B.R. Raju, et al.
DyesandPigments173(2020)107870
2.4.2. N-(2,3,6,7-Tetrahydro-1H-benzo[a]quinolizino[1,9-hi]phenoxazin-
14(5H)-ylidene) benzenaminium chloride 4b
J = 8.0 Hz, 1H, H-13), 8.68 (d, J = 7.6 Hz, 1H, H-10) ppm. 13C NMR δC
(CD3OD, 100.6 MHz), 20.21 (C-1), 20.46 (C-6), 21.56 (C-2), 28.53 (C-
7), 32.47 (NH2CH2CH2CH2Cl), 42.71 (NHCH2CH2CH2Cl), 43.30
(NHCH2CH2CH2Cl), 52.06 (C-3), 52.56 (C-5), 93.28 (C-15), 106.75
(Ar–C), 123.44 (C-13), 124.01 (Ar–C), 124.97 (C-10), 129.22 (Ar–C),
129.89 (C-12), 130.14 (C-8), 131.24 (Ar–C), 132.02 (C-11), 132.26
(Ar–C), 133.76 (Ar–C), 144.78 (Ar–C), 151.73 (Ar–C), 152.82 (Ar–C),
156.92 (C-14) ppm. HRMS: m/z (EI): Found [M+1]+: 454.3900;
The product of the reaction of 1 (0.115 g, 0.525 mmol) in ethanol
(1 mL) and concentrated hydrochloric acid (0.014 mL) with N-phe-
nylnaphthalen-1-amine 2b (0.057 g, 0.262 mmol) (reflux time 17 h),
was chromatographed with dichloromethane and dichloromethane/
methanol 9.5:0.5, to give compound 4b as green blue solid (0.047 g,
yield 20%). Mp 118.7–120 °C. Rf = 0.44 (dichloromethane/methanol,
9:1 vol). FTIR (KBr 1%): νmax 3439, 3000, 1643, 1469, 1284, 1205,
C
25H25Cl2N3O requires [M+1]+: 454.3905.
.
1141, 1098, 1033, 770 cm−1 1H NMR δH (CD3OD, 400 MHz),
2.04–2.18 (m, 4H, 2-H and 6-H), 2.51 (t, J = 6.4 Hz, 2H, 7-H), 2.92–3.0
(m, 2H, 1-H), 3.60–3.70 (m, 2H, 3-H), 3.82 (t, J = 6.4 Hz, 2H, 5-H),
6.83 (s, 1H, 15-H), 7.48 (s, 1H, 8-H), 7.73–7.84 (m, 4H, 4 × Ar–H),
7.87–7.95 (m, 2H, 12-H and 1 × Ar–H), 8.10 (t, J = 7.6 Hz, 1H, 11-H),
2.4.5. 3-Hydroxy-N-(2,3,6,7-tetrahydro-1H-benzo[a]quinolizino[1,9-hi]
phenoxazin-14(5H)-ylidene)propan-1-aminium chloride 4e
The product of the reaction of 1 (0.115 g, 0.525 mmol) in ethanol
(1 mL) and concentrated hydrochloric acid (0.014 mL) with 3-(naph-
thalen-1-ylamino)propan-1-ol 2e (0.053 g, 0.262 mmol) (reflux time
18 h), was chromatographed with dichloromethane and di-
chloromethane/methanol 9.5:0.5, to give compound 4e as green blue
solid (0.051 g, yield 22%). Mp > 300 °C. Rf = 0.48 (dichloromethane/
methanol, 9:1 vol). IR (KBr 1%): νmax = 3450, 2932, 1640, 1588, 1553,
1531, 1471, 1440, 1386, 1355, 1317, 1284, 1217, 1177, 1139, 1101,
8.27 (d, J = 8.4 Hz, 1H, 13-H), 8.89 (d, J = 7.2 Hz, 1H, 10-H) ppm. 13
C
NMR δC (CD3OD, 100.6 MHz), 20.26 (C-1), 20.60 (C-6), 21.66 (C-2),
28.53 (C-7), 51.92 (C-3), 52.41 (C-5), 96.70 (C-15), 106.54 (Ar–C),
119.29 (Ar–C), 123.76 (Ar–C), 124.30 (C-13), 125.24 (C-10), 128.62
(Ar–C), 129.10 (Ar–C), 129.92 (2xAr-C), 130.27 (C-8), 132.14 (C-11),
132.64 (Ar–C, C-12), 133.27 (2 × Ar–C), 144.97 (2xAr-C), 152.16
(Ar–C), 152.65 (Ar–C), 159.18 (C-14), 160.62 (Ar–C) ppm. HRMS: m/z
781 cm−1 1H NMR δH (CD3OD, 400 MHz), 2.04–2.14 (m, 6H, 2-H, 6-H
.
(ESI): Found [M+1]+: 454.1691; C28H24ClN3O requires [M+1]+
454.1688.
