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H), 7.37 [m, 5 H, 2′′′(6′′′)-H, 3′′′(5′′′)-H and 4′′′-H], 5.49 (s, 2 H, solid. (370 mg, 83 %, EtOH/AcOEt) M.p. > 290 °C. IR (KBr): ν = 1682,
˜
CH2) ppm. 13C NMR (75 MHz, CD3OD): δ = 159.4 (2′-C), 153.9 (1′′- 1634, 1495, 1078, 753, 699 cm–1
.
1H NMR (300 MHz, CD3OD): δ =
C), 149.9 [2(6)-C], 149.4 (4-C), 147.9 (6′-C), 146.1 (5′-C), 134.5 (1′′′- 9.22 [dd, J = 6.8 and 1.4 Hz, 2 H, 2(6)-H], 8.78 (tt, J = 7.9 and 1.4 Hz,
C), 130.9 (4′-C), 130.7 [3(5)-C], 130.5, 130.4 (two overlapped signals)
and 130.3 [3′′(5′′)-C, 2′′′(6′′′)-C, 3′′′(5′′′)-C and 4′′′-C], 130.2 (4′′-C),
130.9 (4′-C), 123.9 [2′′(6′′)-C], 110.7 (3′-C), 58.9 (CH2) ppm.
1 H, 4-H), 8.73 (d, J = 1.4 Hz, 1 H, 3′-H or 6′-H), 8.70 (d, J = 1.4 Hz,
1 H, 6′-H or 3′-H), 8.24 [dd, J = 7.9 and 6.8 Hz, 2 H, 3(5)-H], 8.01 [m,
2 H, 2′′(6′′)-H], 7.60 [m, 3 H, 3′′(5′′)-H and 4′′-H], 7.38 [m, 5 H, 2′′′
C23H20BrN5 (446.35): calcd. C 61.89, H 4.52, N 15.69; found C 61.93, (6′′′)-H, 3′′′(5′′′)-H and 4′′′-H], 5.59 (s, 2 H, CH2) ppm. 13C NMR
H 4.41, N 15.55. MS (EI): m/z (%) = 286 (71), 285 (71), 183 (100), 104
(63), 91 (62), 77 (78), 51 (82).
(75 MHz, CD3OD): δ = 155.0, 154.9 and 153.8 (2′-C, 5′-C and 1′′-C),
149.9 (6′-C), 149.8 [2(6)-C], 137.0 (4-C), 133.9 (3′-C), 133.8 (1′′′-C),
131.6, 130.9, 130.6, 130.5 and 130.4 (two overlapped signals) [3(5)-
C, 3′′(5′′)-C, 4′′-C, 2′′′(6′′′)-C, 3′′′(5′′′)-C and 4′′′-C], 124.3 [2′′(6′′)-C],
58.8 (CH2) ppm. C22H19BrN6 (447.34): calcd. C 59.07, H 4.28, N 18.79;
found C 59.01, H 4.13, N 18.99. MS (EI): m/z (%) = 260 (51), 258 (53),
156 (29), 128 (23), 91 (99), 77 (100), 51 (40).
