S. Kothavale, N. Sekar / Dyes and Pigments 136 (2017) 31e45
33
(1.4 g). The filtrate was further concentrated to its half amount and
filtered again to get the second crop of the product (0.4 g).
Yield ¼ 1.8 g (58.25%). Melting point ¼ 128e133 ꢀC. 1H NMR
(0.4 g, 1.902 mmol) and compound 2 (0.75 g, 2.473 mmol) were
refluxed in methanol. (Yield: 0.75 g, 82.23%). Melting
point ¼ 256 ꢀC. 1H NMR (500 MHz, CDCl3):
d
1.22e1.24 (t, J ¼ 5.5,
(500 MHz, CDCl3):
d
1.22e1.24 (t, J ¼ 5.5, 6H), 3.43e3.45 (q, 4H),
6H), 3.43e3.45 (q, 4H), 6.43 (s, 1H), 6.73e6.75 (d, J ¼ 7.5, 2H),
6.43 (s, 1H), 6.73e6.75 (d, J ¼ 7.5, 2H), 7.36e7.38 (d, J ¼ 7.5, 2H),
7.26e7.59 (m, 6H), 8.16e8.18 (d, J ¼ 6.5, 1H). 13C NMR (125 MHz,
7.51e7.59 (m, 3H), 8.16e8.18 (d, J ¼ 6.5, 1H). 13C NMR (125 MHz,
CDCl3):
d 12.37, 29.66, 123.81, 125.26, 127.00, 127.32, 127.47, 127.61,
CDCl3):
d
12.57, 44.51, 111.03, 122.54, 125.46, 129.86, 130.28, 130.32,
129.26, 131.10, 133.30, 140.28, 140.54, 142.21, 147.65, 147.73, 151.86,
152.00. HRMS (ESI): m/z calcd for (M þ H)þ C32H25N5 480.2182;
found 480.2158.
130.41, 132.00, 134.64, 135.35, 149.29, 157.44, 180.19, 180.52.
2.3.2. synthesis of 4-morpholinonaphthalene-1,2-dione (3)
The diketo compound (2.8 g, 10.13 mmol) was dissolved in
minimum amount of water and then morpholine (2.1 mL,
13.173 mmol) was added slowly. Red colored product separated out
immediately. After stirring for 10 min the reaction mixture was
cooled to 0 ꢀC, filtered and dried to get the pure product (1.8 g,
58.25%). Melting point ¼ 164e168 ꢀC. 1H NMR (500 MHz, CDCl3):
2.3.5.2. 4-(Benzo[h]dipyrido[3,2-a:20,3'-c]phenazin-14-yl)morpho-
line (5). Compound 5 was synthesized by following the general
procedure described above 1, 10-phenanthroline-5, 6-diamine
(0.3 g, 1.427 mmol) and compound 3 (0.45 g, 1.855 mmol)
refluxed in methanol. (Yield: 0.5 g, 84.03%). Melting point ¼ 282 ꢀC.
1H NMR (500 MHz, CDCl3):
d
3.32e3.33(3, 4H), 4.07e4.08 (t, J ¼ 4.5,
d
3.35e3.37 (t, J ¼ 4.5, 4H), 3.92e3.94 (t, J ¼ 5, 4H), 5.98 (s, 1H),
4H), 7.46 (s, 1H), 7.72e7.75 (m, 2H), 7.78e7.80 (m, 2H), 8.21e8.23
(m, 1H), 9.22e9.26 (m, 2H), 9.37e9.39 (m, 1H), 9.46e9.48 (dd, J ¼ 8
and 1.5, 1H), 9.56e9.58 (dd, J ¼ 8.5 and 1.5, 1H). 13C NMR (125 MHz,
7.52e7.57 (m, 2H), 7.63e7.66 (t, J ¼ 7.5, 1H), 8.09e8.11 (d, J ¼ 7.5,
1H). 13C NMR (125 MHz, CDCl3): 51.63, 66.21, 109.84, 126.70, 129.80,
130.93, 132.02, 132.06, 134.23, 163.39, 178.71, 180.34.
