X-ray crystallographic and NMR structural studies of trans- 2,3-dichloro-5-ethyl-2,3-dihydrothieno[2 3-b]pyridine syn-1-oxide reactions of thiophene rings with hypochlorite reagents

Journal of Heterocyclic Chemistry

Volumn 36, Issue 4, 1999, Pages 1077-1080

  Klemm, LeRoy H ^a   Weakley, Timothy J R ^a   Yoon, Myungok ^a  

^a UNIVERSITY OF OREGON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HYPOCHLORITE; PYRIDINE DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONTROLLED STUDY; NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 0032835632     PISSN: 0022152X     EISSN: None     Source Type: Journal    
DOI: 10.1002/jhet.5570360440     Document Type: Article

References (21)

1. A. Kergomard and S. Vincent, Bull. Soc. Chim. France, 2197 (1967); A. Kergomard and J. Thiolliere, French Patent 1,405,408; Chem. Abstr., 63, 14815 (1965).
2. A. Kergomard and S. Vincent, Bull. Soc. Chim. France, 2197 (1967); A. Kergomard and J. Thiolliere, French Patent 1,405,408; Chem. Abstr., 63, 14815 (1965).
3. S. F. Birch and W. S. G. P. Norris, J. Chem. Soc., 127, 1934 (1925).
4. L. H. Klemm, R. E. Merrill, and F. H. W. Lee, J. Heterocyclic Chem., 11, 535 (1974).
5. L. H. Klemm and R. E. Merrill, J. Heterocyclic Chem., 9, 293 (1972).
6. It should be noted that a high yield of sulfone 2 results from treatment of benzo[b]thiophene with hydrogen peroxide-acetic acid; see F. G. Bordwell, B. B. Lampert, and W. H. McKellin, J. Am. Chem. Soc., 71, 1702 (1949). However, treatment of thienopyridines with this reagent produces exclusively N-oxides rather than S-oxides; see L. H. Klemm, I. T. Barnish, and R. Zell, J. Heterocyclic Chem., 7, 81 (1970); see L. H. Klemm, S. B. Mathur, R. Zell, and R. E. Merrill, J. Heterocyclic Chem., 8, 931 (1971).
7. It should be noted that a high yield of sulfone 2 results from treatment of benzo[b]thiophene with hydrogen peroxide-acetic acid; see F. G. Bordwell, B. B. Lampert, and W. H. McKellin, J. Am. Chem. Soc., 71, 1702 (1949). However, treatment of thienopyridines with this reagent produces exclusively N-oxides rather than S-oxides; see L. H. Klemm, I. T. Barnish, and R. Zell, J. Heterocyclic Chem., 7, 81 (1970); see L. H. Klemm, S. B. Mathur, R. Zell, and R. E. Merrill, J. Heterocyclic Chem., 8, 931 (1971).
8. It should be noted that a high yield of sulfone 2 results from treatment of benzo[b]thiophene with hydrogen peroxide-acetic acid; see F. G. Bordwell, B. B. Lampert, and W. H. McKellin, J. Am. Chem. Soc., 71, 1702 (1949). However, treatment of thienopyridines with this reagent produces exclusively N-oxides rather than S-oxides; see L. H. Klemm, I. T. Barnish, and R. Zell, J. Heterocyclic Chem., 7, 81 (1970); see L. H. Klemm, S. B. Mathur, R. Zell, and R. E. Merrill, J. Heterocyclic Chem., 8, 931 (1971).
9. P. Geneste, J. Grimaud, J.-L. Olivé, and S. N. Ung, Tetrahedron Letters, 2345 (1975).
10. P. Geneste, J.-L. Olivé, and S. N. Ung, J. Heterocyclic Chem., 14, 449 (1977).
11. However, an experiment using 95% methanol, instead of 95% t-butanol, did produce a 15% yield of 2.
12. P. Geneste, J.-L. Olivé, and S. N. Ung, J. Heterocyclic Chem., 14, 953 (1977).
13. P. Geneste, J.-L. Olivé, S. N. Ung, M. E. A. El Faghi, J. W. Easton, H. Beierbeck, and J. K. Saunders, J. Org. Chem., 44, 2887 (1979).
14. S. C. Abrahams, Acta Crystallogr., 10, 417 (1957).
15. R. Thomas, C. B. Shoemaker, and K. Eriks, Acta Crystallogr., 21, 12 (1966).
16. Note that Geneste et al isolated only three of the four possible stereoisomers in their studies. The cis-syn isomer was not reported.
17. W. Amann and G. Kresze, Tetrahedron Letters, 4909 (1968).
18. Compound 5 was designated as XIX in ref [3].
19. The nmr spectra were obtained on a Varian INOVA 300 instrument.
20. Note that assignments of signals to H-2 and H-3 may be interchanged.
21. These are the same as given in L. H. Klemm, T. J. R. Weakley, R. D. Gilbertson, and Y.-H. Song, J. Heterocyclic Chem., 35, 1269 (1998).