1-{N-Benzyl-N-[5-(p-methoxyphenylazo)pyridin-2-yl]amino}-
pyridinium Bromide (4b): After 7 d of reaction, 4b was obtained
as a brown solid (333 mg, 70 %, EtOH), m.p. 181–183 °C. IR (KBr):
ν = 1599, 1465, 1254, 1216, 1140, 1022, 685 cm–1. 1H NMR (300 MHz,
˜
CD3OD): δ = 9.20 [dd, J = 6.6 and 1.5 Hz, 2 H, 2(6)-H], 8.76 (tt, J =
7.8 and 1.5 Hz, 1 H, 4-H), 8.75 (d, J = 2.3 Hz, 1 H, 6′-H), 8.35 (dd, J =
9.0 and 2.3 Hz, 1 H, 4′-H), 8.23 [dd, J = 7.8 and 6.6 Hz, 2 H, 3(5)-H],
7.95 [d, J = 9.0 Hz, 2 H, 2′′(6′′)-H], 7.42 [m, 6 H, 3′-H, 2′′′(6′′′)-H, 3′′′
(5′′′)-H and 4′′′-H], 7.11 [d, J = 9.0 Hz, 2 H, 3′′(5′′)-H], 5.51 (s, 2 H,
CH2), 3.93 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CD3OD): δ = 164.3
(4′′-C), 159.0 (2′-C), 149.9 [2(6)-C], 149.4 (4-C), 148.2 (1′′-C or 5′-C),
147.2 (6′-C), 146.4 (5′-C or 1′′-C), 134.6 (1′′′-C), 130.6 [3(5)-C], 130.4
(two overlapped signals) [2′′′(6′′′)-C and 3′′′(5′′′)-C], 130.2 (4′′′-C),
130.9 (4′-C), 126.0 [2′′(6′′)-C], 115.5 [3′′(5′′)-C], 110.8 (3′-C), 59.0
(CH2), 56.2 (OCH3) ppm. C24H22BrN5O·H2O: calcd. C 58.31, H 4.89, N
14.17; found C 58.29, H 4.70, N 14.42. MS (EI): m/z (%) = 318 (66),
316 (99), 213 (100), 106 (41), 77 (62).
1-{N-Benzyl-N-[5-(p-methoxyphenylazo)pyrazin-2-yl]amino}-
pyridinium Bromide (5b): After 7 d of reaction, 5b was obtained
as a brown solid (290 mg, 61 %), m.p. 180–182 °C. IR (KBr): ν = 1599,
˜
1499, 1474, 1255, 1140, 1019, 693 cm–1. 1H NMR (500 MHz, CD3OD):
δ = 9.26 [dd, J = 6.9 and 1.6 Hz, 2 H, 2(6)-H], 8.80 (tt, J = 7.9 and
1.6 Hz, 1 H, 4-H), 8.73 (d, J = 1.3 Hz, 1 H, 3′-H), 8.70 (d, J = 1.3 Hz,
1 H, 6′-H), 8.27 [dd, J = 7.9 and 6.9 Hz, 2 H, 3(5)-H], 8.04 [d, J =
9.1 Hz, 2 H, 2′′(6′′)-H], 7.45 [m, 5 H, 2′′′(6′′′)-H, 3′′′(5′′′)-H and 4′′′-H],
7.16 [d, J = 9.1 Hz, 2 H, 3′′(5′′)-H], 5.61 (s, 2 H, CH2), 3.95 (s, 3 H,
CH3) ppm. 13C NMR (75 MHz, CD3OD): δ = 165.3 (4′′-C), 155.3 and
154.6 (2′-C and 5′-C), 149.8 (6′-C), 149.7 [2(6)-C], 148.3 (1′′-C), 136.6
(3′-C), 133.9 (1′′′-C), 131.5 (4-C), 130.9, 130.5 and 130.4 (two over-
lapped signals) [3(5)-C, 2′′′(6′′′)-C, 3′′′(5′′′)-C and 4′′′-C], 126.8 [2′′-
(6′′)-C], 115.7 [3′′(5′′)-C], 58.9 (CH2), 56.3 (CH3) ppm. MS (EI): m/z
(%) = 318 (45), 316 (100), 213 (74), 135 (24), 107 (44), 91 (23), 80
(24), 77 (33). HRMS (ESI-TOF, CH3OH) calculated for C23H21N6O
[M-Br]+ 397.1771, found 397.1782.
