Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Synthesis of 4-Aryl-3(5)-(2-hydroxyphenyl)pyrazoles by Reaction of Isoflavones and their 4-Thio Analogues with Hydrazine Derivatives*

Albert Lévai A E , Artur M. S. Silva B E , José A. S. Cavaleiro B , José Elguero C , Ibon Alkorta C and József Jekő D
+ Author Affiliations
- Author Affiliations

A Department of Organic Chemistry, University of Debrecen, PO Box 20, H-4010 Debrecen, Hungary.

B Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.

C Instituto de Química Médica, C/ Juan de la Cierva, 3, E-28006 Madrid, Spain.

D Department of Chemistry, College of Nyíregyháza, Sóstói u. 31/b, H-4400 Nyíregyháza, Hungary.

E Corresponding authors. Email: alevai@puma.unideb.hu; artur.silva@ua.pt

Australian Journal of Chemistry 60(12) 905-914 https://doi.org/10.1071/CH07268
Submitted: 30 July 2007  Accepted: 13 September 2007   Published: 4 December 2007

Abstract

4-Aryl-3(5)-2-(hydroxyphenyl)pyrazoles have been prepared by the reaction of isoflavones and their 4-thio analogues with hydrazine hydrate and phenylhydrazine in hot pyridine. The reaction mechanism for the formation of these pyrazoles is discussed. All the new compounds have been fully characterized by NMR spectroscopy. In [D6]DMSO, a 1H NMR study allows observation of the presence of both pyrazole annular tautomers, due to the presence of intramolecular hydrogen bonds in each tautomer (OH···N and NH···O). Theoretical calculations have been carried out on tautomers and conformers of compounds 20 (3(5)-(2-hydroxy-4-methoxyphenyl)-5(3)-methyl-4-phenylpyrazole) and 21 (3(5)-(2-hydroxy-4-methoxyphenyl)-4-(2-methoxyphenyl)-5(3)-methylpyrazole), including the absolute shieldings (GIAO/B3 LYP/6–311++G**) of 21.


Acknowledgements

Thanks are due to the Hungarian Scientific Research Fund (grant no. OTKA T049468) and also to the University of Aveiro, ‘Fundação para a Ciência e a Tecnologia,’ and FEDER for funding the Organic Chemistry Research Unit. The technical assistance of Mrs M. Nagy and Mr L. Szabó is highly appreciated.


References


[1]   Elguero J. , Comprehensive Heterocyclic Chemistry (Eds A. R. Katritzky, C. W. Rees) 1984, Vol. 5, pp. 167–303 (Pergamon Press: Oxford).

[2]   Elguero J. , Comprehensive Heterocyclic Chemistry II (Eds A. R. Katritzky, C. W. Rees, E. F. Scriven) 1996, Vol. 3, pp. 1–75 (Pergamon Press: Oxford).

[3]   Elguero J. , Goya P. , Jagerovic N. , Silva A. M. S. , Targets in Heterocyclic Systems – Chemistry and Properties (Eds O. Attanasi, D. Spinelli) 2002, Vol. 6, pp. 52–98 (Italian Society of Chemistry: Rome).

[4]   Eicher T. , Hauptmann S. , The Chemistry of Heterocycles – Structure, Reactions, Synthesis and Application (Transl. H. Suschitzky, J. Suschitzky) 1995, p. 184 (Georg Thieme: Stuttgart).

[5]   K. Takagi, M. Tanaka, Y. Murakami, H. Morita, T. Aoutsuka, Eur. J. Med. Chem. Chim. Ther. 1986, 21,  65.
        |  CAS |  

[6]   B. W. Dymock, X. Barril, P. A. Brough, J. E. Cansfield, A. Massey, E. McDonald, R. E. Hubbard, A. Surgenor, D. Roughley, P. Webb, P. Workman, L. Wright, M. J. Drysdale, J. Med. Chem. 2005, 48,  4212.
        | CrossRef |  CAS |  

[7]   K.-M. J. Cheung, T. P. Matthews, K. James, M. G. Rowlands, K. J. Boxall, S. Y. Sharp, A. Maloney, S. M. Roe, C. Prodromou, L. H. Pearl, G. Wynne Aherne, E. McDonald, P. Workman, Bioorg. Med. Chem. Lett. 2005, 15,  3338.
        | CrossRef |  CAS |  

[8]   P. A. Brough, X. Barril, M. Beswick, B. W. Dymock, M. J. Drysdale, L. Wright, K. Grant, A. Massey, A. Surgenor, P. Workman, Bioorg. Med. Chem. Lett. 2005, 15,  5197.
        | CrossRef |  CAS |  

[9]   X. Barril, M. Beswick, A. Collier, M. J. Drysdale, B. W. Dymock, A. Fink, K. Grant, R. Howes, A. M. Jordan, A. Massey, A. Surgenor, J. Wayne, P. Workman, L. Wright, Bioorg. Med. Chem. Lett. 2006, 16,  2543.
        | CrossRef |  CAS |  

[10]   R. Howes, X. Barril, B. W. Dymock, K. Grant, C. J. Northfield, A. G. S. Robertson, A. Surgenor, J. Wayne, L. Wright, K. James, T. Matthews, K.-M. Cheung, E. McDonald, P. Workman, M. J. Drysdale, Anal. Biochem. 2006, 350,  202.
        | CrossRef |  CAS |  

[11]   R. Ahmad, N. Ahmad, M. Zia-Ul-Haq, A. Wahid, J. Chem. Soc. Pak. 1996, 18,  38.
        |  CAS |  

