Facile, Regioselective Synthesis of Highly Solvatochromic Thiophene-Spaced N-Alkylpyridinium Dicyanomethanides for Second-Harmonic Generation

Journal of Organic Chemistry

Volumn 62, Issue 17, 1997, Pages 5755-5765

  Abbotto, Alessandro ^a   Bradamante, Silvia ^a   Facchetti, Antonio ^a   Pagani, Giorgio A ^a  

^a UNIVERSITY OF MILAN   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

AMPHOLYTE; ANION; HETEROCYCLIC AMINE; THIOPHENE DERIVATIVE;

ALKYLATION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; CHROMATOPHORE; STEREOCHEMISTRY; SYNTHESIS;

EID: 0030826158     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970059x     Document Type: Article

References (89)

1. Williams, D. J. Angew. Chem., Int. Ed. Engl. 1984, 23, 690-703.
2. Prasad, P. N.; Williams, J. Introduction to Nonlinear Optical Effects in Molecules and Polymers; Wiley: New York, 1991.
3. Marder, S. R.; Sohn, J. E.; Stucky, G. D. Materials for Nonlinear Optics: Chemical Perspectives; ACS Symposium Series, Vol. 455; American Chemical Society: Washington, DC, 1991.
4. (a) Chemla, D. S.; Zyss, J. Nonlinear Optical Properties of Organic Molecules and Crystals; Academic Press: New York, 1987.
5. (b) Marder, S. R.; Perry, J. W. Adv. Mater. 1993, 5, 804-815.
6. (c) Burland, D. M.; Miller, R. D.; Walsh, C. A. Chem. Rev. 1994, 94, 31.
7. (d) Bredas, J. L.; Adant, C.; Tackx, P.; Persoons, A.; Pierce, B. M. Chem. Rev. 1994, 94, 243.
8. (e) Dalton, L. R.; Harper, A. W.; Ghosn, R.; Steier, W. H.; Ziari, M.; Fetterman, H.; Shi, Y.; Mustacich, R. V.; Jen, A. K.-Y.; Shea, K. J. Chem. Mater. 1995, 7, 1060-1081.
9. (f) Drost, K. J.; Jen, A. K.-Y.; Rao, V. P. CHEMTECH 1995, 25, 16-25
10. Cheng, L.-T.; Tam, W.; Stevenson, S. H.; Meredith, G. R.; Rikken, G.; Marder, S. R. J. Phys. Chem. 1991, 95, 10631-10643.
11. Cheng, L.-T.; Tam, W.; Marder, S. R.; Stiegman, A. E.; Rikken, G.; Spangler, C. W. J. Phys. Chem. 1991, 95, 10643-10652.
12. Cabrera, I.; Althoff, O.; Mau, H.-T.; Yoon, H. N. Adv. Mater. 1994, 6, 43.
13. Dirk, C.; Katz, H.; Schilling, L. Chem. Mater. 1990, 2, 700.
14. (a) Rao, V. P.; Jen, A. K.-Y.; Wong, K. Y.; Drost, K. J. Tetrahedron Lett. 1993, 34, 1747-1750.
15. (b) Jen, A. K.-Y.; Rao, V. P.; Wong, K. Y.; Drost, K. J. J. Chem. Soc., Chem. Commun. 1993, 90-92.
16. (c) Wong, K. Y.; Jen, A. K.-Y.; Rao, V. P.; Drost, K. J. J. Chem. Phys. 1994, 100, 6818-6825.
17. (a) Gilmour, S.; Marder, S. R.; Perry, J. W.; Cheng, L.-T. Adv. Mater. 1994, 6, 494-496.
18. (b) Jen, A. K-Y.; Rao, V. P.; Drost, K. J.; Wong, K. Y.; Cava, M. P. J. Chem. Soc., Chem. Commun. 1994, 2057-2058.
19. (c) Bedworth, P. V.; Cai, Y.; Jen, A.; Marder, S. R. J. Org. Chem. 1996, 61, 2242-246.
20. (d) Rao, V. P.; Jen, A. K-Y.; Cai, Y. J. Chem. Soc., Chem. Commun. 1996, 1237-1238.
21. (e) Shu, C.-F.; Tsai, W. J.; Chen, J.-Y.; Jen, A. K.-Y.; Zhang, Y.; Chen, T.-A. J. Chem. Soc., Chem. Commun. 1996, 2279-2280.
22. (f) Shu, C.-F.; Tsai, W.-J.; Jen, A. K-Y. Tetrahedron Lett. 1996, 37, 7055-7058.
23. Abe, J.; Shirai, Y. J. Am. Chem. Soc. 1996, 118, 4705-4706.
24. Alcade, E. Adv. Heterocycl. Chem. 1994, 60, 197.
25. (a) Paley, M. S.; Harris, J. M. J. Org. Chem. 1991, 56, 568-574.
26. (b) Nemoto, N.; Abe, J.; Miyata, F.; Hasegawa, M.; Shirai, Y.; Nagase, Y. Chem. Lett. 1996, 851-852.