1-{N-[5-(Benzo[1,3]dioxol-5-ylazo)pyridin-2-yl]-N-benzylamino}-
pyridinium Bromide (4c): After 3 d of reaction, 4c was obtained
as a yellow solid (460 mg, 94 %, EtOH), m.p. 185–187 °C. IR (KBr):
ν = 1617, 1589, 1470, 1259, 1222, 1032, 678 cm–1. 1H NMR (500 MHz,
˜
CD3OD): δ = 9.20 [dd, J = 6.8 and 1.5 Hz, 2 H, 2(6)-H], 8.77 (tt, J =
7.8 and 1.5 Hz, 1 H, 4-H), 8.74 (d, J = 2.4 Hz, 1 H, 6′-H), 8.34 (dd, J =
8.8 and 2.4 Hz, 1 H, 4′-H), 8.23 [dd, J = 7.8 and 6.8 Hz, 2 H, 3(5)-H],
7.63 (dd, J = 8.4 and 2.0 Hz, 1 H, 6′′-H), 7.40 [m, 7 H, 3′-H, 4′′-H, 2′′′
(6′′′)-H, 3′′′(5′′′)-H and 4′′′-H], 7.04 (d, J = 8.4 Hz, 1 H, 7′′-H), 6.11 (s,
2 H, 2′′-H), 5.51 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CD3OD): δ =
159.0 (2′-C), 152.6 (7′′a-C), 150.6 (3′′a-C), 149.9 [2(6)-C], 149.8 (4-C),
149.4 (6′-C), 147.3 and 146.1 (5′-C and 5′′-C), 134.6 (1′′′-C), 130.6
[3(5)-C], 130.4 and 130.3 [2′′′(6′′′)-C and 3′′′(5′′′)-C], 130.2 (4′′′-C),
130.9 (4′-C), 125.7 (6′′-C), 110.7 (3′-C), 109.0 (7′′-C), 103.7 (2′′-C), 99.1
(4′′-C), 58.9 (CH2) ppm. C24H20BrN5O2·1/2H2O: calcd. C 57.73, H 4.24,
N 14.02; found C 58.11, H 4.50, N 13.80. MS (EI): m/z (%) = 330 (100),
318 (38), 242 (38), 227 (90), 121 (73), 79 (50).
1-[N-Benzyl-N-(5-chloro-3-phenylazopyridin-2-yl)amino]pyrid-
inium Bromide (17): After 9 d of reaction, 17 was obtained as a
brown solid (226 mg, 88 %, EtOH), m.p. 179–180 °C. IR (KBr): ν =
˜
1611, 1483, 1440, 757, 707, 672 cm–1
.
1H NMR (500 MHz, CD3OD):
δ = 9.23 [dd, J = 6.8 and 1.5 Hz, 2 H, 2(6)-H], 8.54 (d, J = 2.3 Hz, 1
H, 6′-H), 8.53 (tt, J = 7.9 and 1.5 Hz, 1 H, 4-H), 8.37 (d, J = 2.3 Hz, 1
H, 4′-H), 8.02 [dd, J = 7.9 and 6.8 Hz, 2 H, 3(5)-H], 7.69 [m, 2 H, 2′′
(6′′)-H], 7.54 [m, 3 H, 3′′(5′′)-H and 4′′-H], 7.44 [m, 2 H, 2′′′(6′′′)-H],
7.33 [m, 3 H, 3′′′(5′′′)-H and 4′′′-H], 5.51 (s, 2 H, CH2) ppm. 13C NMR
(125 MHz, CD3OD): δ = 152.9 and 152.2 (2′-C and 1′′-C), 148.6, 148.3
and 148.2 [2(6)-C, 4-C and 6′-C], 139.0 (3′-C), 134.1 (1′′′-C), 133.6
(4′′-C), 129.9 and 129.8 [3(5)-C and 3′′(5′′)-C], 129.6, 129.5 and 129.4
[2′′′(6′′′)-C, 3′′′(5′′′)-C and 4′′′-C], 129.3 (5′-C), 126.4 (4′-C), 123.9 [2′′
(6′′)-C], 60.9 (CH2) ppm. C23H19BrClN5 (480.79): calcd. C 57.46, H
3.98, N 14.57; found C 57.31, H 3.77, N 14.67. MS (EI): m/z (%) = 322
(49), 320 (77), 230 (85), 91 (91), 77 (100), 51 (64).
1-{N-Benzyl-N-[5-(p-nitrophenylazo)pyridin-2-yl]amino}pyrid-
inium Bromide (4d): After 10 d of reaction, 4d was obtained as a
brown solid (245 mg, 50 %, EtOH), m.p. 105–107 °C. IR (KBr): ν =
˜
1651, 1596, 1519, 1479, 1344, 1222, 862 cm–1
.
