DOI QR코드

DOI QR Code

Friedel-Crafts Type alkylation of 1,2,3,4,5,6,7,8,-Octahydroanthracene with Vinylchlorosilanes:Synthesis of Mono,Bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8,-Octahydroanthracenes


Abstract

Friedel-Crafts alkylation reaction of an isomeric mixture of 1,2,3,4,5,6,7,8- (2) and 1,2,3,4,5,6,7,8-octahydrophenanthrene (2') with excess vinylchlorosilanes such as vinyl(methyl)dichlorosilane (1a) and vinyltrichlorosilane (1b) in the presence of aluminum chloride catalyst at 80 $^{\circ}C$ gives only one dialkylated products, 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthrenes [(Cl2XSiCH2CH2)2C14H16: X = Me (4a), Cl (4b)] in good yields, but 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydrophenanthrenes are not obtained. However, monoalkylation of 2 with 1 affords a mixture of both isomeric compounds, 9-[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthracenes 3 and -phenanthrenes 3'. The yield of product 3' is always higher than that of 3. When a mixture of 3 and 3' is alkylated again with 1, only product 4 without phenanthrene type compounds is obtained, indicating that the isomerizations between 2 and 2', or 3 and 3'occur under the alkylation condition. The alkylation with dimethylvinylchlorosilane or trimethylvinylsilane did not proceed. The structure of 4a is determined by X-ray single crystal diffraction analysis.

Keywords

References

  1. Ohshita, J.; Kunai, A. Acta Polym. 1998, 49, 379. https://doi.org/10.1002/(SICI)1521-4044(199808)49:8<379::AID-APOL379>3.0.CO;2-Z
  2. Ishikawa, M.; Ohshita, J.; Nalwa, H. S. Organic Conductive Molecules and Polymers; Wiley: New York, 1997; Vol. 2.
  3. Manhart, S. A.; Adachi, A.; Sakamaki, K.; Okita, K.; Ohshita, J.; Ohno, T.; Hamaguchi, T.; Kunai, A.; Kido, J. J. Organomet. Chem. 1999, 592, 52. https://doi.org/10.1016/S0022-328X(99)00481-7
  4. Bock, H.; Ansari, M.; Nagel, N.; Claridge, R. F. C. J. Organomet. Chem. 1995, 501, 53. https://doi.org/10.1016/0022-328X(95)05593-E
  5. Bock, H.; Ansari, M.; Nagel, N.; Claridge, R. F. C. J. Organomet. Chem. 1996, 521, 51. https://doi.org/10.1016/0022-328X(96)06320-6
  6. Kaim, W.; Bock, H. Chem. Ber. 1978, 111, 3585. https://doi.org/10.1002/cber.19781111107
  7. Song, Y. S.; Kong, S. D.; Khan, S. A.; Yoo, B. R.; Jung, I. N. Organometallics 2001, 20, 5586. https://doi.org/10.1021/om0104161
  8. Lee, B. W.; Yoo, B. R.; Kim, S. I.; Jung, I. N. Organometallics 1994, 13, 1312. https://doi.org/10.1021/om00016a038
  9. Cho, E. J.; Lee, V.; Yoo, B. R.; Jung, I. N.; Sohn, H.; Powell, D. R.; West, R. Organometallics 1997, 16, 4200. https://doi.org/10.1021/om970393j
  10. Cho, E. J.; Lee, V.; Yoo, B. R.; Jung, I. N. J. Organomet. Chem. 1997, 548, 237. https://doi.org/10.1016/S0022-328X(97)00461-0
  11. Yoo, B. R.; Kim, J. H.; Lee, H. J.; Lee, K. B.; Jung, I. N. J. Organomet. Chem. 2000, 605, 239. https://doi.org/10.1016/S0022-328X(00)00319-3
  12. Ahn, S.; Song, Y. S.; Yoo, B. R.; Jung, I. N. Organometallics 2000, 19, 2777. https://doi.org/10.1021/om0000865
  13. Jung, I. N.; Yoo, B. R. Adv. Organomet. Chem. 2000, 41, 145.
  14. Jung, I. N.; Yoo, B. R.; Cho, E. J. Unpublished results.
  15. Fu, P. P.; Harvey, R. G. Chem. Rev. 1978, 78, 317. https://doi.org/10.1021/cr60314a001
  16. Linstead, R. P.; Millidge, A. F.; Thomas, L. S.; Walpole, A. L. J. Chem. Soc. 1937, 1146. https://doi.org/10.1039/jr9370001146
  17. Shadmanov, K. M. Dokl. Akad. Nauk Uzb. SSR. 1963, 20(11), 26
  18. Shadmanov, K. M. Chem. Abstr. 1964, 61, 4286f.
  19. Thomas, C. A. Anhydrous Aluminum Chloride in Organic Chemistry; Reinhold: New York, 1941.
  20. Wierschke, S. G.; Chandrasekhar, J.; Jorgensen, W. L. J. Am. Chem. Soc. 1985, 107, 1496. https://doi.org/10.1021/ja00292a008
  21. Kresge, A. J.; Tobin, J. B. Angew. Chem. Int. Ed. 1993, 32, 721. https://doi.org/10.1002/anie.199307211
  22. Eabon, C.; Bott, R. W. Organometallic Compounds of the Group IV Elements; MacDiarmid, A. G., Ed.; Dekker: New York, 1968; Vol. 1, Part 1, pp 359-437.
  23. Roberts, R. M.; Khalaf, A. A. Friedel-Crafts Alkylation Chemistry; Marcel Dkker, Inc.: New York and Basel, 1984.
  24. Olah, G. A. Fiedel-Crafts and Related Reactions; Jonh Wiley & Sons: New York-London-Sydney, 1963; Volumes I-IV.
  25. Fiedel-Crafts and Relatted Reactions v.1 no.4 Olah,G.A.

Cited by

  1. Friedel—Crafts Type Alkylation of 1,2,3,4,5,6,7,8-Octahydroanthracene with Vinylchlorosilanes: Synthesis of Mono, Bis[2-(chlorosilyl)ethyl]1,2,3,4,5,6,7,8-octahydroanthracenes. vol.34, pp.9, 2002, https://doi.org/10.1002/chin.200309168