27. (a) Berlin, A.; Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1988, 1525-1530.
28. (b) Abbotto, A.; Bradamante, S.; Pagani, G.; Rzepa, H.; Stoppa, F. Heterocycles 1994, 40, 757-776.
29. x of a substituent group X as the fraction of π-charge withdrawn from an adjacent charged trigonal carbon atom and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: (a) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035-1045. (b) Bradamante, S.; Pagani, G. A. Pure Appl. Chem. 1989, 61, 709-716. (c) Barchiesi, E.; Bradamante, S.; Ferraccioli, R.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1990, 375-383.
30. x of a substituent group X as the fraction of π-charge withdrawn from an adjacent charged trigonal carbon atom and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: (a) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035-1045. (b) Bradamante, S.; Pagani, G. A. Pure Appl. Chem. 1989, 61, 709-716. (c) Barchiesi, E.; Bradamante, S.; Ferraccioli, R.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1990, 375-383.
31. x of a substituent group X as the fraction of π-charge withdrawn from an adjacent charged trigonal carbon atom and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: (a) Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1986, 1035-1045. (b) Bradamante, S.; Pagani, G. A. Pure Appl. Chem. 1989, 61, 709-716. (c) Barchiesi, E.; Bradamante, S.; Ferraccioli, R.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1990, 375-383.
32. (a) Buckely, A.; Choe, E.; DeMartino, R.; Leslie, T.; Nelson, G.; Starnatoff, J.; Stuetz, D.; Yoon, H. Polym. Mater. Sci. Eng. 1986, 54, 502.
33. (b) Paley, M. S.; Harris, J. M.; Looser, H.; Baumert, J. C.; Bjorklund, G. C.; Jundt, D.; Twieg, R. J. J. Org. Chem. 1989, 54, 3774-3778.
34. (a) Abbotto, A.; Bradamante, S.; Capri, N.; Rzepa, H.; Williams, D. J.; White, A. J. Org. Chem. 1996, 61, 1770-1778.
35. (b) Bradamante, S.; Facchetti, A.; Pagani, G. A. J. Phys. Org. Chem. 1997, in press.
36. Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 449-455.
37. Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1996, 61, 1761-1769.
38. Ricceri, R.; Abbotto, A.; Facchetti, A.; Gabrielli, G.; Pagani, G. A. Langmuir 1997, 13, 3434-3437.
39. Ricceri, R.; Abbotto, A.; Facchetti, A.; Gabrielli, G.; Pagani, G. A. Langmuir 1997, 13, 4182-4184.
40. Yui, K.; Aso, Y.; Otsubo, T.; Ogura, F. Bull. Chem. Soc. Jpn. 1989, 62, 1539-1546.
41. Nakajima, R.; Iida, H.; Hara, T. Bull. Chem. Soc. Jpn. 1990, 63, 636-637.
42. Kumada, M. Pure Appl. Chem. 1980, 52, 669-679.
43. Nakajima, R.; Jamamoto, A. Hara, T. Bull. Chem. Soc. Jpn. 1990, 63, 1968-1972.
44. During the course of our work, a preparation of 6 was reported from 2-thiophenecarbaldehyde and 4-picoline in acetic anhydride and acetic acid with 66% yield: Pan, H.; Gao, X.; Zhang, Y.; Prasad, P. N.; Reinhardt, B.; Kannan, R. Chem. Mater. 1995, 7, 816-821.
45. Abbotto, A.; Bradamante, S.; Facchetti. A.; Pagani, G. A. Results to be published.
46. Pearson, R. G. In Advances in Linear Free Energy Relationship; Chapman, N. B., Shorter, J., Eds.; Plenum Press: London, 1972; p 281.
47. Suzuki, H.; Kobayashi, T.; Osuka, A. Chem. Lett. 1983, 589-590.