1H NMR (500 MHz,
CD3OD): δ = 9.20 [dd, J = 5.4 and 1.5 Hz, 2 H, 2(6)-H], 8.87 (d, J =
2.5 Hz, 1 H, 6′-H), 8.73 (tt, J = 7.8 and 1.5 Hz, 1 H, 4-H), 8.23 [dd, J =
7.8 and 5.4 Hz, 2 H, 3(5)-H], 8.44 [d, J = 9.3 Hz, 2 H, 3′′(5′′)-H], 8.42
(dd, J = 8.7 and 2.5 Hz, 1 H, 4′-H), 8.11 [d, J = 9.3 Hz, 2 H, 2′′(6′′)-
H], 7.41 [m, 6 H, 3′-H, 2′′′(6′′′)-H, 3′′′(5′′′)-H and 4′′′-H], 5.54 (s, 2 H,
CH2) ppm. 13C NMR (125 MHz, CD3OD): δ = 159.9 (2′-C), 156.9 (1′′-
C), 150.4 (4′′-C), 149.9 [2(6)-C], 149.5 (4-C), 149.1 (6′-C), 144.3 (5′-C),
134.4 (1′′′-C), 130.4 and 130.3 [2′′′(6′′′)-C and 3′′′(5′′′)-C], 130.2 (4′′′-
C), 130.7 [3(5)-C], 131.0 (4′-C), 126.9 [3′′(5′′)-C], 124.6 [2′′(6′′)-C],
110.5 (3′-C), 58.9 (CH2) ppm. C23H19BrN6O2·1/2H2O: calcd. C 55.21,
H 4.03, N 16.80; found C 55.14, H 4.08, N 16.56. MS (EI): m/z (%) =
320 (78), 319 (100), 228 (35), 183 (33), 143 (42), 91 (60), 79 (46), 58
(46).
1-[N-Benzyl-N-(5-phenyl-3-phenylazopyridin-2-yl)amino]pyrid-
inium Bromide (18a): After 7 d of reaction, 18a was obtained as a
dark brown solid. (428 mg, 82 %), m.p. 171–173 °C. IR (KBr): ν =
˜
1620, 1472, 1446, 1210, 1034, 771, 710 cm–1
.
1H NMR (500 MHz,
CD3OD): δ = 9.31 [dd, J = 6.9 and 1.0 Hz, 2 H, 2(6)-H], 8.85 (d, J =
2.0 Hz, 1 H, 6′-H), 8.57 (tt, J = 7.8 and 1.0 Hz, 1 H, 4-H), 8.32 (d, J =
2.0 Hz, 1 H, 4′-H), 8.08 [dd, J = 7.8 and 6.9 Hz, 2 H, 3(5)-H], 7.75 [m,
4 H, 2′′(6′′)-H and 2′′′(6′′′)-H], 7.60–7.46 [m, 8 H, 3′′(5′′)-H, 4′′-H,
3′′′(5′′′)-H, 4′′′-H and 2′′′′(6′′′′)-H], 7.37 [m, 3 H, 3′′′′(5′′′′)-H and 4′′′′-
H], 5.59 (s, 2 H, CH2) ppm. 13C NMR (125 MHz, CD3OD): δ = 153.8
and 153.5 (2′-C and 1′′′-C), 149.1 (4-C), 149.0 [2(6)-C], 148.7 (6′-C),
139.5 (3′-C), 137.2 and 137.1 (5′-C and 1′′′′-C), 135.0 (1′′-C), 133.9
(4′′′-C), 130.6, 130.5, 130.4 and 130.2 [2′′(6′′)-C, 3′′(5′′)-C, 3′′′(5′′′)-C
and 3′′′′(5′′′′)-C], 130.1 (4′′′′-C), 130.0 [3(5)-C], 129.8 (4′′-C), 128.1
1-[N-Benzyl-N-(5-phenylazopyrazin-2-yl)amino]pyridinium
Bromide (5a): After 5 d of reaction, 5a was obtained as a brown [2′′′′(6′′′′)-C], 125.2 (4′-C), 124.5 [2′′′(6′′′)-C], 61.6 (CH2) ppm. MS (EI):
Eur. J. Org. Chem. 2016, 2145–2156
2152 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim