Conformational studies by dynamic NMR. 94. Cogwheel pathway for the stereomutations of durene derivatives containing the mesityl ring

Journal of Organic Chemistry

Volumn 68, Issue 19, 2003, Pages 7266-7273

  Coluccini, Carmine ^a   Grilli, Stefano ^a   Lunazzi, Lodovico ^a   Mazzanti, Andrea ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONS; CRYSTALLIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PERMITTIVITY;

INTERCONVERSION;

AROMATIC HYDROCARBONS;

1,4 BIS(MESITOYL)DURENE; 1,4 BIS(MESITYLETHENYL)DURENE; DURENE DERIVATIVE; HETEROCYCLIC COMPOUND; SOLVENT; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BINDING; CONFORMATIONAL TRANSITION; CORRELATION ANALYSIS; CRYSTALLIZATION; DIELECTRIC CONSTANT; MOLECULAR STABILITY; NUCLEAR MAGNETIC RESONANCE; SOLID STATE; STEREOCHEMISTRY; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 0141677917     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo034737t     Document Type: Article

References (44)

1. Part 93: Casarini, D.; Rosini, C.; Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2003, 68, 1815.
2. In partial fulfillment of the requirements for the PhD in Chemical Sciences, University of Bologna.
3. Bonini, B. F.; Grossi, L.; Lunazzi, L.; Macciantelli, D. J. Org. Chem. 1986, 51, 517. Casarini, D.; Lunazzi, L.; Pasquali, F.; Gasparrini, F.; Villani, C. J. Am. Chem. Soc. 1992, 114, 6521. Casarini, D.; Lunazzi, L.; Verbeek, R. Tetrahedron 1996, 52, 2471. Leardini, R.; Lunazzi, L.; Mazzanti, A.; Nanni, D. J. Org. Chem. 2001, 66, 7879.
4. Bonini, B. F.; Grossi, L.; Lunazzi, L.; Macciantelli, D. J. Org. Chem. 1986, 51, 517. Casarini, D.; Lunazzi, L.; Pasquali, F.; Gasparrini, F.; Villani, C. J. Am. Chem. Soc. 1992, 114, 6521. Casarini, D.; Lunazzi, L.; Verbeek, R. Tetrahedron 1996, 52, 2471. Leardini, R.; Lunazzi, L.; Mazzanti, A.; Nanni, D. J. Org. Chem. 2001, 66, 7879.
5. Bonini, B. F.; Grossi, L.; Lunazzi, L.; Macciantelli, D. J. Org. Chem. 1986, 51, 517. Casarini, D.; Lunazzi, L.; Pasquali, F.; Gasparrini, F.; Villani, C. J. Am. Chem. Soc. 1992, 114, 6521. Casarini, D.; Lunazzi, L.; Verbeek, R. Tetrahedron 1996, 52, 2471. Leardini, R.; Lunazzi, L.; Mazzanti, A.; Nanni, D. J. Org. Chem. 2001, 66, 7879.
6. Bonini, B. F.; Grossi, L.; Lunazzi, L.; Macciantelli, D. J. Org. Chem. 1986, 51, 517. Casarini, D.; Lunazzi, L.; Pasquali, F.; Gasparrini, F.; Villani, C. J. Am. Chem. Soc. 1992, 114, 6521. Casarini, D.; Lunazzi, L.; Verbeek, R. Tetrahedron 1996, 52, 2471. Leardini, R.; Lunazzi, L.; Mazzanti, A.; Nanni, D. J. Org. Chem. 2001, 66, 7879.
7. Casarini, D.; Lunazzi, L. J. Org. Chem. 1996, 61, 6240.
8. (a) Grilli, S.; Lunazzi, L.; Mazzanti, A.; Casarini, D.; Femoni, C. J. Org. Chem. 2001, 66, 488.
9. (b) Casarini, D.; Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2001, 66, 2757.
10. (c) Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2001, 66, 4444.
11. MMFF force field, as implemented in the computer package PC-Model 7.5 (Serena Software: Bloomington, IN).
12. Lindner, A. B.; Grynszpan, F.; Biali, S. E. J. Org. Chem. 1993, 58, 6662.
13. This barrier is sometimes referred to as the γ-barrier to indicate the possibility of conjugation, due to the planarity of the transition state. In the present case conjugation can occur in the transition state between the C=O substituent and the coplanar aromatic ring. See: Anderson, J. E.; Casarini, D.; Lunazzi, L. Tetrahedron Lett. 1988, 29, 3141.
14. (a) Mislow, K. Acc. Chem. Res. 1976, 9, 26,
15. (b) Mislow, K. Chemtracts Org. Chem. 1989, 2, 151.
16. (c) Glaser, R. In Acyclic Organonitrogen Stereochemistry; Lambert, J. B., Takeuchi, Y., Eds.; VCH: New York, 1992; Chapter 4, p 123.
17. Biali, S. E.; Nugiel, D. A.; Rappoport, Z. J. Am. Chem. Soc. 1989, 111,846.
18. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Mazzanti, G. J. Org. Chem. 2001, 66, 748 and references quoted therein.
19. This signal was unambiguously assigned by a 2D heteronuclear correlation (gHMBC sequence) showing the presence of a three-bond long-range coupling between these methyl hydrogens and the aromatic CH carbon of mesitylene. This coupling was not observed in the case of the methyl hydrogens of durene.
