Ali Reza MODARRESI-ALAM, Hossein A. DABBAGH

Dynamic $^1 H-NMR$ demonstration of anomeric effect and structure: conformational and configurational analysis of N-2-(1,4-dioxane)-N'-(p-methylbenzenesulfonyl)- O-(p-methylphenoxy) isourea

The conformational and configurational behavior and the structure of N-2-(1,4-dioxane)-N' -(p-methylbenzenesulfonyl)- O-(p-methylphenoxy) isourea (1) were studied using dynamic NMR. The endo-anomeric effect, hydrogen bonding, temperature, and polarity of solvent control the population of dioxane ring conformers or anomers but not the configuration interconversion of the imine of the imidoyl moiety. Dynamic 1H-NMR, ΔH◦, ΔS◦, ΔG◦, and ΔG‡ analysis of 1 demonstrates that the dioxane ring adopts the chair conformation, that the imidoyl amino group prefers axial conformation, and that the tosyl and tolyl groups about the C=N bond retain the E configuration.

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1. Dabbagh, H. A.; Modarresi-Alam, A. R.; Tadjarodie A.; Taeb, A., Tetrahedron 2002, 58, 2621-2625 and references therein.
2. Dabbagh, H.; Faghihi K. Tetrahedron 2000, 56, 5019-5087
3. Dabbagh, H. A.; Mohammad Salehi, J. J. Org. Chem. 1998, 63, 7619-7627.
4. Dabbagh, H. A.; Malekpoor, S.; Faghihi, K. Iranian Polymer Journal 1998, 7, 149-156.
5. Bryan, L. A.; Smedley, W. M.; Summerbell, R. K. J. Am. Chem. Soc. 1950, 72, 2206-2209.
6. Hariss, R. K.; Spragg, R. A. J. Chem. Soc. (B) 1968, 684.
7. Anet, F. A.; Sandstrom, J.; Chem. Commun. 1971, 1558-1559.
8. Lemieux, R. U. Pure & Appl. Chem. 1971, 25, 527-548.
9. Fuchs, B.; Goldberg, I.; Shmueli, U. J. Chem. Soc. Perkin Trans. 2 1972, 357-365.
10. Jensen, F. R.; Neese, R. A. J. Am. Chem. Soc. 1975, 97, 4345-4348.
11. Fuchs, B.; Ellencweig, A. J. Org. Chem. 1979, 44, 2274-2277.
12. Aped, P.; Apeloig,Y.; Ellencweig, A.; Fuchs, B.; Goldberg, I.; Karini, M.; Tartakovsky, E. J. Am. Chem. Soc. 1987, 109, 1486-1495.
13. Lemaire, M.; Jeminet, G.; Cuer, A.; Gourcy, J.-G.; Dauphin, G. J. Chem. Soc. Perkin Trans. 2 1994, 1299-1302.
14. Caminati, W.; Dell’Erba, A.; Melandri, S.; Favero, P. G. J. Am. Chem. Soc. 1998, 120, 5555-5558.
15. Dabbagh, H. A.; Modarresi-Alam, A. R. J. Chem. Res. (S), 2000, 190-192.
16. Dabbagh, H. A.; Modarresi-Alam, A. R. J Chem. Res. (S), 2000, 44-45.
17. Modarresi-Alam, A. R.; Keykha, H.; Khamooshi, F.; Dabbagh, H. A. Tetrahedron, 2004, 60, 1527-1530.
18. Modarresi-Alam, A. R.; Khamooshi, F.; Rostamizadeh, M.; Keykha, H.; Nasrollahzadeh, M.; Bijanzadeh, H.-R.; Kleinpeter, E. J. Mol. Struct. 2007, 841, 61-66.
