A New Synthesis of Diazenes (Azoalkanes) Using 4-(S,S-Dimethylsulfoximino)- 1,2,4-triazoline-3,5-dione. the Construction of Diazenes from Amino Nitrenes via Base-Induced Sulfoximine Cleavage

Journal of Organic Chemistry

Volumn 62, Issue 11, 1997, Pages 3779-3781

  Meehan, Scott ^a   Little, R Daniel ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0043076061     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970011j     Document Type: Article

References (24)

1. (a) Adam, W.; De Lucchi, O. Angew. Chem., Int. Ed. Engl. 1980, 19, 762.
2. (b) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88.
3. (c) Engel, P. S. Chem Rev. 1980, 99.
4. (a) Barton, D. H. R.; Shioiri, T.; Widdowson, D. A. J. Chem. Soc., C 1971, 1968.
5. (b) Semmelhack, M. F.; Foos, J. S.; Katz, S. J. Am. Chem. Soc. 1973, 95, 7325.
6. (c) Squillacote, M.; De Felippis, J. J. Org. Chem. 1994, 59, 3564.
7. (d) The diazenes illustrated in the table are known and their preparation is recorded in Little, R. D.; Carroll, G. L. J. Org. Chem. 1979, 44, 4720.
8. Lenoir, J. A.; Colebrook, L. D.; Williams, D. F. Can. J. Chem. 1972, 50, 2661.
9. N-Aminourazole was first synthesized by the Thiele and Curtius groups over a century ago. (a) Thiele, J.; Stange, O. Liebigs Ann. Chem. 1894, 283, 1. (b) Curtius, T.; Heidenreich, K. Chem. Ber. 1894, 2684.
10. N-Aminourazole was first synthesized by the Thiele and Curtius groups over a century ago. (a) Thiele, J.; Stange, O. Liebigs Ann. Chem. 1894, 283, 1. (b) Curtius, T.; Heidenreich, K. Chem. Ber. 1894, 2684.
11. (a) Cambell, C. D.; Rees, C. W. Chem. Commun. 1965, 10, 193.
12. (b) Gilchrist, T. L.; Rees, C. W.; Stanton, E. Chem. Commun. 1971, 801.
13. (c) Anderson, D. J.; Horwell, D. C.; Stanton, E.; Gilchrist, T. L.; Rees, C. W. J. Chem. Soc., Perkin Trans. 1 1972, 1317.
14. The mechanism of hydrazine oxidation is not known. There is considerable evidence that a "free" amino-nitrene is not involved. The sulfoximine can be formed by the reaction of DMSO with another electrophilic nitrogen intermediates. See: (a) Atkinson, R. S.; Jones, D. W.; Kelly, B. J. J. Chem. Soc., Perkin Trans, 1 1991, 1344. (b) Atkinson, R. S.; Grimshire, M. J.; Kelly, B. J. Tetrahedron 1989, 43, 2873
15. The mechanism of hydrazine oxidation is not known. There is considerable evidence that a "free" amino-nitrene is not involved. The sulfoximine can be formed by the reaction of DMSO with another electrophilic nitrogen intermediates. See: (a) Atkinson, R. S.; Jones, D. W.; Kelly, B. J. J. Chem. Soc., Perkin Trans, 1 1991, 1344. (b) Atkinson, R. S.; Grimshire, M. J.; Kelly, B. J. Tetrahedron 1989, 43, 2873
16. Little, R. D. Chem. Rev. 1996, 96, 93.
17. Fulvene adducts with STAD (1) must be hydrogenated at low temperature using diimide to avoid rearrangements. Attempts to convert the initially formed adduct to diazene without first reducing the Δ-5,6 π bond would afford an unstable material that would lose nitrogen and regenerate the fulvene. (a) Adam, W.; Erden, I. Angew. Chem., Int. Ed. Engl. 1978, 17, 210. (b) Olsen, H. Angew. Chem. Suppl. 1982, 893. (c) Zhang, X.; Khan, S. I.; Foote, C. S. J. Org. Chem. 1995, 60, 4102. Adducts that do not rearrange can be conveniently hydrogenated over Pd/C.
18. Fulvene adducts with STAD (1) must be hydrogenated at low temperature using diimide to avoid rearrangements. Attempts to convert the initially formed adduct to diazene without first reducing the Δ-5,6 π bond would afford an unstable material that would lose nitrogen and regenerate the fulvene. (a) Adam, W.; Erden, I. Angew. Chem., Int. Ed. Engl. 1978, 17, 210. (b) Olsen, H. Angew. Chem. Suppl. 1982, 893. (c) Zhang, X.; Khan, S. I.; Foote, C. S. J. Org. Chem. 1995, 60, 4102. Adducts that do not rearrange can be conveniently hydrogenated over Pd/C.
19. Fulvene adducts with STAD (1) must be hydrogenated at low temperature using diimide to avoid rearrangements. Attempts to convert the initially formed adduct to diazene without first reducing the Δ-5,6 π bond would afford an unstable material that would lose nitrogen and regenerate the fulvene. (a) Adam, W.; Erden, I. Angew. Chem., Int. Ed. Engl. 1978, 17, 210. (b) Olsen, H. Angew. Chem. Suppl. 1982, 893. (c) Zhang, X.; Khan, S. I.; Foote, C. S. J. Org. Chem. 1995, 60, 4102. Adducts that do not rearrange can be conveniently hydrogenated over Pd/C.
20. Little, R. D.; Brown, L. M. J. Am. Chem. Soc. 1992, 114, 3071 and references therein.
21. Little, R. D.; Billera, C. B. Tetrahedron Lett. 1988, 29, 5711.
22. See also, (a) Carpino, L. A. J. Am. Chem. Soc. 1957, 79, 4427. (b) Carpino, L. A.; Göwecke, S. J. Org. Chem. 1964, 29, 2824. (c) Carpino, L. A. J. Org. Chem. 1965, 30, 737.
23. See also, (a) Carpino, L. A. J. Am. Chem. Soc. 1957, 79, 4427. (b) Carpino, L. A.; Göwecke, S. J. Org. Chem. 1964, 29, 2824. (c) Carpino, L. A. J. Org. Chem. 1965, 30, 737.
24. See also, (a) Carpino, L. A. J. Am. Chem. Soc. 1957, 79, 4427. (b) Carpino, L. A.; Göwecke, S. J. Org. Chem. 1964, 29, 2824. (c) Carpino, L. A. J. Org. Chem. 1965, 30, 737.