Multi-(5-phenyl-1,3,4-oxadiazo-2-yl)benzenes
J. Phys. Chem. B, Vol. 114, No. 2, 2010 767
removed by rotary evaporation under vacuum, and the crude
product was extracted with CHCl3 and water. The organic layer
was dried over anhydrous Na2SO4 and concentrated under
vacuum to give a white solid (5.7 g, 96%). mp 255-256 °C.
fluorescence spectra (pdf, 42 pages). This material is available
References and Notes
1H NMR (400 MHz, CDCl3, δ): 8.84 (s, 3H), 3.97 (s, 9H). 13
C
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NMR (100 MHz, CDCl3, δ): 165.1, 134.4, 131.0, 52.7. MS (EI)
252 (M+). HRMS (EI) calcd for C12H12O6 252.0634 (M+), obsd.
252.0633. Anal. Calcd for C12H12O6: C, 57.14; H, 4.80. Found:
C, 57.04; H, 4.57.
Reaction Sequence for the Preparation of 1,3,5-Tri[5-
phenyl-(1,3,4)-oxadiazol-2-yl]benzene (6). Benzene-1,3,5-tri-
carboxylic Acid Trihydrazide. To a solution of benzene-1,3,5-
tricarboxylic acid trimethyl ester (5.0 g, 19.8 mmol) in EtOH
(30 mL) and toluene (30 mL) under nitrogen atmosphere was
added hydrazine hydrate (14.5 mL, 297.0 mmol). The solution
was heated at 110 °C for 24 h, and the crude product was
precipitated during reaction. The product was collected by
filtration and washed with EtOH and toluene to give a white
solid (4.6 g, 92%). mp >400 °C. 1H NMR (400 MHz, DMSO-
d6, δ): 9.83 (s, 3H), 8.30 (s, 3H), 4.57 (br, 6H). 13C NMR (100
MHz, DMSO-d6, δ): 164.7, 133.6, 127.9. MS (EI) 252 (M+).
HRMS (EI) calcd for C9H12N6O3 252.0971 (M+), obsd. 252.0976.
Anal. Calcd for C9H12N6O3: C, 42.86; H, 4.80; N, 33.32. Found:
C, 42.62; H, 4.74; N, 33.22.
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N′,N′′′,N′′′′′-Tri(benzoyl)benzene-1,3,5-tricarboxylic Acid Tri-
hydrazide. A solution of benzene-1,3,5-tricarboxylic acid tri-
hydrazide (1.0 g, 4.0 mmol) in dry NMP (10 mL) at 0 °C was
kept for 20 min. Benzoyl chloride (1.4 mL, 12.3 mmol) was
added into the solution, and the solution was allowed to stand
overnight. The solution was added dropwise into water, and a
white solid was precipitated. The white crude product was
collected by filtration and washed with hot EtOH to give a white
1
solid (2.2 g, 99%). mp 279-295 °C. H NMR (400 MHz,
DMSO-d6, δ): 10.85 (s, 3H), 10.65 (s, 3H), 8.64 (s, 3H), 7.94
(d, J ) 7.2 Hz, 6H), 7.63-7.51 (m, 9H). 13C NMR (100 MHz,
DMSO-d6, δ): 165.5, 164.7, 133.3, 132.2, 131.8, 129.6, 128.4,
127.3. MS (FAB) 565 (M+ + H). HRMS (FAB) calcd for
C30H25N6O6 565.1836 (M+ + H), obsd. 565.1823. Anal. Calcd
for C30H24N6O6: C, 75.29; H, 6.32; N, 11.71 Found: C, 75.29;
H, 6.32; N, 11.85.
1,3,5-Tri[5-phenyl-(1,3,4)-oxadiazol-2-yl]benzene(6).N′,N′′′,N′′′′′-
Tri(benzoyl)benzene-1,3,5-tricarboxylic acid trihydrazide (1.5
g, 2.7 mmol) was dissolved in POCl3 (27 mL). The solution
was heated at 105 °C overnight. The solution was added
dropwise into ice water, and a brown solid precipitated. The
crude product was collected by filtration and washed with
NaHCO3(aq). The solid was purified by chromatography on silica
gel using Et2O/CHCl3(1:5) as the eluent to give product (1.2 g,
1
91%). mp 350-351 °C. H NMR (400 MHz, CDCl3, δ): 9.07
(s, 3H), 8.24-8.22 (m, 6H), 7.62-7.57 (m, 9H). 13C NMR (100
MHz, CDCl3, δ): 165.3, 162.6, 132.2, 129.1, 127.19, 127.15,
126.2, 123.2. MS (EI) 510 (M+). HRMS (EI) calcd for
C30H18N6O3 510.1440 (M+), obsd. 510.1433. Anal. Calcd for
C30H18N6O3: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.12; H,
3.58; N, 16.42.
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2004, 16, 4556.
Acknowledgment. The present work was supported by the
Ministry of Eduction and National Taiwan University, National
Science Council of Taiwan (NSC-95-2113-M002-021-MY3,
NSC-98-2119-M-002-006-MY3, and NSC-97-3114-M-002-
005), and Academia Sinica (Thematic Project).
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Supporting Information Available: 1H and 13C NMR
spectra and their preparation procedures and UV-vis and