Synthesis of (3,4-bis{[2-hydroxy-3-methoxy-5-(4-methylphenyl azo)benzylidene]-amino}phenyl) phenyl methanone as a novel azo Schiff base

A. A. jarrahpour*, M. Zarei

Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran Tel. 0098 711 2284822,  Fax: 0098 711 2280926

E-mail: [email protected],  [email protected]

Received: 16 January 2004 / Accepted: 23 February 2004 / Published: 24 February 2004 

Keywords : Schiff base,Azo aldehyde,(3,4-diaminophenyl)phenyl methanone,biological activity,dyes. 

Schiff bases are used as substrates in the preparation of a large of bioactive and industrial compounds  via ring closure, cycloaddition, replacement reactions, etc [1] . In additon, Schiff bases  are well known to have biological activites such as antibacterial [2-5],  antifungal [4-6],  antitumor [7-9], and herbicidal activities [10].  Also Schiff bases are used as ligands  for complexation of some metal ion 11]. Azo compounds  are widely used  as dyes  and pigments [12]. Another  area of  application  of aromatic azo compounds is  analytical chemistry  where some of these compounds  are used  as indicators  in pH, redox  or  complexometric titrations 13-14]. On the other hand azo compounds  show  biological activities  containing  antibacterial [15-16], pesticidal [10] activities. According to above  facts, we decided to synthesize a  new azo Schiff base 3  as potential biological and complexometric agent .  Its biological activities and its uses in analytical works are under study.

Azo aldehyde 2  was  synthesized according to a reported  method [17]. To  a stirred  solution  of azo aldehyde 2  (1.08 g, 3.76 mmol )  in  dry CH₂Cl₂  (30.00 mL) at  0 ^oC  were  successively  added  (3,4-diaminophenyl)phenyl methanone 1(0.40 g, 1.88 mmol) and a excces of anhydrous MgSO₄ (2.00 g,16.67 mmol) . The resulting  mixture  was  stirred  for  6 hours  at room temperature [18]. The mixture was  filtered and washed with dichloromethane . Then the solvent was  evaporated under reduced pressure to  give azo Schiff base 3  as a red solid which was recrystalized from ethanol 95%   (1.28 g, 91 %)

m.p. 140-142 ^oC.

IR (KBr) (cm^-1): 1604.7 (C=N), 1658.9 (C=O), 3155.3-3649.1 (OH) .

¹H-NMR (CDCl ₃) (250 MHz) (ppm): 3.91 (2 OMe, s, 6H), 3.98 (2 OMe, s, 6H )  6.89-7.01 (C₆H₅COC₆H₃, m, 8H), 7.24-7.85 (MeOC₆H₄N₂C₆H₂(OH)(OMe), m, 12H), 8.70 (2HC=N, s, 2H), 13.89 (2OH, br, 2H) .

¹³C- NMR (CDCl ₃ ) (62.90 MHz) (ppm): 56.43, 56.55, 105.73, 114.40, 114.73, 114.13, 118.67, 122.41, 123.13, 124.67, 127.82, 128.65, 130.37, 132.16, 132.40, 133.65, 138.86, 146.00, 147.10, 149.54, 154.23

MS (m/z, %): 492 (C₆H₅COC₆H₃N=CC₆H₃OHOMeN=CC₆H₃OHOMeN, 3.6), 478 (C₆H₅COC₆H₃ (N=C C₆H₃OHOMe)₂, 31.9),464 (C₆H₅COC₆H₃N=CC₆H₃OHOMeN=NC₆H₄OMe, 2.2),343 (C₆H₅CO C₆H₃N=CC₆H₃OHOMeN, 11.8), 135 (MeOC₆H₄N=N, 10.7), 108 (MeOC₆H₅, 100.0), 105 (C₆H₅CO, 42.3), 77 (C₆H₅, 71.8) .  

Acknowledgment

The authors thank the Shiraz University Research council for financial support (Grant No. 81-SC-1540-C220 ).

References

1.   Aydogan, F.;Öcal, N.;Turgut, Z.; and Yolacan, C.  Bull. Korean Chem .Soc.  2001, 22, 476-480 .

2.   Kabeer, A . S.;Baseer, M. A.;Mote, N. A.  Asian J. Chem.  2001, 13 (2), 496-500 .

3.   El-masry, A. H.; Fahmy,H. H.; Abdelwahed, S. H. A.  Molecules   2000, 5, 1429-1438 .  

4.   More, P. G.; Bhalvankar, R . B.; Pattar, S. C. J. Indian Chem. Soc. 2001, 78(9), 474-475 .      

5.   Pandeya, S. N.; Sriram, D.; Nath, G.; De Clercq, E.  IL Farmaco  1999, 54, 624-628 .  

6.   Singh, W. M.; Dash, B. C.  Pesticides   1988, 22(11), 33-37 .     

7.   Hodnett, E. M. and Mooney, P. D.  J. Med. Chem.   1970, 13, 786 .  

8.   Hodnett, E. M. and  Dunn, W. J.  J. Med. Chem.   1970, 13, 768-770 . 

9.   Nofal, Z. M. N.; El-Zahar, M. I. And  Abd El-Karim, S. S.  Molecules   2000, 5, 99-113 .  

10. Samadhiya, S.; Halve, A.   Orient. J .Chem.   2001, 17 (1), 119-122 .   

11. Tai, X.; Yin, X.; Chen, Q.  and Tan, M.   Molecules   2003, 8, 439-443 .    

12. Zollinger, H.   Color Chemistry , second ed. ,  VCH, Weinheim  1991  .  

13. Croot, P. L.  and  Johansson, M.   Electroanalysis   2000, 12, 565-576 .     

14. Choi, D.; Lee, S. K.; Chung, T. D.  and Kim, H.  Electroanalysis   2000, 12, 477-482 .    

15. Jolly, V. S.; Pathak, P.; Jain, R.   J. Indian  Chem. Soc.  1993, 70, 505-507 .  

16. Halve, A.; Goyal, A.  Orient. J .Chem.  1996, 12(1), 87-88 . 

17. Furniss, B. S.; Hannaferd,A. J.; Rogers, V.; Smith, P. W. G.; Tatchell, A. R. Vogel^,s  Textbook  of Practical Organic Chemistry, 4^th  ed.,Longman Inc. New York  1981, P   716 .  

18. Matsui, S.; Hashimoto, Y.; Saigo, K.  Synthesis  1998, 1161-1166 .        

 Sample Availability : Available from  MDPI.

 © 2004 MDPI. All rights reserved