CDCl3):
d 53.16, 67.10, 112.80, 123.93, 124.20, 125.68, 127.35, 127.73,
127.91, 129.37, 130.20, 131.70, 133.36, 133.47, 137.15, 139.46, 139.90,
143.54, 146.68, 147.05, 151.39, 151.75, 153.26. HRMS (ESI): m/z calcd
for (M þ H)þ C26H19N5O 418.1662; found 418.1650
2.3.3. synthesis of 5-morpholinoacenaphthylene-1,2-dione (8)
Compound 7 (1 g, 3.831 mmol) was dissolved in N, N dimethyl
acetamide (10 mL), K2CO3 (0.79 g, 5.747 mmol) and CuI (0.72 g,
3.831 mmol) followed by morpholine (0.49 mL, 5.747 mmol) was
added and the mixture was heated at 90 ꢀC for 4 h. Water was
added to the red colored reaction mixture at room temperature.
The solid precipitated out was filtered, dried and purified by col-
umn chromatography using 20% EtOAc in hexane to get the pure
product. (0.61 g, 59.80%) Melting point ¼ 222e227 ꢀC. 1H NMR
2.3.5.3. 4-(Acenaphtho[10,2':5,6]pyrazino[2,3-f][1,10]phenanthrolin-
12-yl)morpholine (9). Compound 9 was synthesized by following
the general procedure described above 1, 10-phenanthroline-5, 6-
diamine (0.23 g, 1.12 mmol) and intermediate 8 (0.3 g, 1.12 mmol)
refluxed in methanol. (Yield: 0.28 g, 57.57%). Melting point >300 ꢀC.
1H NMR (500 MHz, CDCl3):
d 3.41 (t, 4H), 4.08 (t, 4H), 7.23e7.25(d,
(500 MHz, CDCl3):
d
3.38e3.40 (t, J ¼ 4.5, 4H), 4.02e4.04 (t, J ¼ 4.5,
J ¼ 7.5, 1H), 7.79e7.82 (m, 3H), 8.23e8.25 (d, J ¼ 8.5, 1H), 8.34e8.35
4H), 7.20e7.21 (d, J ¼ 8, 1H), 7.72e7.75 (t, J ¼ 7.5, 1H), 7.99e8.00 (d,
(d, J ¼ 7, 1H), 8.43e8.45 (d, J ¼ 7.5, 1H), 9.27 (m, 2H), 9.66e9.69 (t,
J ¼ 7, 1H), 8.04e8.05 (d, J ¼ 8, 1H), 8.23e8.25 (d, J ¼ 8.5, 1H). 13
C
J ¼ 7, 2H). 13C NMR (125 MHz, CDCl3):
d 53.51, 66.73, 112.01, 114.30,
NMR (125 MHz, CDCl3):
d
52.51, 66.84,115.13,121.92,123.43,124.05,
116.60, 118.89, 122.35, 123.26, 126.53, 128.32, 129.39, 134.25, 135.51,
135.90, 136.96, 137.16, 137.52, 137.87, 152.58, 152.74, 153.84. HRMS
(ESI): m/z calcd for (M þ H)þ C28H19N5O 442.1662; found 442.1631.
124.83, 127.08, 128.88, 129.49, 148, 154.68, 186.24, 189.51.
2.3.4. synthesis of 3-morpholinophenanthrene-9,10-dione (12)
Compound 11 (1 g, 3.483 mmol), K2CO3 (0.72 g, 5.224 mmol),
CuI (0.13 g, 0.696 mmol) were dissolved in DMF (10 mL). Mor-
pholine (0.45 g, 5.224 mmol) was slowly added and the mixture
was heated at 90 ꢀC for 4 h. After completion water was added to
the reaction mixture and extracted with ethyl acetate (3 ꢁ 50 mL).
The organic layer was evaporated on rotavapour after passing
through anhydrous Na2SO4 and the crude product obtained was
purified on column chromatography (15% EtOAc in hexane) to get
the pure product (0.47 g, 46.07%). Melting point ¼ 252e256 ꢀC. 1H
2.3.5.4. 4-(Dibenzo[a,c]dipyrido[3,2-h:20,3'-j]phenazin-12-yl)mor-
pholine (13). Compound 13 was synthesized by following the
general procedure described above phenanthroline-5, 6-diamine
(0.21 g, 1.023 mmol) and compound 8 (0.3 g, 1.023 mmol) were
refluxed in methanol. (Yield ¼ 0.220 g, 46.02%). Melting point
>300 ꢀC. 1H NMR (500 MHz, CDCl3):
d 3.20 (t, 4H), 3.87 (t, 4H),
6.55e6.57 (d, J ¼ 7.5, 1H), 6.76 (s, 1H), 7.20e7.27 (m, 2H), 7.64e7.85
(m, 4H), 8.19e8.20 (d, J ¼ 4.5, 1H), 8.68e8.69 (d, J ¼ 6, 1H),
8.79e8.81 (d, J ¼ 6, 1H), 8.98e9.00 (m, 2H). HRMS (ESI): m/z calcd
for (M þ H)þ C30H21N5O 468.1819; found 468.1800.
NMR (500 MHz, CDCl3):
d
3.54e3.56 (t, J ¼ 5, 4H), 3.73e3.75 (t,
J ¼ 5.5, 4H), 7.00e7.05 (dd, J ¼ 9 and 2.5,1H), 7.49e7.53 (t, J ¼ 8,1H),
7.59e7.60 (d, J ¼ 2.5, 1H), 7.73e7.76 (td, J ¼ 7.5 and 1.5, 1H),
7.87e7.89 (d, J ¼ 9, 1H), 7.96e7.98 (dd, J ¼ 8 and 1.5, 1H), 8.40e8.41
3. Result and discussion
(d, J ¼ 7.5, 1H). 13C NMR (125 MHz, CDCl3):
d
51.97, 71.28, 113.10,
3.1. Discussion of synthesis
119.04, 126.62, 130.20, 134.20, 134.85, 136.74, 137.68, 140.65, 141.05,
142.46, 160.96, 181.91, 186.20.
Synthesis of compounds 4 and 5 were accomplished by reacting
N, N-diethyl aniline and morpholine with intermediate 1 in
methanol-water mixture and in neat water respectively. Michael
2.3.5. General procedure for the synthesis of compound 4, 5, 9, 13
The respective diketo compound and 1, 10-phenanthroline-5, 6-
diamine were dissolved in methanol followed by catalytic amount
of acetic acid and the mixture was refluxed for 5e6 h. The mixture
was cooled to room temperature and the solid separated was
filtered, washed with small amount of cold methanol followed by
hexane and dried well to get red colored product.
addition reaction of morpholine with a, b unsaturated ketone was
found much easier in the presence of sulfonate salt. After the
addition of morpholine to the slightly wet sulfonate salt red colored
intermediate 3 was formed immediately, and after a span of 24 h at
room temperature black colored intermediate 2 was formed
[66,75e77]The intermediates 2 and 3 were treated with 1, 10-
phenanthroline-5, 6-diamine in methanol at reflux condition for
5e6 h to obtain the desired compounds 4 and 5 respectively
(Scheme 1). 1, 10-Phenanthroline-5,6-diamine was synthesized by
following the reported procedure [78]. Intermediates 7 and 11 were
2.3.5.1. 4-(Benzo[h]dipyrido[3,2-a:20,3'-c]phenazin-14-yl)-N,N-dieth-
ylaniline (4). Compound 4 was synthesized by following the gen-
eral procedure described above. 1, 10-Phenanthroline-5, 6-diamine