J. Chil. Chem. Soc., 58, Nº 2 (2013)
3.2. General procedure
CDCl3): d 9.51 (s, 1H), 9.18 (s, 1H), 8.64 (d, 1H, J 7.6 Hz), 8.55 (s, 1H), 8.43
(dd, 1H, J 8, 1.2 Hz), 8.34 (s, 2H), 7.94 (d, 2H, J 7.2 Hz), 7.83 (t, 1H, J 8
Hz), 7.69 (t, 1H, 7.2 Hz), 7.58 (t, 2H, 7.6 Hz); 13C NMR (100 MHz, CDCl3):
d 195.47, 150.61, 149.09, 143.88, 143.57, 141.22, 138.79, 137.98, 136.93,
133.27, 133.08, 133.24, 130.79, 130.37, 130.24, 130.19, 128.63, 125.21,
122.68; IR (KBr): ν 3090, 1649, 1533, 1348, 1297 cm-1; Anal. Calcd for
C21H13N3O3: C, 70.98; H, 3.69; N, 11.83. Found: C, 71.16; H, 3.56; N, 11.90.
3-Phenyl-7-benzoyl-quinoxaline (17e): 1H NMR (CDCl , 400MHz):
d 9.43 (s, 1H), 8.51 (s, 1H), 8.28-8.25 (m, 4H), 7.29 (s, 1H), 73.91 (d, 1H, J
1.2 Hz), 7.68-7.53 (m, 6H); 13C NMR (CDCl , 100MHz): d 195.63, 153.31,
144.41, 144.16, 140.63, 137.88, 137.12, 1336.24, 132.89, 132.33, 130.82,
130.26, 130.16, 130.09, 129.30, 128.54, 127.77, 127.60; IR (KBr): ν 3053,
1650, 1595, 1454, 1294 cm-1.; Anal. Calcd for C21H14N2O: C, 81.27; H, 4.55;
N, 9.03. Found: C, 81.50, H, 4.516, N, 9.070.
A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),
o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol
(5 mL) was stirred at room temperature. The progress of the reaction was
monitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,
the solid which separated was filtered and then recrystallized from ethanol to
afford pure product.
3.3. Spectral data of some compounds
2,3-Bis(4-flouro-phenyl)quinoxaline (11a): 1H NMR (400 MHz, CDC1 )
δ 7.97 (dd, 2H, J 6.4, 3.6 Hz), 7.60 (dd, 2H, J 6.4, 3.2 Hz), 7.33-7.30 (m, 4H3),
6.86 (t, 4H, J 8.8 Hz);13C NMR (100 MHz, CDC1 ) δ 161.99, 152.20, 141.23,
135.02, 131.82, 131.74, 130.23, 129.16, 115.65, 3115.43; IR (KBr): ν 3061,
1599, 1555, 1511, 1344, 1225, 839, 786 cm-1.
2,3-Bis(4-flouro-phenyl)-6-methylquinoxaline (11b): 1H NMR (400
MHz, CDC13) δ 6.58 (t, 4H, J 8.8 Hz), 2.43 (s, 3H), 7.85 (d, 1H, J 8.8 Hz),
7.73 (s, 1H), 7.42 (d, 1H, J 8.8 Hz), 7.30 (dd, 4H, J 8.00, 5.2 Hz); 13C NMR
(100 MHz, CDC13): δ 161.89, 152.05, 151.29, 141.28, 140.84, 139.69, 135.16,
135.13, 132.59, 131.77, 131.72, 131.69, 128.65, 127.96, 115.59, 115.37, 21.94;
IR (KBr): ν 2925, 2580, 1657, 1597, 1264, 1159, 833, 696 cm-1.
1
3-Naphthyl-7-benzoyl-quinoxaline (18e): H NMR (CDCl 400MHz): d
9.31 (s, 1H), 8.59 (s, 1H), 8.35 (s, 2H), 8.23 (d, 1H, J 9.2 Hz), 8.036, (d, 1H, J 8.4
Hz), 8.01 (d, 1H, J 6.4 Hz), 7.94 (d, 2H, J 8 Hz), 7.48 (d, 1H, J 7.2 Hz), 7.68
(t, 2H, J 7.6 Hz), 7.60-7.53 (m, 4H); 13C NMR (CDCl3, 100MHz): d 195.65,
155.97, 147.77, 144, 140.41, 138.31, 137.08, 134.61, 134.07, 133.01, 132.38,
131.01, 130.67, 130.40, 130.23, 130.14, 128.90, 128.79, 128.60, 127.46,
126.89, 126.54, 125.46, 124.89; IR (KBr): ν 3050, 1697, 1651, 1446,1289 cm-
1.; Anal. Calcd for C25H16N2O: C, 83.31; H, 4.47; N, 7.77. Found: C, 82.63, H,
4.523, N, 6.903.
1
Dibenzo[a,c]phenazine (12a): H NMR (400 MHz, CDC13): δ 9.18 (d,
2H, J 7.6 Hz), 8.34 (d, 2H, J 8 Hz), 8.12 (dd, 2H, J 6.4, 3.6 Hz), 7.66-7.51 (m,
6H); 13C NMR (100 MHz, CDC13): δ 143.54, 143.28, 133.15, 131.42, 130.88,
130.57, 129.04, 127.38, 124.03; IR (KBr): ν 3055, 1600, 1490, 1350, 760,720
cm-1.