19. Fuchs B.; Ellencweig, A. Tetrahedron 1984, 40, 2011-2021.
20. Booth, H.; Dixon, J. M.; Kedhair, K. A.; Readshaw, S. A. Tetrahedron 1990, 46, 1625-1652.
21. Booth, H.; Readshaw, S. A. Tetrahedron 1990, 46, 2097-2110.
22. Booth, H.; Khedhair, K. A.; Readshaw, S. A. Tetrahedron 1987, 43, 4699-4723.
23. Booth, H.; Grindley, T. B.; Khedhair, K. A. J. Chem. Soc. Chem. Commun. 1982, 1047-1048.
24. Fuchs, B.; Ellencweig, A. Nouv. J. De Chimi. 1979, 3, 145-147.
25. Fuchs, B.; Ellencweig, A.; Tartakovsky, E.; Aped, P. Angew. Chem. Int. Ed. Engl. 1986, 25, 287-289.
26. Lambert, J. B. J. Am. Chem. Soc. 1967, 89, 1836-1840.
27. Lambert, J. B. Acc. Chem. Res. 1971, 4, 87-94.
28. Lambert, J. B.; Featherman, S. I. Chem. Rev. 1975, 75, 611-626.
29. Lambert, J. B.; Keske, R. G. Tetrahedron Lett. 1967, 4755-4758.
30. Juaristi, E.; Cuevas, G. Tetrahedron 1992, 48, 5019-5087 and references there in.
31. G¨unnter, H. NMR Spectroscopy, 2nd Ed., pp.119, John Wiley, New York, 1995.
32. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds, Chap.10, pp. 712, John Wiley, New York, 1994.
33. Lambert, J. B.; Wharry, S. M. J. Org. Chem. 1981, 46, 3193-3196.
34. Cai, J.; Davies, A. G.; Schiesser, C. H. J. Chem. Soc. Perkin Trans. 2 1994, 1151-1156.
35. Thomas, W. A. Prog. NMR Spectrosc. 1997, 30, 183-207.
36. Zaccari, D. G.; Snyder, J. P.; Peralta, J. E.; Taurian, O. E.; Contreras, R. H.; Barone, V. Molec. Phys. 2002, 100, 705-715.
37. Giralt, E.; Pericas, M. A.; Riera, A. Tetrahedron 1983, 39, 3959-3963.
38. Pinto, B. M.; Johnston, B. D.; Nagelkerke, R. J. Org. Chem. 1988, 53, 5668-5672.
39. Elliel, E. L. Acc. Chem. Res. 1970, 3, 1-8.
40. Elliel, E. L.; Knoeber, M. C. J. Am. Chem. Soc. 1968, 90, 3444-3458.
41. Pierson, G. O.; Runquist, O. A. J. Org. Chem. 1968, 33, 2572-2574.
42. Schaefer, J. J. Org. Chem. 1968, 33, 4558-4559.
43. Gatti, G.; Segre, A. L.; Morandi, C. Tetrahedron 1967, 23, 4385-4393.
44. Kozlowska-Gramsz, E.; Descotes, G. J. Heterocyclic Chem. 1983, 20, 671-672.
45. Kozlowska-Gramsz, E.; Descotes, G. Can. J. Chem. 1982, 60, 558-563.
46. Booth, H.; Khedhair, K. A. J. Chem. Soc. Chem. Commun. 1985, 467-468.
47. Tvaroska, I.; Carrel, J. P. J. Chem. Res. (S) 1991, 6-7.
48. Dabbagh, H. A.; Najafi Chermahinia, A. R.; Modarresi-Alam A. R.; Teimouria A. J. Iran. Chem. Soc. 2006, 3, 51-58. b) Dabbagh, H. A.; Najafi Chermahinia, A. R.; Modarresi-Alam A. R. Bull. Korean Chem. Soc. 2005, 26, 1229-1234.
49. Salzner, U.; Schleyer, P. V. R. J. Org. Chem. 1994, 59, 2138-2155.
50. Adam, W.; Peters, E.- M.; Peters, K.; Schnering, H. G.; Voerkel, V. Chem. Ber. 1992, 125, 1263-1266.