Tetrazole and triazole

Tetrazoles and triazole synthesis and applications

1. Shrikant G. Pharande Tetrazoles and Triazoles Synthesis and applications

2. 1, 5 di -substituted tetrazole 5 -substituted tetrazole Tetrazoles

3. 1.Introduction - five-membered, doubly unsaturated ring consisting of one carbon and four nitrogen atoms

4. 1.Introduction - five-membered, doubly unsaturated ring consisting of one carbon and four nitrogen atoms - they are unknown to nature

5. 1.Introduction - five-membered, doubly unsaturated ring consisting of one carbon and four nitrogen atoms - they are unknown to nature - divided in three types parent monosubstituted disubstituted

6. 1.Introduction - five-membered, doubly unsaturated ring consisting of one carbon and four nitrogen atoms - they are unknown to nature - divided in three types - exist in the tautomeric forms Mol Divers. 2015,19(1):189-212

7. 1.Introduction - tetrazoles are stable to various chemical reagents such as oxidants, acids , bases, alkylating agents, dienophiles , etc.

8. 1.Introduction - tetrazoles are stable to various chemical reagents such as oxidants, acids , bases, alkylating agents, dienophiles , etc. - thermal stability is high

9. 1.Introduction - tetrazoles are stable to various chemical reagents such as oxidants, acids , bases, alkylating agents, dienophiles , etc. - thermal stability is high - tetrazoles are medicinally important Mol Divers. 2015,19(1):189-212

10. Chemical Reviews ,41,1,1947 First synthesized tetrazole by J. A. Bladin in 1885 2. Synthesis

11. 2. Synthesis Unsubstituted tetrazole Z. Anorg. Allg. Chem. 2008, 17111723

12. 2. Synthesis R = alkyl or aryl Eur. J. Org. Chem., 2012, 31, 6101. 5- sub. tetrazoles

13. 2. Synthesis 5- sub. tetrazoles by deprotection

14. 2. Synthesis 1, 5- sub. tetrazoles By using Ugi-azide Tetrahedron 67 (2011) 8902-8909 J. Mex. Chem. Soc. 2013, 57(4)

15. 2. Synthesis One pot ugi-azide reaction J. Mex. Chem. Soc. 2013, 57(4)

16. Ugi-azide reaction mechanism J. Mex. Chem. Soc. 2013, 57(4)

17. Ugi-azide reaction literature survey Org. Biomol . Chem., 2013, 11, 6036. 29-66% 8 examples

18. One pot ugi-azide / cyclisation EUR. J. ORG. CHEM., 16, 2014, 3379–3386

19. Enantioselective Passerini -Type Reaction Angew. Chem. Int. Ed. 2008, 47, 9454 –9457

20. Enantioselective isoquinoline-tetrazole by ugi-azide

21. 3. Reactivity 5- sub. Tetrazoles - alkylation Eur. J. Org. Chem., 2012, 31, 6101.

22. 3. Reactivity 5- sub. Tetrazoles - arylation Eur. J. Org. Chem., 2012, 31, 6101.

23. 4. Applications Medicinal chemistry Chemistry of Heterocyclic Compounds, Vol. 43, No. 1, 2007

24. 4. Applications Medicinal chemistry Chemistry of Heterocyclic Compounds, Vol. 43, No. 1, 2007

25. 4. Applications agrochemistry J. Agric. Food Chem. 1989, 37, 196-200 J. Agric. Food Chem. 2004, 52, 8081-8085

26. 4. Applications Other applications – in fluorescent Inorganica Chimica Acta 432 (2015) 50 Dalton Trans., 2014, 43, 6429–6435

27. 4. Applications Other applications - components of various combustible and thermally decomposing systems including solid propellants, blowing agents and initiating explosives. -selective recovering of palladium from the industrial wastes

28. 1,2,3 triazoles

29. 1.Introduction five-membered ring of two carbon atoms and three nitrogen atoms Divided in three main groups Monocyclic 1,2,3 triazole benzotriazole 1,2,3 triazolium salt

30. 1.Introduction Medicinal chemistry Agrochemicals Fluorescent materials dyes Polymer chemistry Chem. Rev. 2008, 108, 2952–3015

31. 2. Synthesis 1. Without using catalyst 2. By using catalyst Chem. Rev. 2008, 108, 2952–3015

32. 2. Synthesis J. Am. Chem. Soc, 2005 , 127, 210-216 . Organometallics 2007 , 26, 4389-4391 . Mechanism

33. 2. Synthesis Ugi - triazoles – linked triazole 99-100% 20 examples Bioorg . Med. Chem. Lett . 22 (2012) 2598–2603 R 2 = n-butyl, 2-F, 4- Cl , Bn R 1 = 2-Br, 2-Cl, 2-F, 4-F

34. 2. Synthesis Ugi - triazoles – 6 component ugi ACS Comb. Sci. 2014, 16, 176−183 17 examples 81-92%

35. 2. Synthesis Ugi - triazoles – peptoid mimics Org. Biomol . Chem., 2011, 9, 5024–5027

36. 2. Synthesis Ugi - triazoles – fused triazole Tetrahedron Lett . 2004, 45 , 8439 86-98% 7 examples

37. 2. Synthesis Ugi - triazoles – fused triazole 39-94% 13 examples Org. Biomol . Chem., 2014, 12, 6986–6989

38. 2. Synthesis Ugi - triazoles – macrocycles in pot Oxazole intermediate Org. Lett ., 2006, 8, 4145

39. 2. Synthesis Ugi - triazoles – click and post condensation Eur. J. Org. Chem.,2013, 1223 One example by using terminal alkyne

40. 3. Reactivity Alkyl nucleophilic sub. reaction 1:1.7 Farmaco 60 (2005) 367–375 Pd catalysed arylation at c5 Org. Lett., 9, 2007, 2333

41. 4. Applications Medicinal chemistry Chem. Asian J. 2011, 6, 2696 – 2718

42. 4. Applications I Agrochemistry Org. Biomol . Chem., 2015, 13, 477–486 PCT Int. Appl. (2013), WO 2013037289 A1 J. Agric. Food Chem. 2006, 54, 1361-1372

43. 4. Applications Fluorescent compounds Org. Biomol . Chem., 2014, 12, 5158 Synthesis 2014, 46, 3239–3248 Organogelator and fluorescent Tetrahedron 71 (2015) 2124. fluoroionophores Chem. Commun ., 2014, 50, 14167 Antimicrobial and fluorescent Eur. J. Med. Chem. 77 ,2014,145.