast. Eng.: New York, 1998; p 571.
37. (a) Lundquist, P. M.; Wortmann, R.; Geletneky, C.; Twieg, R. J.; Jurich, M; Lee, V. Y.; Moylan, C. R.; Burland, D. M. Science 1996, 274, 1182.
38. (b) Würthner F.; Yao S.; Schilling J.; Wortmann R.; Redi-Abshiro M.; Mecher E.; Gallego F.; Meerholz K. ATOP Dyes - Optimization of a Merocyanine Chromophore for High Refractive Index Modulation in Photorefractive Materials. Submitted.
39. Moerner, W. E.; Silence S. M.; Hache F.; Bjorklund G. C. J. Opt. Soc. Am. B 1994, 22, 320.
40. The heating rate was 20 K/min.
41. Müller, T. J. J.; Ansorge, M.; Aktah, D. Angew. Chem., Int. Ed. 2000, 39, 1253.
42. (a) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627.
43. (b) Sonogashira, K. In Metal catalyzed Cross-coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998; p 203.