:
and NHCH2CH2CH2OH), 2.88 (t, J = 6.4 Hz, 2H, 1-H), 2.95 (t,
J = 6.0 Hz, 2H, 7-H), 3.60–3.67 (m, 4H, 3-H and 5-H), 3.75 (t,
J = 7.2 Hz, 2H, NHCH2CH2CH2OH), 3.82 (t, J = 6.0 Hz, 2H,
NHCH2CH2CH2OH), 6.77 (s, 1H, 15-H), 7.34 (s, 1H, 8-H), 7.72 (t,
J = 7.2 Hz, 1H, 12-H), 7.83 (t, J = 7,2 Hz, 1H, 11-H), 8.21 (d,
J = 8.4 Hz, 1H, 13-H), 8.71 (d, J = 7.6 Hz, 1H, 10-H) ppm. 13C NMR δC
(CD3OD, 100.6 MHz), 20.27 (C-1), 20.53 (C-6), 21.62 (C-2), 28.56 (C-
7), 32.17 (NH2CH2CH2CH2OH), 42.94 (NHCH2CH2CH2OH), 51.97 (C-
3), 52.47 (C-5), 60.54 (NHCH2CH2CH2OH), 93.35 (C-15), 106.69
(Ar–C), 123.40 (C-13), 124.13 (Ar–C), 125.10 (C-10), 128.77 (Ar–C),
129.96 (C-12), 130.11 (C-8), 131.65 (Ar–C), 132.08 (C-11), 132.36
(Ar–C), 133.33 (Ar–C), 144.77 (Ar–C), 152.0 (Ar–C), 152.56 (Ar–C),
157.15 (C-14) ppm. HRMS: m/z (ESI): Found [M+1]+: 436.1785;
2.4.3. N-(2,3,6,7-Tetrahydro-1H-benzo[a]quinolizino[1,9-hi]phenoxazin-
14(5H)-ylidene)propan-1-aminium chloride 4c
The product of the reaction of 1 (0.115 g, 0.525 mmol) in ethanol
(1 mL) and concentrated hydrochloric acid (0.014 mL) with N-pro-
pylnaphthalen-1-amine 2c (0.048 g, 0.262 mmol) (reflux time 17 h),
was chromatographed with dichloromethane and dichloromethane/
methanol 9.5:0.5, to give compound 4c as blue green solid (0.047 g,
yield 20%). Mp 223–225 °C. Rf 0.35 (dichloromethane/methanol,
9.5:0.5 vol). FTIR (KBr 1%): νmax 3438, 3000, 1642, 1468, 1285, 1207,
1150, 1090, 1030, 774 cm−1 1H NMR δH (CD3OD, 400 MHz): 1.14 (t,
.
J = 7.6 Hz, 3H NHCH2CH2CH3), 1.90 (sext, J = 7.2 Hz, 2H,
NHCH2CH2CH3), 2.04–2.16 (m, 2H, 6-H and 2-H), 2.90–2.99 (m, 2H, 7-
H and 1-H), 3.58–3.66 (m, 4H, 3-H, 5-H and NHCH2CH2CH3), 6.82 (s,
1H, 15-H), 7.40 (s, 1H, 8-H), 7.77 (td, J = 7.2 and 1.6 Hz, 1H, 12-H),
7.86 (td, J = 7.6 and 1.2 Hz, 1H, 11-H), 8.28 (d, J = 8.0 Hz, 1H, 13-H),
8.79 (d, J = 7.6 Hz, 1H, 10-H) ppm. 13C NMR δC (CD3OD, 100.6 MHz),
11.80 (NHCH2CH2CH3), 20.31 (C-1), 20.57 (C-6), 21.64 (C-2), 22.99
(NHCH2CH2CH3), 28.56 (C-7), 47.09 (NHCH2CH2CH3), 51.94 (C-3),
52.43 (C-5), 93.48 (C-15), 106.72 (Ar–C), 123.42 (C-13), 124.29
(Ar–C), 125.18 (C-10), 128.68 (Ar–C), 130.04 (C-12), 130.13 (C-8),
131.88 (Ar–C), 132.14 (C-11), 132.54 (Ar–C), 133.31 (Ar–C), 144.89
(Ar–C), 152.20 (Ar–C), 152.53 (Ar–C), 157.40 (C-14) ppm. HRMS: m/z
C
25H26ClN3O2 requires [M+1]+: 436.1794.
