1406
A. A. Vasilev et al.
(d, 1H, J3HH 8.64, CH), 7.22–7.25 (m, 2H, CH), 7.31–7.35 (m,
1H, CH), 7.39 (d, 1H, J3HH 7.87, CH), 7.42–7.45 (dd, 1H, CH),
7.61 (d, 1H, J3HH 7.74, CH), 7.76–7.79 (m, 1H, CH), 7.92–7.95
7.72–7.80 (m, 2H, CH), 7.82–8.05 (m, 4H, CH), 8.15–8.21 (m,
1H, CH), 8.53–8.62 (m, 2H, CH). nmax (KBr)/cmꢀ1 1709, 1672,
1587, 1521, 1346, 1237, 751. Anal. Calc. for C33H20N4O6S
(600.60): C 65.99, H 3.36, N 9.33. Found: C 66.40, H 3.51,
N 9.74 %.
(m, 1H, CH), 8.45 (d, 1H, J3 7.74, CH), 8.61–8.65 (m, 2H,
HH
CH), 8.68–8.69 (m, 1H, CH). dC (CDCl3) 11.1 (CH3), 21.2
(CH2), 49.2 (CH2), 86.3 (CH), 108.6 (CH), 121.6 (CH), 123.4
(CH), 124.1 (CH), 124.5 (CH), 127.8 (CH), 129.0 (CH), 129.4
(CH), 130.6 (CH), 131.3 (CH), 132.3 (CH), 132.5 (CH), 138.5
(CH), 149.9 (CH). nmax (KBr)/cmꢀ1 1714, 1671, 1587, 1364,
1240, 749. m/z (8 kV) 464 (100 %, [Mþ]). Anal. Calc. for
C29H22N2O2S (462.56): C 75.30, H 4.79, N 6.06. Found: C
75.67, H 4.21, N 6.03 %.
4-[(3-Methyl-3H-benzothiazole-2-ylidene)methyl]-N-2-
methylpyridinium-1,8-naphthalimide iodide (7h)
Yield: 70 %. Mp 221–2238C. dH (250 MHz, DMSO-d6) 1.78
(s, 3H, NCH3), 3.12 (s, 3H, NþCH3), 6.79 (s, 1H, CH), 7.37–7.41
(m, 2H, CH), 7.62–7.71 (m, 3H, CH), 7.62–7.72 (m, 3H, CH),
8.05 (t, 1H, J3 7.04, CH), 8.48 (d, J3 7.79, CH), 8.67
HH
HH
(d, J3HH 7.31, CH), 8.77 (d, J3HH 8.05, CH). nmax (KBr)/cmꢀ1
1772, 1736, 1664, 1587, 1509, 1471, 1327, 1226, 1018, 778,
748. m/z (8 kV) 578 (100 %, [Mþ]). Anal. Calc. for
C27H20IN3O2S ( 577.44): C 56.16, H 3.49, N 7.28. Found (%):
C 56.78, H 3.21, N 7.75 %.
4-[(3-Butyl-3H-benzothiazole-2-ylidene)methyl]-N-
phenyl-1,8-naphthalimide (7d)
Yield: 51 %. Mp 201–2038C. dH (250 MHz, DMSO-d6) 0.91
(t, 3H, CH3), 1.27–1.35 (m, 2H, CH2), 3.22–3.34 (m, 2H, CH2),
4.08 (t, 2H, NCH2), 6.78 (s, 1H, CH), 7.15 (d, 1H, J3 7.68,
HH
4-[(1-Methylquinoline-4(1H)-ylidene)methyl]-N-2-
methylpyridinium-1,8-naphthalimide iodide (7i)
CH), 7.39–7.62 (m, 8H, CH), 7.89 (d, 1H, J3HH 7.75, CH), 8.00–
8.07 (dd, 1H, CH), 8.51 (d, 1H, J3HH 7.73, CH), 8.64 (d, 1H, J3
HH
7.73, CH), 8.72 (d, 1H, J3HH 8.48, CH). dH (500 MHz, CDCl3)
0.83 (t, 3H, CH3), 1.24–1.29 (m, 2H, CH2), 1.30–1.49 (m, 2H,
CH2), 1.62 (br s, 2H, NCH2), 7.04–7.06 (dd, 1H, CH), 7.20 (s, 1H,
CH), 7.22 (d, 1H, J3HH 7.79, CH), 7.25 (d, 1H, J3HH 7.14, CH),
7.31–7.34 (m, 1H, CH), 7.41–7.51 (m, 1H, CH), 7.62 (d, 1H,
J3HH 7.66, CH), 7.78–7.80 (m, 1H, CH), 8.45 (d, 1H, J3HH 7.73,
CH), 8.61 (d, 1H, J3HH 8.49, CH), 8.65 (d, 1H, J3HH 7.26, CH).
Yield: 63 %. Mp 312–3148C. dH (250 MHz, DMSO-d6) 3.57
(s, 3H, NCH3), 3.63 (s, 3H, NþCH3), 6.76 (d, 1H, J3 7.75,
HH
CH), 7.12 (s, 1H, CH), 7.21 (d, 1H, J3HH 7.88, CH), 7.33–7.44
(m, 3H, CH), 6.62 (dd, 1H, J3HH 7.29, CH), 7.87 (dd, 2H, J3
HH
8.05, CH), 7.98–8.00 (m, 2H, CH), 8.13 (d, 1H, J3HH 8.10, CH),
8.38 (d, 1H, J3HH 8.75, CH), 8.42 (d, 1H, J3HH 8.01, CH), 8.56
(d, 1H, J3HH 7.03, CH), 8.93 (d, 1H, J3HH 8.25, CH). nmax (KBr)/
cmꢀ1 1752, 1719, 1632, 1582, 1540, 1517, 1377, 1322, 1002,
739. m/z (8 kV) 572 (100 %, [Mþ]). Anal. Calc. for
C29H22IN3O2 (571.41): C 60.96, H 3.88, N 7.35. Found: C
60.51, H 3.54, N 7.38 %.
n
max (KBr)/cmꢀ1 1712, 1670, 1584, 1364, 1237, 750. m/z (8kV)
477 (100 %, [Mþ]). Anal. Calc. for C30H24N2O2S (476.59): C
75.60, H 5.08, N 5.88. Found: C 76.08, H 5.05, N 5.73 %.
