Nitronyl and imino nitroxides: Improvement of Ullman's procedure and report on a new efficient synthetic route

Chemistry - A European Journal

Volumn 7, Issue 9, 2001, Pages 2007-2014

  Hirel, Catherine ^a   Vostrikova, Kira E ^a   Pécaut, Jacques ^a   Ovcharenko, Victor I ^b   Rey, Paul ^a  

^a CEA GRENOBLE   (France)

^b INTERNATIONAL TOMOGRAPHY CENTER   (Russian Federation)

Author keywords

Amines; Heterocycles; Imidazolidines; Imidazolines nitroxides

Indexed keywords

CRYSTAL STRUCTURE; ETHANOL; X RAYS;

IMIDAZOLIDINES;

NITROGEN COMPOUNDS;

2,3 BIS(HYDROXYAMINO) 2,3 DIMETHYLBUTANE; AMINE; IMIDAZOLIDINE DERIVATIVE; IMIDAZOLINE DERIVATIVE; NITROXIDE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CRYSTAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; SYNTHESIS;

EID: 0035805361     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20010504)7:9<2007::AID-CHEM2007>3.0.CO;2-7     Document Type: Article

References (45)

1. J. H. Osiecki, E. F. Ullman, J. Am. Chem. Soc. 1968, 90, 1078.
2. E. F. Ullman, J. H. Osiecki, D. G. B. Boocock, R. Darcy, J. Am. Chem. Soc. 1972, 94, 7049.
3. E. F. Ullman, L. Call, J. H. Osiecki, J. Org. Chem. 1970, 35, 3623.
4. For recent reviews, see: V. I. Ovcharenko, R. Z. Sagdeev. Russ. Chem. Rev. 1999, 65, 345; Magnetism: A Supramolecular Function (Ed.: O. Kahn), Kluwer, Dordrecht, 1996; Mol. Cryst. Liq. Cryst. (Eds.: K. Itoh, J. S. Miller, T. Takui), 1997, 305/306, 1; Mol. Cryst. Liq. Cryst. (Ed.: O. Kahn), 1999, 334/335, 1.
5. For recent reviews, see: V. I. Ovcharenko, R. Z. Sagdeev. Russ. Chem. Rev. 1999, 65, 345; Magnetism: A Supramolecular Function (Ed.: O. Kahn), Kluwer, Dordrecht, 1996; Mol. Cryst. Liq. Cryst. (Eds.: K. Itoh, J. S. Miller, T. Takui), 1997, 305/306, 1; Mol. Cryst. Liq. Cryst. (Ed.: O. Kahn), 1999, 334/335, 1.
6. For recent reviews, see: V. I. Ovcharenko, R. Z. Sagdeev. Russ. Chem. Rev. 1999, 65, 345; Magnetism: A Supramolecular Function (Ed.: O. Kahn), Kluwer, Dordrecht, 1996; Mol. Cryst. Liq. Cryst. (Eds.: K. Itoh, J. S. Miller, T. Takui), 1997, 305/306, 1; Mol. Cryst. Liq. Cryst. (Ed.: O. Kahn), 1999, 334/335, 1.
7. For recent reviews, see: V. I. Ovcharenko, R. Z. Sagdeev. Russ. Chem. Rev. 1999, 65, 345; Magnetism: A Supramolecular Function (Ed.: O. Kahn), Kluwer, Dordrecht, 1996; Mol. Cryst. Liq. Cryst. (Eds.: K. Itoh, J. S. Miller, T. Takui), 1997, 305/306, 1; Mol. Cryst. Liq. Cryst. (Ed.: O. Kahn), 1999, 334/335, 1.
8. M. Kinoshita, Physica B 1995, 213-214, 257, and references therein.
9. R. Chiarelli, M. Novak, A. Rassat, J.-L. Tholance, Nature 1993, 363, 147.
10. A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392.
11. A. Caneschi, D. Gatteschi, P. Rey, Prog. Inorg. Chem. 1991, 39, 331.
12. 2 has been reported. H. G. Aurich, H. Czepluch, K. Hahn, Tetrahedron Lett. 1977, 50, 4373.
13. M. Lamchen, T. W. Mittag, J. Chem. Soc. C 1966, 2300.
14. R. Sayre, J. Am. Chem. Soc. 1955, 77, 6689.
15. V. I. Ovcharenko, V. I. Fokin, P. Rey, Proc. VI Int. Conf. Mol. Mag. Mol. Cryst. Liq. Cryst. 1999, 334, 109; V. I. Ovcharenko, V. I. Fokin, G. V. Romanenko, I. V. Korobkov, P. Rey, Russ. Chem. Bull. 1999, 48, 1519.
