1577 (NO), 1603 (C=N), 2722 (OMe), 3110 (C-H), 3425 (NH). 1H-NMR (300 MHz, DMSO-d6) δ: 2.76 (s, 3H,
Me), 4.00 (s, 3H, OMe), 7.45 (s, 1H, H 3), 7.49 (d, J=6.0 Hz, 1H, H 3`), 7.67 (dd, 4J= 9.0 Hz, 3J= 3.0 Hz, 1H, H
7), 7.89 (d, J= 3.0 Hz, 1H, H 4`), 7.95 (d, J = 9.0 Hz, 1H, H 8), 8.21 (s, 1H, H 5), 8.86 (s, 1H, C=N), 13.0 (s,
1H, NH); 13C-NMR (75 MHz; CD3OD): 19.7 (Me), 55.6 (OMe), 100.6 (C 5), 103.0 (C 3), 115.3 (C 4`, 3`),
121.3 (C 7), 124.0 (C 4a), 124.8 (C=N), 133.6 (C 8), 146.4 (C 8a), 148.9 (C 4), 151.0 (C 5`), 151.1 (C 6),
152.3 (C 2`), 157.5 (C 2); MS ES+, [M+H, 100%]: 327.1. Accurate mass calculated for C16H14N4O4 + H:
327.109. Found: 327.1085, error: -0.9171 ppm.
3.1.5.9 4-((2-(6-Methoxy-2-methylquinolin-4-yl)hydrazono)methyl)benzoic acid (7i). Product isolated as
a yellow solid (130 mg, 78%). Mp: 272-275 ᵒC; IR (cm-1): 1577 (C=C), 1603 (C=N), 1675 (C=O), 2648
1
(OMe), 2928 (CH3), 3004(C-H), 3314 (2ᵒ amine); H-NMR (300 MHz, DMSO-d6) δ ppm: 2.71 (s, 3H, CH3),
3.98 (s, 3H, OMe), 7.51 (s, 1H, H 3`), 7.57 (d, J = 9.3 Hz, 1H, H 7`), 7.90 (d, J= 9.3 Hz, 1H, H 8`), 7.97-8.05
(m, 5H, H 2, 3, 5, 6, 5`), 8.11 (s, 1H, N=C), 8.87 (s, 1H, NH), 13.0 (br s, 1H, OH); 13C-NMR (75 MHz; DMSO-
d6): 20.0 (Me), 56.6 (OMe), 100.6 (C 5`), 102.9 (C 3`), 115.5 (C 4`a), 121.9 (C 7`), 124.5 (C 8`), 127.4 (C 3,
5), 129.8 (C 2, 6), 132.1 (C 1), 134.3 (C 4), 137.8 (C=N), 147.5 (C 8`a), 150.7 (C 4`), 152.5 (C 6`), 157.4 (C
2`), 166.8 (C=O); MS ES+, [M+H, 100%]: 336.1. Accurate mass calculated for C19H17N3O3 + H: 336.135.
Found: 336.1339, error: -1.19 ppm.
3.1.5.10 6-Methoxy-2-methyl-4-(2-(4-nitrobenzylidene)hydrazinyl)quinoline (7j). Product isolated as a
bright yellow solid (133 mg, 92%). Mp: 220-223 ᵒC; IR (cm-1): 1341 (N=O), 1574 (C=C), 1510 (C=N), 2856
1
(OMe), 2917 (CH3), 3366 (2ᵒ amine); H-NMR (300 MHz, DMSO-d6): 2.64 (s, 3H, CH3), 3.96 (s, 3H, OMe),
7.42 (s, 1H, H 3), 7.47 (d, J = 9.0 Hz, 1H, H 7), 7.82 (d, J = 9.0 Hz, 1H, H 8), 7.95 (d, 2H, J = 8.7 Hz, H 2`,
6`), 7.98 (s, 1H, H 5), 8.03 (d, 2H, J = 8.7 Hz, H 3`, 5`), 8.70 (br s, 1H, N=CH), 12.73 (s, 1H, NH); 13C-NMR
(75 MHz; DMSO-d6; Quat. C4, 8a, 4` not observed): 21.9 (Me), 56.1 (C, OMe), 100.8 (C 5), 101.9 (C 3),
115.9 (C 4a), 126.9 (C 7, 3`, 5`), 128.5 (C 1`), 129.8 (C 2`, 6`), 131.5 (C 8), 138.3 (C=N), 156.7 (C 2), 166.9
(C 6); MS ES-, [M+H, 100%]: 337.1. Accurate mass calculated for C18H16N4O3 + H: 337.130. Found:
337.1293, error: -0.593 ppm.
3.1.5.11 5-((2-(6-Methoxy-2-methylquinolin-4-yl)hydrazono)methyl)benzene-1,3-diol (7k). Product
isolated as a bright yellow solid (0.12 g, 75%). Mp: >300 ᵒC; IR (cm-1): 1599 (C=C), 1643 (C=N), 2961
1
(OMe), 2997 (CH3), 3081(C-H), 3295 (NH); H-NMR (400 MHz, DMSO-d6): 2.72 (s, 3H, CH3), 3.99 (s, 3H,
OMe), 6.38 (s, 1H, H 6`), 6.73 (s, 2H, H 2`, 4`), 7.40 (s, 1H, H 3), 7.62 (d, J = 5.4 Hz, 1H, H 7), 7.64 (d, J = 5.7
Hz, 1H, H 8), 8.09 (s, 1H, H 5), 8.63 (s, 1H, HC=N), 9.57 (s, 2H, 2 x OH), 12.3 (s, 1H, NH); 13C-NMR (75 MHz;
DMSO-d6): 19.9 (Me), 56.5 (OMe), 99.9 (C 5), 102.9 (C 3), 105.2 (C 6`), 105.6 (C 2`, 4`), 115.3 (C 4a), 124.7
(C 7), 135.2 (C 4, 3`), 149.9 (C=N), 150.8 (C 8a), 152.2 (C 6), 157.5 (C 2), 158.8 (C 1`, 5`); MS ES+, [M+H,
100%]: 324.6. Accurate mass calculated for C18H17N3O3 + H: 324.135. Found: 324.1339, error:-1.234 ppm.
3.1.5.12
3’-((2-(6-Methoxy-2-methylquinolin-4-yl)hydrazono)methyl)phenol (7l). Product isolated
as a beige solid (0.5 g, 33%). Mp: >300 ᵒC; IR (cm-1): 1570 (C=C), 1606 (C=N), 2895 (OMe), 2965 (CH3),
3157 (C-H), 3284 (OH); 1H-NMR (400 MHz, DMSO-d6): 2.73 (s, 3H, CH3), 3.99 (s, 3H, OMe), 6.91 (d, J = 6.0
Hz, 1H, H 6`), 7.30-7.34 (m, 3H, H 2`, 3`, 5`), 7.47 (s, 1H, H 3), 7.63 (d, J = 9.3 Hz, 1H, H 7), 7.91 (d, J=9.0
Hz, 1H, H 8), 8.07 (s, 1H, H 5), 8.7 (s, 1H, N=CH), 9.75 (s, 1H, OH); 13C-NMR (75 MHz; DMSO-d6): 19.9
(Me), 56.6 (OMe), 100.0 (C 5), 103.0 (C 3), 113.5 (C 2`), 115.3 (C 6`), 117.9 (C 4a), 118.7 (C 7), 121.4 (C
4`), 124.7 (C 8), 129.9 (C 5`), 133.8 (C 3`), 134.9 (C=N), 149.5 ( C 8a), 150.8 (C 4), 152.2 ( C 6), 157.5 (C 1`),