A. Y. E. Abadi et al.
Ar–H), 8.41 (d, 1H, J = 7.6 Hz, Ar–H), 8.23–8.20 (m, 1H, Ar–H), 8.02–7.98 (m,
1H, Ar–H), 7.96–7.90 (m, 2H, Ar–H), 7.90–7.88 (m, 2H, Ar–H), 7.55 (d, 1H,
J = 2 Hz, Ar–H), 7.40 (s, 2H, NH2), 7.20 (d, 1H, J = 8.8, Ar–H), 7.15 (dd, 1H,
J1 = 2 Hz, J2 = 8.4 Hz, Ar–H), 5.83 (s, 1H, CH) ppm; 13C NMR (100 MHz,
DMSO-d6): d = 159.8, 147.0, 142.5, 141.9, 140.9, 140.5, 140.1, 133.7, 132.0,
131.9, 131.2, 131.0, 130.7, 130.6, 129.7, 129.5, 128.9, 128.8, 128.1, 125.9, 125.2,
122.6, 119.9, 112.6, 56.8, 34.6 ppm; MS (m/z, %): 468 (M?, 6).
3-Amino-2-cyano-1-(3-methoxyphenyl)-1H-benzo[a]pyrano[2,3-c]phenazine
(Table 2, entry 2): yield of method A: 0.374 g (87 %), method B: 0.387 g (90 %),
yellow solid, m.p.: 240–242 °C; IR (KBr): mmax = 3449, 3300, 3165, 2175, 1663,
1599, 1595, 1485, 1449, 1428, 1398, 1385, 1347, 1314, 1288, 1261, 1163, 1103, 1048,
1025, 992, 947, 871, 752 cm-1; 1H NMR (400 MHz, DMSO-d6): d = 9.16 (d, 1H,
J = 8 Hz, Ar–H), 8.40 (d, 1H, J = 8 Hz, Ar–H), 8.23–8.21 (m, 1H, Ar–H), 8.13–8.10
(m, 1H, Ar–H), 7.98–7.93 (m, 1H, Ar–H), 7.91–7.88 (m, 3H, Ar–H), 7.39 (s, 2H, NH2),
7.12 (t, 1H, J = 8 Hz, Ar–H), 7.00 (t, 1H, J = 2 Hz, Ar–H), 6.90 (d, 1H, J = 8 Hz,
Ar–H), 6.67 (dd, 1H, J1 = 2 Hz, J2 = 7.6 Hz, Ar–H), 5.43 (s, 1H, CH), 3.67 (s, 3H,
OCH3) ppm; 13C NMR (100 MHz, DMSO-d6): d = 160.4, 159.5, 147.2, 146.5, 141.9,
141.0, 140.4, 140.1, 131.2, 130.9, 130.6, 130.3, 129.9, 129.5, 129.4, 129.1, 126.0,
125.2, 122.5, 120.7, 120.1, 114.3, 114.2, 111.9, 58.2, 55.3, 37.7 ppm; MS (m/z, %):
430 (M?, 33).
Results and discussion
First, to find optimization conditions, the one-pot four-component reaction of
2-hydroxynaphthalene-1,4-dione, o-phenylenediamine, 2,4-dichlorobenzaldehyde,
and malononitrile in the presence of caffeine as catalyst was selected as model. So,
2-hydroxynaphthalene-1,4-dione (1 mmol) and o-phenylenediamine (1 mmol) were
mixed at 75 °C for\5 min until an orange solid of benzo[a]phenazine was formed
without using any catalyst under solvent-free conditions. Then, in method A, 2,4-
dichlorobenzaldehyde (1 mmol), malononitrile (1 mmol), and caffeine as catalyst
were added, the flask was fitted with a condenser, and the resulting mixture in
ethanol (10 mL) was heated to reflux under stirring. The use of different amounts of
catalyst (20, 25, 30, 35 mol %) at different temperatures (25, 50, 75 °C) were
investigated (Table 1). The best result was obtained with 30 mol % of caffeine as
catalyst at 75 °C in ethanol under reflux conditions and afforded 3-amino-2-cyano-
1-(2,4-dichlorophenyl)-1H-benzo[a]pyrano[2,3-c]phenazine in 30 min with 93 % of
yield.
Then, optimization conditions for method B, the same as above model using
different amounts of catalyst (10, 20, 30 mol %) at various powers (100, 180,
300 W) was investigated (Table 1). The best result was obtained with 20 mol % of
caffeine as catalyst at 180 W afforded 3-amino-2-cyano-1-(2,4-dichlorophenyl)-1H-
benzo[a]pyrano[2,3-c]phenazine in 7 min with 95 % of yield.
Using these optimized reaction conditions, the scope and efficiency of the
reaction were explored for the synthesis of a wide variety of substituted
benzo[a]pyrano[2,3-c]phenazine derivatives. The results are summarized in
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