16. V. I. Ovcharenko, V. I. Fokin, P. Rey, Proc. VI Int. Conf. Mol. Mag. Mol. Cryst. Liq. Cryst. 1999, 334, 109; V. I. Ovcharenko, V. I. Fokin, G. V. Romanenko, I. V. Korobkov, P. Rey, Russ. Chem. Bull. 1999, 48, 1519.
17. A. R. Forrester, J. M. Hay, R. H. Thomson, Organic Chemistry of Stable Free Radicals, Academic Press, London, 1968, p. 180.
18. L. B. Volodarsky, V. A. Reznikov, V. I. Ovcharenko, Synthetic Chemistry of Stable Nitroxides, CRC, Boca Raton, 1994, p. 23.
19. J.F.W. Keana, Spin Labeling in Pharmacology (Ed.: J. L. Holtzmann), Academic Press, New York, 1984, p. 1.
20. R. Brière, H. Lemaire, A. Rassat, Bull. Soc. Chim. Fr. 1965, 3273.
21. G. Chapelet-Letourneux, H. Lemaire, A. Rassat. Bull. Soc. Chim. Fr. 1966, 3283.
22. T. Toda, E. Mori, K. Maruyama, Bull. Chem. Soc. Jpn. 1972, 45, 1904.
23. We noticed that use of crude 2,3-dimethyl-2,3-dinitrobutane, which probably contains brominated derivatives as impurity, often leads to the undesired methyl-substituted nitronyl nitroxide.
24. 4 (1 mL) were added successively to the solution (1 mL). Development of a pink color due to the presence of the corresponding nitronyl nitroxide indicates that compound 2 is present. This test is not quantitative because the nitroxide is not stable in this solution, and the color fades rapidly.
25. C.-M. Che, K.-Y. Wong, H.-W. Lam, K.-F. Chin, Z.-Y. Zhou, T. C. W. Mak, J. Chem. Soc. Dalton Trans. 1993, 857.
26. K. Hofmann, The Chemistry of Heterocyclic Compound (Ed.: A. Weissberger), Interscience Publishers, New York, 1953, p. 213.
27. L. F. Fieser, M. Fieser, Reagents for Organic Synthesis, Vol. I, Wiley, New York, 1967, p. 187.
28. S. Witek, A. Bielawska, J. Bielawski, J. Heterocycl. Chem. 1980, 14, 1313.
29. D. Cuvinot, P. Mangeney, A. Alexkis, J.-F. Normant, J. Org. Chem. 1989, 54, 2420.
30. G. Parrinello, R. Mülhaupt, J. Org. Chem. 1990, 55, 1772.
31. H.-W. Wanzlick, W. Löchel, Chem. Ber. 1953, 86, 1463.
32. Compound 5e is better obtained from acetaldehyde dimethylacetal because condensation with the unprotected acetaldehyde resulted in some trimer, which is found as impurity in the imidazolidine.
33. The structure is unexceptional. Structural features are reported in the CCDC data.
34. D. G. B. Boocock, R. Darcy, E. F. Ullman, J. Am. Chem. Soc. 1968, 90, 5945.
35. D. G. B. Boocock, E. F. Ullman, J. Am. Chem. Soc. 1968, 90, 6873.
36. H. Chikashita, S. Nishida, M. Miyazaki, Y. Morita, K. Itoh, Bull. Chem. Soc. Jpn. 1987, 60, 737.
37. K. M. Ibne-Rasa, J. O. Edwards, J. Am. Chem. Soc. 1962, 84, 763.
38. M. F. Asaro, I. Nakayama, R. B. Wilson, Jr., J. Org. Chem. 1992, 57, 778.
39. Y. Pei, O. Kahn, M. A. Aebersold, L. Ouahab, F. Le Berre, L. Pardi, J.-L. Tholence, Adv. Mater. 1994, 6, 681.
40. If it is put in a fridge, the precipitate is easier to filter but this does not increase the yield.
41. Reported yield for condensation in refluxing chloroform.
42. F. Lanfranc de Panthou, Thesis dissertation, Grenoble (France), 1994.
43. P. Rey, D. Luneau, Supramolecular Engineering of Synthetic Metallic Materials (Eds.: J. Veciana, C. Rovira, D. B. Amabilino), NATO ASI Series, Kluwer, 1999, 518, p. 145.
44. SAINT Version 4.050, Copyright 1992-1995, Siemens Analytical X-ray Instruments.
45. SHELXTL Version 5.030. Copyright 1994, Siemens Analytical X-ray Instruments.