48. Hessler, J. C. Am. Chem. J. 1908, 39, 63 (cf. Beilstein H, 9, 872 or Chem. Abstr. 1908, 2, 1003).
49. Hessler, J. C. Am. Chem. J. 1908, 39, 63 (cf. Beilstein H, 9, 872 or Chem. Abstr. 1908, 2, 1003).
50. Hessler, J. C. Am. Chem. J. 1908, 39, 63 (cf. Beilstein H, 9, 872 or Chem. Abstr. 1908, 2, 1003).
51. Albers, W. M.; Canters, G. W.; Reedijk, J. Tetrahedron 1995, 51, 3895-3904.
52. Reichardt, C. Solvent Effects in Organic Chemistry; Verlag Chemie: New York, 1979; Chapter 6.
53. Chen, C.-T.; Marder, S. R. Adv. Mater. 1995, 7, 1030-1033.
54. Bosshard, C.; Sutter, K.; Prêtre, P.; Hulliger, J.; Flörsheimer, M.; Kaatz, P.; Günter, P. In Organic Nonlinear Optical Materials In Advances in Nonlinear Optics; Garito, A. F., Kajzar, F., Eds.; Gordon and Breach Publishers: Basel, 1995; Vol. 1.
55. See also, more recently: (a) Blenkle, M.; Boldt, P.; Bräuchle, C.; Grahn, W.; Ledoux, I.; Nerenz, H.; Stadler, S.; Wichern, J.; Zyss, J. J. Chem. Soc., Perkin Trans. 2 1996, 1377-1384. (b) Alain, V.; Fort, A.; Barzoukas, M.; Chen, C.-T.; Blanchard-Desce, M.; Marder, S. R.; Perry, J. W. Inorg. Chim. Acta 1996, 242, 43-49. (c) Ashwell, G. J.; Walker, T. W.; Gentle, I. R.; Foran, G. J.; Bahra, G. S.; Brown, C. R. J. Mater. Chem. 1996, 6, 969-974. (d) Ashwell, G. J.; Jackson, P. D.; Jefferies, G.; Gentle, I. R.; Kennard, C. H. L. J. Mater. Chem. 1996, 6, 137-141.
56. See also, more recently: (a) Blenkle, M.; Boldt, P.; Bräuchle, C.; Grahn, W.; Ledoux, I.; Nerenz, H.; Stadler, S.; Wichern, J.; Zyss, J. J. Chem. Soc., Perkin Trans. 2 1996, 1377-1384. (b) Alain, V.; Fort, A.; Barzoukas, M.; Chen, C.-T.; Blanchard-Desce, M.; Marder, S. R.; Perry, J. W. Inorg. Chim. Acta 1996, 242, 43-49. (c) Ashwell, G. J.; Walker, T. W.; Gentle, I. R.; Foran, G. J.; Bahra, G. S.; Brown, C. R. J. Mater. Chem. 1996, 6, 969-974. (d) Ashwell, G. J.; Jackson, P. D.; Jefferies, G.; Gentle, I. R.; Kennard, C. H. L. J. Mater. Chem. 1996, 6, 137-141.
57. See also, more recently: (a) Blenkle, M.; Boldt, P.; Bräuchle, C.; Grahn, W.; Ledoux, I.; Nerenz, H.; Stadler, S.; Wichern, J.; Zyss, J. J. Chem. Soc., Perkin Trans. 2 1996, 1377-1384. (b) Alain, V.; Fort, A.; Barzoukas, M.; Chen, C.-T.; Blanchard-Desce, M.; Marder, S. R.; Perry, J. W. Inorg. Chim. Acta 1996, 242, 43-49. (c) Ashwell, G. J.; Walker, T. W.; Gentle, I. R.; Foran, G. J.; Bahra, G. S.; Brown, C. R. J. Mater. Chem. 1996, 6, 969-974. (d) Ashwell, G. J.; Jackson, P. D.; Jefferies, G.; Gentle, I. R.; Kennard, C. H. L. J. Mater. Chem. 1996, 6, 137-141.
58. See also, more recently: (a) Blenkle, M.; Boldt, P.; Bräuchle, C.; Grahn, W.; Ledoux, I.; Nerenz, H.; Stadler, S.; Wichern, J.; Zyss, J. J. Chem. Soc., Perkin Trans. 2 1996, 1377-1384. (b) Alain, V.; Fort, A.; Barzoukas, M.; Chen, C.-T.; Blanchard-Desce, M.; Marder, S. R.; Perry, J. W. Inorg. Chim. Acta 1996, 242, 43-49. (c) Ashwell, G. J.; Walker, T. W.; Gentle, I. R.; Foran, G. J.; Bahra, G. S.; Brown, C. R. J. Mater. Chem. 1996, 6, 969-974. (d) Ashwell, G. J.; Jackson, P. D.; Jefferies, G.; Gentle, I. R.; Kennard, C. H. L. J. Mater. Chem. 1996, 6, 137-141.
59. (a) Ashwell, G. J.; Dawnay, E. J. C.; Kuczynski, A. P.; Szablewski, M.; Sandy, I. M.; Bryce, M. R.; Grainger, A. M.; Hasan, M. J. Chem. Soc., Faraday Trans. 1990, 86, 1117-1121.