20. Casarini, D.; Lunazzi, L. J. Org. Chem. 1996, 61, 6240.
21. QCPE program no. 633, Indiana University: Bloomington, IN.
22. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
23. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
24. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
25. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
26. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
27. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
28. As was often observed in conformational processes the ΔG‡ value is independent of temperature, indicating a negligible ΔS‡ value. See: Hoogosian, S.; Bushweller, C. H.; Anderson, W. G.; Kigsley, G. J. Phys. Chem. 1976, 80, 643. Lunazzi, L.; Cerioni, G.; Ingold, K. U. J. Am. Chem. Soc. 1976, 98, 7484. Bernardi, F.; Lunazzi, L.; Zanirato, P.; Cerioni, G. Tetrahedron 1977, 33, 1337. Lunazzi, L.; Magagnoli, C.; Guerra, M.; Macciantelli, D. Tetrahedron Lett. 1979, 3031. Anderson, J. E.; Tocher, D. A.; Casarini, D.; Lunazzi, L. J. Org. Chem. 1991, 56, 1731. Cremonini, M. A.; Lunazzi, L.; Placucci, G.; Okazaki, R.; Yamamoto, G. J. Am. Chem. Soc. 1992, 114, 6521. Borghi, R.; Lunazzi, L.; Placucci, G.; Cerioni, G.; Foresti, E.; Plumitallo, A. J. Org. Chem. 1997, 62, 4923.
29. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
30. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
31. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
32. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
33. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
34. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1997, 62, 7592. Casarini, D.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 1998, 63, 4991. Bonini, B. F.; Fochi, M.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 2596. Grilli, S.; Lunazzi, L.; Mazzanti, A. J. Org. Chem. 2000, 65, 3563. Dell'Erba, C.; Gasparrini, F.; Grilli, S.; Lunazzi, L.; Mazzanti, A.; Novi, M.; Pierini, M.; Tavani, C.; Villani, C. J. Org. Chem. 2000, 65, 1663. Grilli, S.; Lunazzi, L.; Mazzanti, A.; Pinamonti, M. J. Org. Chem. 2002, 67, 5733.
35. 6 solution) owing to the increased viscosity.
36. In the case of 1 these separations were barely detectable, being only 0.005 ppm for the p-methyl signals of mesitylene and 0.006 ppm for the methyl signals of durene (see Figure 1).
37. Landolt-Börnstein, Band II, Teil 6; Springer-Verlag: Berlin, Germany, 1959.
38. The two minor lines of the p-methyl group of mesitylene (at 2.55 ppm) are so close as to make their separation barely distinguishable.
39. Methylene chloride was selected because, even at temperatures in the range -80 to - 85 °C, it is capable of dissolving compound 2 quite rapidly and is still fluid enough as to yield sufficiently resolved spectra for distinguishing the signals of the syn from those of the anti form. At lower temperatures the time required to dissolve the compound was too long, thus allowing the equilibrium to be established before the sample could be transferred into the NMR probe.
40. 2 increases from 2.9:1 to 5.2:1 by lowering of the temperature from -60 to -90 °C. The more stable species increases its proportion not only according to the Boltzamann equation but also because of the larger value of the dielectric constant at lower temperatures.19
41. Taha, M.; Marks, V.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2000, 65, 8621. Marks, V.; Gottlieb, H. E.; Melman, A.; Byk, G.; Cohen, S.; Biali, S. E. J. Org. Chem. 2001, 66, 6711. Marks, V.; Nahmany, M.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2002, 67, 7898.
42. Taha, M.; Marks, V.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2000, 65, 8621. Marks, V.; Gottlieb, H. E.; Melman, A.; Byk, G.; Cohen, S.; Biali, S. E. J. Org. Chem. 2001, 66, 6711. Marks, V.; Nahmany, M.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2002, 67, 7898.
43. Taha, M.; Marks, V.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2000, 65, 8621. Marks, V.; Gottlieb, H. E.; Melman, A.; Byk, G.; Cohen, S.; Biali, S. E. J. Org. Chem. 2001, 66, 6711. Marks, V.; Nahmany, M.; Gottlieb, H. E.; Biali, S. E. J. Org. Chem. 2002, 67, 7898.
44. Roberts, R. M.; El-Khawaga, A. M.; Roengsumram, S. J. Org. Chem. 1984, 49, 1380.