Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Methimazole-disulfide as an Anti-Thyroid Drug Metabolite Catalyzed the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens

  • Eshghi, H. (Department of Chemistry, Ferdowsi University of Mashhad) ;
  • Tayyari, S.F. (Department of Chemistry, Ferdowsi University of Mashhad) ;
  • Rezvani-Amin, Z. (Department of Chemistry, Ferdowsi University of Mashhad) ;
  • Roohi, H. (Department of Chemistry, Sistan & Baluchestan University)
  • Published : 2008.01.20
Download PDF
⟨ Previous Next ⟩

Abstract

The regioselective ring opening of epoxides using elemental iodine and bromine in the presence of methimazole (MMI, a anti-thyroid drug) and its metabolite methimazole-disulfide as new catalysts are studied. MMI easily converted in vitro to MMI-disulfide without any double activation presented in vivo. FT-Raman and UV spectroscopies are used to study the interaction of iodine with these catalysts. The results indicate that both catalysts are efficient in polyiodide formation, but MMI-disulfide can catalyze this reaction in higher yield and regioselectivity. The complex [(MMI-disulfide)I]+.I3- is considered to be formed initially which could be bulkier by addition of excess of iodine in the course of the reaction. These bulky nucleophiles have a fundamental role in the high regioselectivity by attacking the less sterically hindered epoxide carbon. In this study we suggest that MMI is readily converted to MMI-disulfide by interaction with iodine or activated iodine in thyroid gland, and this process is responsible for high anti-thyroid activity of MMI.

