Paper
2-Chloro-3-(diphenylamino)naphthalene-1,4-dione (11).26,27
RSC Advances
2H), 7.77 (m, 4H), 7.50 (m, 3H), 7.30 (bs, NH2); 13C NMR (100
MHz, CDCl3 + DMSO-d6): d 125.0, 126.0, 126.1, 126.9, 127.1,
127.1, 127.5, 128.2, 128.9, 129.0, 131.2, 131.9, 133.0, 134.0,
134.2, 134.3, 135.5, 153.9, 179.4, 180.7; anal. calcd for
Yellow ne needle shaped crystals from methanol which on
exposure in air changed color yellow to uorescent light green;
ꢂ
yield 62%; mp: 130–132 C IR (KBr): 1592 and 1678 (>C]O of
quinone) cmꢁ1; 1H NMR (400 MHz, CDCl3): d 8.22 (m, 1H), 8.15
(m, 3H), 8.09 (m, 3H), 7.81 (m, 1H), 7.75 (m, 6H); 13C NMR (100
MHz, CDCl3): d 127.3, 127.3, 128.7, 131.2, 131.4, 134.3, 134.7,
157.2, 179.9, 180.1; MS: 360 (M+). Anal. calcd for C22H14ClNO2
(360): C, 73.44; H, 3.92; N, 3.89; found: C, 72.96; H, 3.98; N, 3.92;
Beilstein test:34 Cl positive.
2-Chloro-3-(4-hydroxyphenylamino)naphthalene-1,4-dione
(12).26,27 Violet powder from methanol; yield 96%; mp: 181 ꢂC; IR
(KBr): 1593 and 1678 (>C]O of quinone) 3269 (N–H), 3468 (O–
H) cmꢁ1; 1H NMR (400 MHz, CDCl3): d 8.19 (d, J ¼ 7.6, 1H), 8.12
(d, J ¼ 7.6, 1H), 7.90 (s, 1H), 7.75 (t, J ¼ 7.6, 1H), 7.69 (t, J ¼ 7.6,
1H), 7.35 (d, 2H), 7.05 (d, 2H), 4.75 (s, 1H). 13C NMR (100 MHz,
CDCl3 + acetone-d6): d 112.1, 114.4, 126.2, 126.9, 127.0, 129.3,
129.4, 131.9, 134.3, 139.0, 142.0, 155.51, 179.9, 180.1; anal. calcd
for C16H10ClNO3 (300): C, 64.12; H, 3.36; N, 4.67; found: C,
63.92; H, 3.42; N, 4.72; Beilstein test:34 Cl positive.
C
20H13NO2S (331): C, 72.49; H, 3.95; N, 4.23; S, 9.68; found: C,
71.92; H, 3.92; N, 4.27; S, 9.60.
2-Phenylamino-3-(phenylthio)naphthalene-1,4-dione (17).26,27
Brown solid from methanol; yield 99%; mp 143–145 ꢂC; IR (KBr):
1589 and 1664 (>C]O of quinone), 3265 (N–H) cmꢁ1; H NMR
1
(400 MHz, CDCl3): d 8.18 (d, J ¼ 7.6, 1H), 8.13 (d, J ¼ 7.6, 1H), 7.93
(bs, 1H), 7.76 (t, J ¼ 7.6, 1H), 7.69 (t, J ¼ 7.6, 1H), 7.17–7.15 (t, 2H),
7.13–6.98 (m, 4H), 6.75–6.68 (m, 4H); anal. calcd for C22H15NO2S
(357): C, 73.93; H, 4.23; N, 3.92; S, 8.97; found: C, 74.22; H, 4.21;
N, 3.98; S, 9.03.