2.4.6. 3-Carboxy-N-(2,3,6,7-tetrahydro-1H-benzo[a]quinolizino[1,9-hi]
phenoxazin-14(5H)-ylidene)propan-1-aminium chloride 4f
The product of the reaction of 1 (0.254 g, 1.0 mmol) in ethanol
(2 mL) and concentrated hydrochloric acid (0.027 mL) with 4-(naph-
thalen-1-ylamino)butanoic acid 2f (0.115 g, 0.50 mmol) (reflux time
17 h), was chromatographed with dichloromethane and di-
chloromethane/methanol 9.5:0.5, to give compound 4f as green blue
solid (0.88 g, yield 19%). Mp 154.6–156.8 °C. Rf = 0.42 (di-
chloromethane/methanol, 9:1 vol). IR (KBr 1%): νmax = 2923, 2853,
1731, 1721, 1637, 1589, 1545, 1499, 1435, 1375, 1334, 1322, 1290,
(ESI): Found [M+1]+: 420.1855; C25H26ClN3O requires [M+1]+
420.1845.
:
1230, 1182, 1162, 1146, 1127, 1100, 1054, 1001, 918, 807, 753 cm−1
.
1H NMR δH (CD3OD, 400 MHz), 2.0–2.16 (m, 6H, 2-H, 6-H and
NHCH2CH2CH2CO2H), 2.59 (t, J = 7.2 Hz, 2H, NHCH2CH2CH2CO2H),
2.75 (t, J = 5.6 Hz, 2H, 1-H), 2.88 (t, J = 6.0 Hz, 2H, 7-H), 3.55–3.64
(m, 6H, 3-H, 5-H, and NHCH2CH2CH2CO2H), 6.63 (s, 1H, 15-H), 6.94
(s, 1H, 8-H), 7.65 (t, J = 7.2 Hz, 1H, 12-H), 7.77 (t, J = 7.6 Hz, 1-H, 11-
H), 8.06–8.16 (m, 1H, 13-H), 8.57 (d, J = 8.0 Hz, 1H, 10-H) ppm. 13C
NMR δC (CD3OD, 100.6 MHz), 20.17 (C-1), 20.57 (C-2), 21.54 (C-6),
2.4.4. 3-Chloro-N-(2,3,6,7-tetrahydro-1H-benzo[a]quinolizino[1,9-hi]
phenoxazin-14(5H)-ylidene)propan-1-aminium chloride 4d
The product of the reaction of 1 (0.335 g, 0.153 mmol) in ethanol
(1 mL) and concentrated hydrochloric acid (0.040 mL) with N-(3-
chloropropyl)naphthalen-1-amine 2d (0.167 g, 0.076 mmol) (reflux
time 24 h), was chromatographed with dichloromethane and di-
chloromethane/methanol 9.5:0.5, to give compound 4d as blue green
solid (0.017 g, yield 5%). Mp 209.3–210.8 °C. Rf = 0.60 (di-
chloromethane/methanol, 9:1 vol). IR (KBr 1%): νmax = 3428, 3223,
3027, 2961, 2929, 1707, 1640, 1588, 1543, 1472, 1438, 1385, 1358,
1314, 1282, 1217, 1176, 1136, 1099, 1047, 893, 780 cm−1. 1H NMR δH
(CD3OD, 400 MHz), 2.05–2.14 (m, 4H, H-2 and H-6), 2.33 (quint,
J = 6.4 Hz, 2H, NHCH2CH2CH2Cl), 2.83–2.92 (m, 2H, H-1), 2.95 (t,
J = 6.0 Hz, 2H, H-7), 3.60–3.69 (m, 4H, H-3 and H-5), 3.78 (t,
J = 6.8 Hz, 2H, NHCH2CH2CH2Cl), 3.83 (t, J = 6.4 Hz, 2H,
NHCH2CH2CH2Cl), 6.73 (s, 1H, H-15), 7.33 (s, 1H, H-8), 7.71 (t,
J = 7.2 Hz, 1H, H-12), 7.82 (t, J = 7.6 Hz, 1H, H-11), 8.21 (d,
24.70
(NHCH2CH2CH2CO2H),
28.49
(C-7),
31.84
(NHCH2CH2CH2CO2H), 44.58 (NHCH2CH2CH2CO2H), 51.97 (C-3),
52.35 (C-5), 93.44 (C-15), 106.70 (Ar–C), 123.32 (C-13), 124.94
(Ar–C), 125.43 (C-10), 128.90 (Ar–C), 130.06 (C-12), 131.17 (C-8),
131.97 (Ar–C), 132.10 (C-11), 133.12 (Ar–C), 133.38 (Ar–C), 144.54
(Ar–C), 151.60 (Ar–C), 152.59 (Ar–C), 157.10 (C-14), 175.91 (C]O)
ppm.
C
HRMS:
m/z
(ESI):
Found
[M+1]+
:
464.1745;
26H26ClN3O3requires [M+1]+: 464.1743.
2.4.7. 9,10,11,13,14,15-Hexahydro-6H-naphtho[2,3-a]quinolizino[1,9-
hi]phenoxazin-6-iminium chloride 5
The product of the reaction of 1 (0.115 g, 0.525 mmol) in ethanol
3