Octachloroazulene

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15302-15307

  Lou, Yan ^a   Chang, Joanne ^a   Jorgensen, Jeffrey ^a   Lemal, David M ^a  

^a Dartmouth College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

RADICAL CONDITIONS;

CALCIUM COMPOUNDS; CATALYSIS; MERCURY (METAL); SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

DECHLORINATION;

1,3,4,5,6,7 HEXACHLOROAZULENE; AZULENE DERIVATIVE; CALCIUM CARBONATE; CYCLOPENTADIENE DERIVATIVE; DECACHLOROTETRAHYDROAZULENE; HEXACHLOROBUTADIENE; NONACHLORODIHYDROAZULENE; OCTACHLOROAZULENE; PERHALOAZULENE; PHOSPHATE; PHOSPHAZENE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHLORINATION; DECHLORINATION; REACTION ANALYSIS; REDUCTION; SYNTHESIS;

EID: 0037176291     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja012051h     Document Type: Article

References (34)

1. Zeller, K.-P. Azulene. In Houben-Weyl, Methoden de Organischen Chemie, 4th Ed.; Vol. 5, Part 2C. p 127. Lemal, D. M.; Goldman, G. D. J. Chem. Educ. 1988, 65, 923 and references therein.
2. Zeller, K.-P. Azulene. In Houben-Weyl, Methoden de Organischen Chemie, 4th Ed.; Vol. 5, Part 2C. p 127. Lemal, D. M.; Goldman, G. D. J. Chem. Educ. 1988, 65, 923 and references therein.
3. Yates, K. Hückel Molecular Orbital Theory; Academic Press: New York, 1978; pp 78-84.
4. Stroh, R. In Houben-Weyl Methoden der Organischen Chemie 4th Ed.; Vol. 5/3. p 670.
5. Fuller, G. J. Chem. Soc. 1965, 6264. See also: Maynard, J. T. J. Org. Chem. 1962, 28, 112.
6. Fuller, G. J. Chem. Soc. 1965, 6264. See also: Maynard, J. T. J. Org. Chem. 1962, 28, 112.
7. Reiter, S. E.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1977, 99, 4199. Copland, D.; Leaver, D.; Menzies, W. B. Tetrahearon Lett. 1977. 639.
8. Reiter, S. E.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1977, 99, 4199. Copland, D.; Leaver, D.; Menzies, W. B. Tetrahearon Lett. 1977. 639.
9. Raasch, M. S. J. Org. Chem. 1980, 45, 856.
10. Meerwein, H.; Florian, W.; Schön, N.; Stopp, G. Liebigs Ann. Chem. 1961, 641, 1.
11. Kanematsu, K.; Kazunobu, H.; Dantsuji, H. Heterocycles 1981, 16, 1145.
12. For other [6+4] cycloadditions of fulvenes, see Dunn, L. C.; Chang, Y.-M.; Houk, K. N. J. Am. Chem. Soc. 1976,98,7095. Mukherjee, D.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1978, 101, 251. Dunn, L. C.; Houk, K. N. Tetrahedron Lett. 1978, 3411: and ref 5.
13. For other [6+4] cycloadditions of fulvenes, see Dunn, L. C.; Chang, Y.-M.; Houk, K. N. J. Am. Chem. Soc. 1976,98,7095. Mukherjee, D.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1978, 101, 251. Dunn, L. C.; Houk, K. N. Tetrahedron Lett. 1978, 3411: and ref 5.
14. For other [6+4] cycloadditions of fulvenes, see Dunn, L. C.; Chang, Y.-M.; Houk, K. N. J. Am. Chem. Soc. 1976,98,7095. Mukherjee, D.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1978, 101, 251. Dunn, L. C.; Houk, K. N. Tetrahedron Lett. 1978, 3411: and ref 5.
15. To disfavor Diels-Alder addition relative to the desired [6+4] pathway with the help of steric hindrance, we substituted the 1,3-dichloro- and 1,2,3-trichloro-6-(dimethylamino)fulvenes (Hafner, K.; Schmidt, F. Tetrahedron Lett. 1973, 5101) for 8 in the reaction with 7. Azulene yields remained poor, however, probably because of the instability of these fulvenes.