2-(4-Hydroxyphenylamino)-3-(phenylthio)naphthalene-1,4-
dione (18).26,2ꢂ7 Shining brown solid from methanol; yield 88%;
mp 220–221 C; IR (KBr): 1546 and 1624 (>C]O of quinone),
3315 (N–H), 3375 (O–H) cmꢁ1; H NMR (400 MHz, CDCl3): d
1
8.18 (d, J ¼ 7.2, 1H), 8.12 (d, J ¼ 7.2, 1H), 7.90 (bs, 1H), 7.68–
7.76 (m, 3H) 7.31 (m, 1H), 7.03–7.05 (m, 3H), 6.77–6.80
(m, 2H), 6.62 (m, 3H); anal. calcd for C22H15NO3S (373): C,
70.76; H, 4.05; N, 3.75; S, 8.59; found: C, 70.02; H, 4.01; N, 3.70;
S, 8.63.
2-(Diphenylamino)-3-(phenylthio)naphthalene-1,4-dione
(19).26,27 Red oil; yield 90%; IR (KBr): 1590 and 1678 (>C]O of
quinone) cmꢁ1; 1H NMR (400 MHz, CDCl3): d 8.04–8.08 (m, 4H),
7.94–7.98 (m, 2H), 7.60–7.80 (m, 4H), 7.43–7.49 (m, 3H), 7.02–
7.11 (m, 3H), 6.60–6.69 (m, 3H); 13C NMR (100 MHz, CDCl3): d
127.0, 127.3, 127.6, 127.8, 128.0 (4C), 129.4, 129.5, 130.7, 131.7,
131.8, 134.0, 134.4, 137.5, 178.5, 180.8. anal. calcd for
2-3-Chloro-1,4-dioxo-1,4-dihydronaphthalen-2-ylaminobenzo-
nitrile (13).26,27 The general procedure was followed for 24 h to
give orange crystals on crystallization with EtOAc–hexane; yield
ꢂ
76%; mp: 233–234 C; IR (KBr): 554, 680, 734, 836, 879, 1002,
1158, 1229, 1274, 1380, 1478, 1539, 1591, 1679, 2364, 3450,
cmꢁ1; 1H NMR (CDCl3): d 7.08 (d, J ¼ 7.6 Hz, 1H), 7.31 (d, J ¼ 7.6
Hz, 1H), 7.56–7.82 (m, 4H), 7.67 (s, 1H) 8.19 (dd, J ¼ 7.6 Hz, 1.0
Hz, 2H); 13C NMR (CDCl3): 99.6, 113.3, 117.1, 118.3, 119.4,
127.3, 128.8, 130.1, 131.3, 133.9, 134.2, 135.1, 136.6, 151.7,
152.2, 178.3, 179.1; MS: 309 (MH+); anal. calcd (C17H9ClN2O2):
C, 66.14; H, 2.94; N, 9.07; found: C, 65.85; H, 2.70; N, 8.94;
Beilstein test:34 Cl positive.
C
28H19NO2S (434): C, 77.57; H, 4.42; N, 3.23; S, 7.40; found: C,
77.42; H, 4.38; N, 3.18; S, 7.45.
2,20-(1,4-Dioxo-1,4-dihydronaphthalene-2,3-diyl)bis(azane-
diyl)dibenzonitrile (14).26,27 Dark red solid aer crystallization
with EtOAc; yield 55%; mp 258–259 ꢂC; IR (KBr): 505, 617, 645,
716, 761, 793, 851, 912, 1016, 1095, 1135, 1241, 1287, 1332,
2-(Diphenylamino)-3-(naphthalene-1-ylthio)naphthalene-
1,4-dione (20).26,27 Yellow powder from methanol; yield 98%;
ꢂ
mp: 120–121 C; IR (KBr): 1590 and 1678 (>C]O of quinone)
cmꢁ1 1H NMR (400 MHz, CDCl3): d 8.04–8.08 (m, 4H), 7.94–
;
7.7.98 (m, 2H), 7.60–7.80 (m, 9H), 7.43–7.49 (m, 6H); 13C NMR
(100 MHz, CDCl3 + DMSO-d6): d 125.6, 125.8, 125.9, 126.0, 126.6,
127.0, 127.5, 127.7, 128.3, 128.6, 130.0, 130.6, 130.7, 131.3,
131.5, 132.8, 133.0, 133.3, 158.5, 178.8, 181.1; anal. calcd for
1
1383, 1469, 1509, 1598, 1677, 2222, 2366, 3265, 3416 cmꢁ1; H
NMR (CDCl3 + DMSO-d6): d 6.72–7.32 (m, 6H), 7.67–7.80 (m,
6H), 8.15 (dd, J ¼ 5.5 Hz, 3.0 Hz, 2H); 13C NMR (100 MHz, CDCl3
+ DMSO-d6): d 99.1, 118.5, 119.0, 119.8, 120.8, 126.9, 131.9,
134.8, 135.4, 137.0, 151.2, 181.8; MS: M+ (M+ + 1): 391; anal.