Keywords

References

  1. Buxeraud, J. In Traite de Chimie Therapeutique; Tec et Doc Lavoisier: Paris, 1995; vol. 4, ch. 18
  2. Roy, G.; Nethaji, M.; Mugesh, G. Org. Biomol. Chem. 2006, 4, 2883 https://doi.org/10.1039/b604060h
  3. Roy, G.; Mugesh, G. Phosphorus, Sulfur, and Silicon 2005, 180, 891 https://doi.org/10.1080/10426500590906391
  4. Laurence, C.; El-Ghomari, M. J.; Le Questel, J.-Y.; Berthelot, M.; Mokhlisse, R. J. Chem. Soc., Perkin Trans. 2 1998, 1545
  5. Laurence, C.; El-Ghomari, M. J.; Berthelot, M. J. Chem. Soc., Perkin Trans. 2 1998, 1163
  6. Laurence, C.; El-Ghomari, M. J.; Lucon, M. J. Chem. Soc., Perkin Trans. 2 1998, 1159
  7. Corban, G. J.; Hadjikakou, S. K.; hadjiliadis, N.; Kubicki, M.; Tiekink, E. R. T.; Butler, I. S.; Drougas, E.; Kosmas, A. M. Inorg. Chem. 2005, 44, 8617 https://doi.org/10.1021/ic0484396
  8. Buxeraud, J.; Absil, A. C.; Claude, J.; Raby, C.; Catanzano, G.; Beck, C. J. Med. Chem. 1985, 20, 43
  9. Raby, C.; Lagoree, A. C.; Jambut-Absil, A. C.; Buxeraud, J.; Catanzano, G. Endocrinology 1990, 126, 1683 https://doi.org/10.1210/endo-126-3-1683
  10. Sharghi, H.; Massah, A. R.; Eshghi, H.; Niknam, K. J. Org. Chem. 1998, 63, 1455 https://doi.org/10.1021/jo971453y
  11. Sharghi, H.; Eskandari, M. M. Tetrahedron 2003, 59, 8509 https://doi.org/10.1016/j.tet.2003.09.033
  12. Sharghi, H.; Paziraee, Z.; Niknam, K. Bull. Korean Chem. Soc. 2002, 23, 1611 https://doi.org/10.5012/bkcs.2002.23.11.1611
  13. Nakashima, T.; Taurog, A. Clin. Endocrinol. 1979, 10, 637 https://doi.org/10.1111/j.1365-2265.1979.tb02122.x
  14. Melander, A.; Hellengren, B.; Rosendal-Helgesen, S.; Sjoberg, A. K.; Wahlin-Boll, E. Eur. J. Clin. Pharmacol. 1980, 17, 295 https://doi.org/10.1007/BF00625803
  15. Jansson, R.; Dalhberg, P. A.; Lindstrom, B. Int. J. Clin. Pharmacol. Ther. Toxicol. 1983, 21, 505
  16. Konaklieva, M. I.; Dahi, M. L.; Turos, E. Tetrahedron Lett. 1992, 33(47), 7093 https://doi.org/10.1016/S0040-4039(00)60844-4
  17. Corey, E. J.; Brunelle, D. J. Tetrahedron Lett. 1976, 3409
  18. Frank, R. L.; Blegen, J. R. Organic Syntheses, Coll. Vol. 3 1955, 116
  19. Semnani, A.; Shamsipur, M. J. Chem. Soc., Dalton Trans. 1996, 2215
  20. Mizuno, M.; Tanaka, J.; Harada, I. J. Phys. Chem. 1981, 85, 1789 https://doi.org/10.1021/j150613a006
  21. Andrews, L. J.; Prochaska, E. S.; Loewenschuss, A. Inorg. Chem. 1980, 19, 463 https://doi.org/10.1021/ic50204a036
  22. Lang, R. P. J. Phys. Chem. 1974, 78, 1657 https://doi.org/10.1021/j100609a012
  23. Buckles, R. E.; Yuk, J. P.; Popov, A. I. J. Am. Chem. Soc. 1952, 74, 4379 https://doi.org/10.1021/ja01137a041
  24. Deplano, P.; Ferraro, J. R.; Mercuri, M. L.; Trogu, E. F. Coord. Chem. Rev. 1999, 188, 71 https://doi.org/10.1016/S0010-8545(98)00238-0
  25. Nour, E. M.; Shahada, L. M. A. Spectrochim. Acta Part A 1988, 44, 1277 https://doi.org/10.1016/0584-8539(88)80169-7
  26. Nour, E. M. Spectrochim. Acta Part A. 1991, 47, 743 https://doi.org/10.1016/0584-8539(91)80145-9
  27. Nour, E. M. Spectrochim. Acta Part A. 1999, 56, 167
  28. Nour, E. M.; Chen, L. H.; Laane, J. J. Phys. Chem. 1986, 90, 2841 https://doi.org/10.1021/j100404a014
  29. Taurog, A.; Dorris, M. L.; Guziec, F. S. Endocrinology 1989, 124, 30 https://doi.org/10.1210/endo-124-1-30
  30. Aragoni, M. C.; Arca, M.; Demartin, F.; Devillanova, F. A.; Garau, A.; Isaia, F.; Lippolis, V.; Verani, G. J. Am. Chem. Soc. 2002, 124, 4538 https://doi.org/10.1021/ja012731k
  31. Bajwa, J. S.; Anderson, R. C. Tetrahedron Lett. 1991, 32, 3021 https://doi.org/10.1016/0040-4039(91)80676-W
  32. Chini, M.; Crotti, P.; Gardelli, C.; Macchia, F. Tetrahedron 1992, 48, 3805 https://doi.org/10.1016/S0040-4020(01)92271-9
  33. Suh, Y. G.; Koo, B. A.; Ko, J. A.; Cho, Y. S. Chem. Lett. 1993, 1907
  34. Iranpoor, N.; Kazemi, F.; Salehi, P. Synth. Commun. 1997, 27, 1247 https://doi.org/10.1080/00397919708003362
  35. Sabitha, G.; Babu, R. S.; Rajkumar, M.; Reddy, C. S.; Yadav, J. S. Tetrahedron Lett. 2001, 42, 3955 https://doi.org/10.1016/S0040-4039(01)00622-0
  36. Reddy, M. A.; Surendra, K.; Bhanumathi, N.; Rao, K. R. Tetrahedron 2002, 58, 6003 https://doi.org/10.1016/S0040-4020(02)00614-2

Cited by

  1. A novel method for sensing of methimazole using gold nanoparticle-catalyzed chemiluminescent reaction vol.26, pp.3, 2011, https://doi.org/10.1002/bio.1207
  2. A Kinetic Study on Electrooxidation of Propyl-Thiouracil: An Anti-Hyperthyroid Drug by Potassium Iodide vol.160, pp.10, 2013, https://doi.org/10.1149/2.043310jes
  3. ChemInform Abstract: Methimazole-Disulfide as an anti-Thyroid Drug Metabolite Catalyzed the Highly Regioselective Conversion of Epoxides to Halohydrins with Elemental Halogens. vol.39, pp.23, 2008, https://doi.org/10.1002/chin.200823038
  4. A novel method for methimazole determination using CdSe quantum dots as fluorescence probes vol.165, pp.1-2, 2009, https://doi.org/10.1007/s00604-008-0120-4
  5. Fe(HSO4)3 and Fe(HSO4)3/DMSO as Efficient, Heterogeneous, and Reusable Catalyst Systems for the Oxidative Coupling of Thiols vol.184, pp.11, 2008, https://doi.org/10.1080/10426500802704654