4-[(3-Benzyl-3H-benzothiazole-2-ylidene)methyl]-N-
phenyl-1,8-naphthalimide (7e)
Preparation of 3-Chloro-7H-benzo[de]benzo[4,5]imidazo
[2,1-a]isoquinolin-7-one (6c) and 3-Chloro-7H-benzo[de]
naphtho[20,30:4,5]imidazo[2,1-a]isoquinolin-7-one (6d)
Yield: 78 %. Mp 264–2658C. dH (250 MHz, DMSO-d6) 5.66
(s, 2H, NCH2), 6.74 (s, 1H, CH), 7.46–7.62 (m, 8H, CH),
8.16–8.22 (dd, 1H, CH), 8.66–8.81 (m, 9H, CH), 8.83 (d, 1H,
J3HH 8.07, CH). nmax (KBr)/cmꢀ1 1711, 1674, 1530, 1371, 1349,
1243, 764. m/z (8kV) 512 (100 %, [Mþ]). Anal. Calc. for
C33H22N2O2S (510.6): C 77.62, H 4.34, N 5.49. Found: C
77.59, H 4.35, N 5.12 %.
4-Chloronaphthalene anhydride (4e) (0.01 mol) and phenylene-
1,2-diamine (5h) (0.01 mol) or naphthalene-2,3-diamine (5i)
(0.01 mol) were dissolved in acetic acid (100 mL) and the
mixture was stirred and heated under reflux for 4 h. The mixture
was allowed to cool to room temperature and the resulting
precipitate was filtered off, washed with acetic acid, and dried in
a vacuum desiccator. The target compounds were purified by
silica gel column chromatography (eluent: petroleum ether/
dichloromethane/ethyl acetate with increasing polarity) fol-
lowed by recrystallisation from toluene.
4-[(Benzyl-3H-benzothiazole-2-ylidene)methyl]-N-(4-
nitrophenyl)-1,8-naphthalimide (7f)
Yield: 81 %. Mp 310–3128C. dH (250 MHz, DMSO-d6) 5.62
(s, 2H, CH2), 6.72 (s, 1H, CH), 7.11–7.20 (m, 1H CH), 7.36–7.43
(m, 7H, CH), 7.73–7.79 (m, 4H, CH), 7.85 (d, 1H J3 8.10,
3-Chloro-7H-benzo[de]benzo[4,5]imidazo[2,1-a]
isoquinolin-7-one (6c)
Yield: 98 %. Mp 294–2968C, lit 293–2948C.[36]
HH
CH), 8.40 (d, 2H, J3HH 8.86, CH), 8.45 (d, 1H, J3HH 8.27, CH),
8.48 (d, 1H, J3 7.54, CH), 8.56 (d, 1H, J3 8.55, CH). dH
HH
HH
(500 MHz, CDCl3) 6.08 (br s, 2H, CH2), 6.35 (s, 1H, CH), 6.62
(br s, 2H, CH), 6.79–6.82 (m, 2H, CH), 6.94 (t, 1H, CH), 7.21–
3-Chloro-7H-benzo[de]naphtho[20,30:4,5]imidazo[2,1-a]
isoquinolin-7-one (6d)
7.24 (m, 6H, CH), 7.39–7.41 (br s, 6H, CH), 7.43 (d, 1H, J3
HH
8.51, CH). nmax (KBr)/cmꢀ1 1693, 1651, 1533, 1347, 1237, 735.
Anal. Calc. for C33H21N3O4S (555.60): C 71.34, H 3.81, N 7.56.
Found: C 71.48, H 3.54, N 7.32 %.
Yield: 76 %. Mp . 3508C.
Synthesis of Dyes 7j and 7k
3-Chloro-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-
7-one (6c) (0.001 mol) or 3-chloro-7H-benzo[de]naphtho
[20,30:4,5]imidazo[2,1-a]isoquinolin-7-one (6d) (0.001 mol)
and the appropriate intermediate 6b (0.003 mol) were mixed in a
Schlenk flask and suspended in NMP (15 mL). The reaction
mixture was heated to 1208C and a mixture of DIPEA
(0.006 mol) and pyridine (0.0012 mol) was rapidly added. The
4-[(3-(4-Nitrobenzyl)-3H-benzothiazole-2-ylidene)
methyl]-N-4-nitrophenyl-1,8-naphthalimide (7g)
Yield: 68 %. Mp . 3508C. dH (250 MHz, DMSO-d6) 5.82
(s, 2H, NCH2), 6.74 (s, 1H, CH), 7.02–7.14 (m, 2H, CH),
7.18–7.22 (m, 1H, CH), 7.33 (br s, 1H, CH), 7.39 (d, 1H, J3
HH
7.87, CH), 7.45–7.58 (m, 2H, CH), 7.63 (d, 1H, J3HH 8.54, CH),