60. (b) Ashwell, G. J. Thin Solid Films 1990, 187, 155-165.
61. (c) Ashwell, G. J.; Malhotra, M.; Bryce, M. R.; Grainger, A. M. Synth. Met. 1991, 41-43, 3173-3176.
62. (d) Ashwell, G. J.; Hargreaves, R. C.; Baldwin, C. E.; Bahra, G. S.; Brown, C. R. Nature 1992, 357, 393-395.
63. Reutov, O. A.; Beletskaya, I. P.; Kurts, A. L. Ambident Anions; Consultants Bureau: New York, 1983.
64. See, for instance, the investigation on the C/O alkylation ratio of lithium enolates: (a) Jackman, L. M.; Lange, B. C. J. Am. Chem. Soc. 1981, 103, 4494. (b) Jackman, L. M.; Dunne, T. S. J. Am. Chem. Soc. 1985, 107, 2805.
65. See, for instance, the investigation on the C/O alkylation ratio of lithium enolates: (a) Jackman, L. M.; Lange, B. C. J. Am. Chem. Soc. 1981, 103, 4494. (b) Jackman, L. M.; Dunne, T. S. J. Am. Chem. Soc. 1985, 107, 2805.
66. (a) Jackman, L. M.; Rakiewicz, E. F. J. Am. Chem. Soc. 1991, 113, 1202.
67. (b) Abbotto, A.; Streitwieser, A. J. Am. Chem. Soc. 1995, 117, 6358-6359.
68. (c) Abu-Hasanayn, F.; Stratakis, M.; Streitwieser, A. J. Org. Chem. 1995, 60, 4688-4689.
69. (d) Abu-Hasanayn, F.; Streitwieser, A. J. Am. Chem. Soc. 1996, 118, 8136-8137.
70. Pearson, R. G. Hard and Soft Acids and Bases; Dowden, Hutchinson and Ross: Stroudsville, PA, 1973.
71. See ref 18 and: (a) Abbotto, A.; Alanzo, V.; Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1991, 481-488. (b) Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444-448. (c) Gatti, C.; Ponti, A.; Gamba, A.; Pagani, G. A. J. Am. Chem. Soc. 1992, 114, 8634-8644.
72. See ref 18 and: (a) Abbotto, A.; Alanzo, V.; Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1991, 481-488. (b) Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444-448. (c) Gatti, C.; Ponti, A.; Gamba, A.; Pagani, G. A. J. Am. Chem. Soc. 1992, 114, 8634-8644.
73. See ref 18 and: (a) Abbotto, A.; Alanzo, V.; Bradamante, S.; Pagani, G. A. J. Chem. Soc., Perkin Trans. 2 1991, 481-488. (b) Abbotto, A.; Bradamante, S.; Pagani, G. A. J. Org. Chem. 1993, 58, 444-448. (c) Gatti, C.; Ponti, A.; Gamba, A.; Pagani, G. A. J. Am. Chem. Soc. 1992, 114, 8634-8644.
74. Witanowski, M.; Stefaniak, L.; Webb, G. A. In Annual Reports on NMR Spectroscopy; Webb, G. A., Ed.; Academic Press: London, 1986; Vol. 18.
75. A positive value of Δq corresponds to an increase in π-electron density.
76. 19
77. Metzger, R. M.; Heimer, N. E.; Ashwell, G. J. Mol. Cryst. Liq. Cryst. 1984, 107, 133.
78. Stewart, J. J. P. QCPE 455, 1990.
79. Less polar solvents could not be considered due to solubility limits.
80. See ref 34, p. 117.
81. Oudar, J. L.; Chemla, D. S. J. Chem. Phys. 1977, 66, 2664.
82. Dulcic, A.; Flytzanis, C. Opt. Commun. 1978, 25, 402.
83. Benson, H. G.; Murrell, J. N. J. Chem. Soc., Faraday Trans.2 1972, 68, 137-143.
84. 3 is expected to be larger, as can be seen from Table 1).
85. -48 esu at λ = 1.9 μm, respectively. Full data of the measures currently in progress will be reported elsewhere.
86. Rossi, R.; Carpita, A.; Ciofalo, M.; Nouben, J. L. Gazz. Chim. Ital. 1985, 115, 575.
87. Gronowitz, S.; Lilijefors, S. Chem. Scr. 1979, 13, 39.
88. Kellogg, R. M.; Groen, M. B.; Wynberg, H. J. Org. Chem. 1967, 32, 3093.
89. McCullough, R. D.; Lowe, R. D.; Jayaraman, M.; Anderson, D. L. J. Org. Chem. 1993, 58, 904-912.