calcd (C24H14N4O2): C, 73.84; H, 3.61; N, 14.35; found: C, 74.02;
H, 3.82; N, 14.60.
C
32H21NO2S (484): C, 79.48; H, 4.38; N, 2.90; S, 6.63; found: C,
78.98; H, 4.34; N, 2.92; S, 6.58.
2-(3-Methoxyphenylthio)-3-(phenylamino)naphthalene-1,4-
dione (21).26,27 Shining brown solid from methanol; yield 99%;
2-Amino-3-phenylsulfanyl-[1,4]naphthoquinone (15).26,27 Red
crystals aer crystallization with methanol; yield 92%; mp 160–
ꢂ
mp: 143–145 C; IR (KBr): 1587 and 1662 (>C]O of quinone),
2359 and 2925 (OMe), 3310 (N–H) cmꢁ1 1H NMR (400 MHz,
;
ꢂ
161 C; IR (KBr): 1598 and 1676 (>C]O of quinone), 3243 and
1
3462 (NH2) cmꢁ1; H NMR (300 MHz, CDCl3): d 8.08 (m, 2H),
CDCl3): d 8.18 (d, J ¼ 7.6, 1H), 8.13 (d, J ¼ 7.6, 1H), 7.96 (bs, 1H),
7.77 (t, J ¼ 7.6, 1H), 7.69 (t, J ¼ 7.6, 1H) 7.19–7.17 (t, 2H, Ar-H),
7.15–7.09 (t, 1H, Ar-H), 6.96–6.92 (t, 1H, Ar-H), 6.73–6.71 (d, 2H,
Ar-H), 6.60–6.58 (d, 1H, Ar-H), 6.38–6.39 (d, 1H), 6.22 (s, 1H, Ar-
H), 3.63 (s, 3H, OCH3), mass (Fab): M+ ¼ 387, M+ + 1 ¼ 388, M+ +
2 ¼ 389; 13C NMR (400 MHz, CDCl3): d 55.0, 112.0, 112.7, 113.0,
114.1, 120.6, 123.0, 124.6, 126.7, 127.0, 127.7, 129.0, 130.3,
132.7, 133.3, 134.7, 136.3, 142.6, 159.3, 180.7, 181.0; anal. calcd
for C23H17NO3S (387): C, 71.30; H, 4.42; N, 3.62; S, 8.28; found:
C, 71.24; H, 4.39; N, 3.58; S, 8.32.
7.65 (m, 2H), 7.38 (m, 2H), 7.26 (s, 3H), 7.09 (bs, 2H); 13C NMR
(100 MHz, CDCl3 + DMSO-d6): d 126.0, 126.9, 127.1, 127.3, 129.5,
131.1, 132.9, 134.2, 135.5, 136.5, 153.9, 179.3, 180.7; anal. calcd
for C16H11NO2S (281): C, 68.31; H, 3.94; N, 4.98; S, 11.40; found:
C, 67.98; H, 3.88; N, 4.93; S, 11.35.
2-Amino-3-(naphthalen-1-ylsulfanyl)-[1,4]naphthoquinone
(16).26,27 Brown powder from methanol; yield 90%; mp 170–171
ꢂC; IR (KBr): 1585 and 1662 (>C]O of quinone), 3270 and 3440
(NH2) cmꢁ1; 1H NMR (300 MHz, CDCl3): d 8.17 (m, 2H), 7.98 (m,
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RSC Adv., 2014, 4, 12441–12447 | 12445