[12]   J. Catalán, F. Fabero, M. S. Guijano, R. M. Claramunt, M. D. S. Maria, M. C. Foces-Foces, F. H. Cano, J. Elguero, R. Sastre, J. Am. Chem. Soc. 1990, 112,  747.
        | CrossRef |   

[13]   J. Catalán, F. Fabero, R. M. Claramunt, M. S. D. Maria, M. C. Foces-Foces, F. H. Cano, M. Martinez-Ripoll, J. Elguero, R. Sastre, J. Am. Chem. Soc. 1992, 114,  5039.
        | CrossRef |   

[14]   D. C. G. A. Pinto, A. M. S. Silva, J. A. S. Cavaleiro, C. Foces-Foces, A. L. Llamas-Saiz, N. Jagerovic, J. Elguero, Tetrahedron 1999, 55,  10187.
        | CrossRef |  CAS |  

[15]   D. C. G. A. Pinto, A. M. S. Silva, J. A. S. Cavaleiro, J. Heterocycl. Chem. 2000, 37,  1629.
        |  CAS |  

[16]   D. C. G. A. Pinto, A. M. S. Silva, L. M. P. M. Almeida, J. A. S. Cavaleiro, J. Elguero, Eur. J. Org. Chem. 2002,  3807.
        | CrossRef |  CAS |  

[17]   A. Lévai, A. M. S. Silva, D. C. G. A. Pinto, J. A. S. Cavaleiro, I. Alkorta, J. Elguero, J. Jekő, Eur. J. Org. Chem. 2004,  4672.
        | CrossRef |   

[18]   A. Lévai, A. M. S. Silva, J. A. S. Cavaleiro, I. Alkorta, J. Elguero, J. Jekő, Eur. J. Org. Chem. 2006,  2825.
        | CrossRef |   

[19]   W. Baker, G. G. Clarke, J. B. Harborne, J. Chem. Soc. 1954,  998.
        | CrossRef |  CAS |  

[20]   (a) V. Szabó, J. Borda, V. Végh, Magy. Kém. Foly. 1977, 83,  394.
         
         (b) V. Szabó, J. Borda, V. Végh, Magy. Kém. Foly. 1977, 83,  434.
         

[21]   (a) V. Szabó, J. Borda, V. Végh, Acta Chim. Acad. Sci. Hung. 1978, 98,  457.
         
         (b) M. S. Frasinyuk, V. P. Khilya, Chem. Heterocycl. Comp. 1999, 35,  3.
        | CrossRef |   

[22]   W. Baker, R. Robinson, J. Chem. Soc. 1926,  2713.
        | CrossRef |  CAS |  

[23]   W. Baker, R. Robinson, J. Chem. Soc. 1929,  152.
        | CrossRef |  CAS |  

[24]   W. Baker, F. M. Eastwood, J. Chem. Soc. 1929,  2897.
        | CrossRef |  CAS |  

[25]   T. C. Chadha, H. S. Mahal, K. Venkataraman, J. Chem. Soc. 1933,  1459.
        | CrossRef |  CAS |  

[26]   I. M. Heilbron, D. H. Hey, B. Lythgoe, J. Chem. Soc. 1936,  295.
        | CrossRef |  CAS |  

[27]   T. R. Seshadri, S. Varadarajan, Proc. Ind. Acad. Sci. 1953, 37A,  784.
        |  CAS |  

[28]   V. Szabó, E. Farkas, A. Lévai, Acta Phys. Chim. Debrecenina 1970,  191.
         

[29]   D. F. Diedrich, T. A. Scahill, S. L. Smith, J. Chem. Eng. Data 1977, 22,  448.
        | CrossRef |  CAS |  

[30]   A. Lévai, T. Patonay, A. Székely, E. B. Vass, W. Adam, J. Heterocycl. Chem. 2000, 37,  1065.
         

[31]   W. Adam, P. B. Rao, H. G. Degen, A. Lévai, T. Patonay, C. R. Saha-Möller, J. Org. Chem. 2002, 67,  259.
        | CrossRef |  CAS |  

[32]   R. W. Taft, I. C. Lewis, J. Am. Chem. Soc. 1958, 80,  2436.
        | CrossRef |  CAS |  

[33]   C. Cativiela, J. I. G. Laureiro, J. Elguero, E. Elguero, Gazz. Chim. Ital. 1991, 121,  477.
        |  CAS |  

[34]   Frisch M. J. , Trucks G. W. , Schlegel H. B. , Scuseria G. E. , Robb M. A. , Cheeseman J. R. , Montgomery J. A. Jr , Vreven T. , et al., Gaussian 03 2003 (Gaussian, Inc.: Pittsburgh, PA).

[35]   (a) A. D. Becke, Phys. Rev. A. 1988, 38,  3098.
        | CrossRef |  CAS |  
         (b) A. D. Becke, J. Chem. Phys. 1993, 98,  5648.
        | CrossRef |  CAS |  
         (c) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37,  785.
        | CrossRef |  CAS |  

[36]   (a) R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys. 1971, 54,  724.
        | CrossRef |  CAS |  
         (b) M. J. Frisch, J. A. Pople, R. Krishnam, J. S. Binkley, J. Chem. Phys. 1984, 80,  3265.
        | CrossRef |  CAS |  

[37]   (a) R. Ditchfield, Mol. Phys. 1974, 27,  789.
        | CrossRef |  CAS |  
         (b) F. London, J. Phys. Radium 1937, 8,  397.
        | CrossRef |  CAS |  




* Dedicated to Professor Gábor Tóth on the occasion of his 65th birthday.


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