16. Perchlorination of benzenoid hydrocarbons commonly proceeds beyond complete substitution, as additional chlorines relieve steric repulsions by rehybridizing sp2 carbons. Ballester, M. Perchloro-organic Chemistry: Structure, Spectroscopy and Reaction Pathways. In Adv. Phys. Org. Chem.; Bethell, D., Ed.; Academic Press: London, 1989; Vol. 25, p 267.
17. Bolton, R.; Hamilton, D. G.; Sandall, J. P. B. J. Chem. Soc., Perkin Trans. 2 1991, 431. These authors carried out the chlorination of 7 with N-chlorosuccinimide.
18. The EA of the chlorine atom is 3.62 eV, higher even than that of the fluorine atom (3.40 eV). Trainham, R.; Fletcher, G. D.; Larson, D. J. J. Phys. B: At. Mol. Phys. 1987, 20. L777. Blondel, C.; Cacciani, P.; Delsart, C.; Trainham, R. Phys. Rev. A 1989, 40, 3698.
19. The EA of the chlorine atom is 3.62 eV, higher even than that of the fluorine atom (3.40 eV). Trainham, R.; Fletcher, G. D.; Larson, D. J. J. Phys. B: At. Mol. Phys. 1987, 20. L777. Blondel, C.; Cacciani, P.; Delsart, C.; Trainham, R. Phys. Rev. A 1989, 40, 3698.
20. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902.
21. Schwesinger, R.; Willaredt, J.; Schlemper, H.; Keller, M.; Schmitt, D.; Fritz, H. Chem. Ber. 1994, 127, 2435.
22. "Spontaneous" aromatization was much slower in hexane than in THF.
23. Early efforts to dehydrochlorinate decachloro compound 11 to obtain 3 included pyrolysis. Heating 11 at 250 °C gave a pale yellow mixture, so no azulenes were present. The major products were 1H-heptachloronaphthalene and, in smaller amount, octachloronaphthalene (see the Experimental Section). Because pyrolysis of hexachloroazulene 10 under the same conditions destroyed it without giving any identifiable compound, it is unlikely that azulenes were intermediates in the pyrolysis of 11.
24. Turro, N. J. Modern Molecular Photochemistry; Benjamin/Cummings: Menlo Park, CA, 1978; pp 147-8.
25. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratman, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; and Pople, J. A. Gaussian 98, revision A.5; Gaussian. Inc.; Pittsburgh, PA, 1998.
26. Data collection and structure solution were conducted at the X-ray Crystallographic Laboratory, 160 Kolthoff Hall, Department of Chemistry, University of Minnesota.
27. An empirical correction for absorption anisotropy, Blessing, R. Acta Crystallogr. 1995, A51, 33-38.
28. SAINT V6.1; Bruker Analytical X-ray Systems: Madison, WI.
29. SIR92; Altomare, A.; Cascamo, G.; Giacovazzo, C.; Guargliardi, A. J. Appl. Crystallogr. 1993, 26, 343-350.
30. SHELXTL-Plus V5.10; Bruker Analytical X-ray Systems: Madison, WI 1998.
31. Spek, A. L. Acta Crystallogr. 1990, A46, C34. Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; Utrecht University: Utrecht. The Netherlands, 2000.
32. Spek, A. L. Acta Crystallogr. 1990, A46, C34. Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; Utrecht University: Utrecht. The Netherlands, 2000.
33. Garciá, R.; Riera, J.; Carilla, J.; Juliá, L.; Molins, E.; Miravitlles, C. J. Org. Chem. 1992, 57, 5712.
34. Jakobsson, E.; Eriksson, L.; Bergman, Å. Acta Chem. Scand. 1992, 46, 527.