1
11-Methyl-dibenzo[a,c]phenazine (12b): H NMR (400 MHz, CDC13):
4. CONCLUSION
δ 9.14 (2H, dd, J 6.00, 1.6 Hz), 8.32 (d, 2H, J 8 Hz), 7.97 (d, 1H, J 8.4 Hz),
7.58 (s, 1H), 7.53-7.52 (m, 5H), 2.54 (s, 3H); 13C NMR (100 MHz, CDC13):
δ 143.29, 143.27, 142.72, 141.81, 141.41, 133.45, 133.06, 132.87, 131.49,
131.45, 131.20, 131.07, 130.01, 129.10, 128.92, 127.29, 127.15, 123.95, 23.20;
IR (KBr): ν 3055, 2910,1620, 1500, 1350, 760, 720 cm-1.
In summary, we have presented a new application of lead dichloride
(PbCl2) as an effective and heterogeneous catalyst for the synthesis of many
quinoxalines and phenazines based on the condensation of 1,2-dicarbonyl
compounds with o-phenylenediamines under mild reaction conditions.
Availability and stability of the catalyst, simple work-up procedure and the
high yields, short reaction times, and mild reaction conditions make this
method a valid contribution to the existing methodologies.
11-Benzoyl-dibenzo[a,c]phenazine (12e): 1H NMR (CDCl , 400MHz): d
9.43 (dd, 1H, J 8 Hz, 1.2 Hz), 9.35 (dd, 1H, J 8 Hz, 1.2 Hz), 8.730 (d, 1H, J 1.6
Hz), 8.58 (d, 2H, J 8 Hz), 8.44 (d, 1H, J 8.8 Hz), 8.55 (dd, 1H, J 8.8 Hz, 2 Hz),
7.99-7.97 (m, 2H), 7.87-7.68 (m, 5H), 7.60 (t, 2H, J 8 Hz); 13C NMR (CDCl3,
100MHz): d 196.07, 184.81, 153.70, 143.74, 143.45, 141.05, 137.92, 137.38,
132.95, 132.84, 132.48, 132.18, 130.99, 130.75, 130.23, 129.94, 129.40,
128.58, 128.12, 126.69, 126.36, 123.01; IR (KBr): ν 3050, 1650, 1600, 1445,
1320 cm-1.; Anal. Calcd. for C27H16N2O: C, 84.36; H, 4.20; N, 7.29. Found: C,
84.48, H, 4.183, N, 7.375.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge partial support of this work by the
Yasouj University Iran.
1
Acenaphtho[1,2-b] quinoxaline (13a): H NMR (400 MHz, CDC1 ): δ
REFERENCES
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122.96; IR (KBr): ν 3050, 1610, 1430, 1300, 830, 760 cm-1.
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400MHz): d 8.61 (d, 1H, J 1.6 Hz), 8.50 (d, 1H, J 6.8 Hz), 8.44 (d, 1H, J 6.38
Hz), 8.34 (d, 1H, J 8.8 Hz), 8.28 (dd, 1H, J 8.6 Hz, 2 Hz), 8.18 (dd, 2H, J 8
Hz, 6 Hz), 7.96-786 (m, 4H), 7.67 ( t, 1H, J 7.6 Hz), 7.57 (t, 2H, J 7.6 Hz); IR
(KBr): ν 3038, 1646, 1595, 1437, 1300 cm-1.; Anal. Calcd for C25H14N2O: C,
83.78; H, 3.94; N, 7.82. Found: C, 83.46, H, 3.745, N, 7.607.
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3-(2-Naphthyl)-7-benzoyl-quinoxaline (14e): 1H NMR (400 MHz,
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8.32 (s, 2H), 8.09-8.05 (m, 2H), 7.95-7.93 (m, 3H), 7.68 (t, 1H, J 7.6 Hz), 7.64-
7.55 (m, 4H); 13C NMR (100 MHz, CDCl3): d 195.68, 153.21, 145.21, 144.58,
144.28, 140.63, 137.89, 137.18, 134.44, 133.56, 133.37, 132.95, 132.68,
132.39, 130.34, 130.18, 130.09, 129.25, 129.05, 128.57, 127.89, 127.70,
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CDCl ): d 9.42 (s, 1H), 8.52 (s, 1H), 8.292(s, 2H), 7.93 (d, 2H, J 7.2 Hz), 7.83
(t, 2H3, J 7.6 Hz), 7.67 (d, 1H, J 7.6 Hz), 7.58-7.51 (m, 3H), 7.14 (dd, 1H, J 8,
2 Hz), 3.98 (s, 3H); 13C NMR (CDCl3, 100 MHz): d 195.67, 160.44, 153.13,
144.51, 144.13, 140.72, 137.94, 137.65, 137.15, 132.90, 132.33, 130.32,
130.27, 130.17, 130.11, 128.56, 120.13, 116.88, 112.86, 55.54; IR (KBr): ν
3090, 2950, 1649, 1598, 1329, 1297 cm-1; Anal. Calcd for C22H16N2O2: C,
77.63; H, 4.74; N, 8.23. Found: C, 77.80; H, 4.61; N, 8.15.
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1
3-(3-Nitrophenyl)-7-benzoyl-quinoxaline (16e): H NMR (400 MHz,
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1657