7th International Conference of Chemical Societies from South-East European Countries on Chemistry Beauty and Application Bucharest, 15-17

7 September 2010

A convenient synthesis of new aryl substituted bis1,3,4-oxadiazoles and their photophysical properties
Codruta C. Paraschivescu,1 Ana-Maria Dit,1 Alina Jurca,1 Mihaela Matache,1 Victor Achim,1 Cristian Dobrota,1 Niculina D. Bogdan,2 Alina Nicolescu,3,4 Calin Deleanu3,4 1University of Bucharest , Department of Chemistry, 90-92 Panduri Street, District 5, 050663, Bucharest, Romania 2Technical University of Munich, Department of Chemistry, Marie Curie Excellence Team, 4 Lichtenbergstr., 85747, Garching, Germany. 3 Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41-A, 700487 Iasi, Romania. 4 Institute of Organic Chemistry, Spl. Independentei 202-B, 060023 Bucharest, Romania.

Introduction
Bis-1,3,4-oxadiazoles have been reported to bear a good antiinflamatory, antibacterial or antifungal activity.1 In addition, they have been used as dyes, fluorescent materials or polymers precursors.2 Due to their remarkable photophysical properties, they have been successfully used in preparation of the Organic Light-Emitting Diodes (OLED). 3 The synthesis of the oxadiazole ring developed along two strategies: dehydration of N,N-diacylhydrazines 1 using a dehydration agent such as phosphorous oxychloride4 and oxidative cyclization of acylhydrazines 2 using an oxidative agent such as acetic anhydride5 or more recently, hypervalent iodine reagents6, particularly, the trivalent iodine containing bis(trifluoroacetoxy)iodobenzene (PIFA). 7

Structural analysis

1H

NMR spectrum of 5g (top) and 6g (bottom) confirming formation of the oxadiazole ring ES-MS spectrum of 6g

Fluorescence assays
PIFA

The absorption and emission spectra of the aryl substituted bis1,3,4-oxadiazoles were recorded in DCM or MeCN (10-6 to 10-5 M solution). The UV-Vis spectra of these compounds present intense UV absorption bands ranging from 250 to 300 nm, since the studied compounds emit blue light (in the range of 355-465 nm) upon UV 120 irradiation. 144 nm
113 nm
100

Synthesis of new bis-1,3,4-oxadiazoles

The new bis-1,3,4-oxadiazoles derived from o-phtalaldehyde were synthesized using BTI as oxidative cyclization reagent.

80

UV-Vis absorption spectra for 6a (blue line) and 6g (red line) and room-temperature fluorescence spectra for 6a (green line) and 6g (black line)

intensity (a.u.)

60

40

20

0 250 300 350 400 450 500 550

wavelength (nm)

Entr y 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

Ar Ph 4-Br-Ph 4-Cl-Ph 3-Cl-Ph 4-I-Ph 4-Me-Ph 4-OMe-Ph 4-NO2-Ph 2,4,5triOMe-Ph 4-pyridil

Aryliden 5a 5b 5c 5d 5e 5f 5g 5h 5i 5j

(%) 82 75 75 70 68 82 81 65 87 86

t.t. (C) 221-4 211-2 182-5 193-7 201-4 225-8 204-6 213-5 212-3 191-3

Bis-1,3-4oxadiazole 6a 6b 6c 6d 6e 6f 6g 6h 6i 6j

(%) 85 83 92 81 63 88 91 60 87 88

t.t. (C) 124-6 249-0 212-4 133-6 217-9 175-6 165-6 246-8 212-3 210-2

Conclusions and perspectives

Synthesis of new bis-1,3,4-oxadiazoles using a trivalent iodine reagent on a ortho-disubstituted substrate Simple methodology for preparation of systems heterocyclic

Detailed investigation of the photophysical properties

References
1. F. A. Omar, N.M. Mahfouz, M. A. Rahman, Eur. J. Med. Chem., 1996, 31, 819. 2. (a) C. Adachi, T. Tsutsui, S. Saito, Appl. Phys. Lett., 1990, 56, 799; (b) H. Kovacs, A.P. Delman, B.B. Simms, J. Polym. Sci. Part A1, 1970, 8, 869. 3. Adachi, C., Tsutsui, T., Saito, S, Appl. Phys. Lett., 1990, 56, 799. 4. Al-Talib, M., Tashtoush, H., Odeh, N., Synth. Commun., 1990, 20(12), 1811. 5. Elwahy, A.H.M., Ahmed, M.M., El-Sadek, M., J.Chem.Research (S), 2001, 175 6. Stang, P.J., Zhdankin, V.V., Chem.Rev., 1996, 96, 1123 7. Shang, J. Reiner, J. Chang, K. Zhao, Tetrahedron Lett., 2005, 46, 2701.

Acknowledgments
This research was funded by The Romanian Ministry of Education and Research, grant 43/2005, IDEI 176/2007 and PNII 11023/2007 CEEX