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Mehdi Rimaz et al. / Chinese Journal of Catalysis 37 (2016) 517–525
1H NMR (300 MHz, CDCl3) δ 2.42 (s, 3H), 6.05 (s, 2H), 6.94 (d,
1H, J = 8.1), 7.52 (d, 2H, J = 8.1), 7.56–7.69 (m, 4H), 7.70 (s, 1H).
13C NMR (75 MHz, CDCl3) δ 19.9, 101.5, 106.5, 107.9, 108.1,
109.4, 122.1, 126.0, 129.7, 130.8, 131.6, 132.3, 136.2, 148.5,
157.0, 159.1. Anal. found, C, 58.56; H, 3.53; N, 7.69. C18H13BrN2O2
requires C, 58.56; H, 3.55; N, 7.59.
N, 7.90. C17H12BrClN2 requires C, 56.77; H, 3.36; N, 7.79.
3‐(4‐Chlorophenyl)‐6‐(3‐methoxyphenyl)‐4‐methylpyridazine
(29): white crystals, 77%, mp 150 °C. IR (KBr): νmax = 3007,
2936, 2835, 1595, 1581, 1493, 1390, 1255, 1174, 1035, 843,
795 cm–1. 1H‐NMR (300 MHz, CDCl3) δ 2.45 (s, 3H), 3.92 (s, 3H),
7.06 (d, J = 8.4 Hz, 1H), 7.44 (t, J = 8.4 Hz, 1H), 7.51 (d, J = 8.7 Hz,
2H), 7.64–7.61 (m, 3H), 7.74 (s, 1H), 7.81 (s, 1H).13C NMR (75
MHz, CDCl3) δ 19.8, 54.6, 110.9, 120.2, 124.7, 127.5, 128.9,
129.5, 129.8, 131.0, 131.6, 135.4, 136.0, 137.5, 157.3, 159.5.
Anal. found, C, 69.60; H, 4.84; N, 9.21. C18H15ClN2O requires C,
69.57; H, 4.86; N, 9.01.
3‐(4‐Chlorophenyl)‐6‐phenyl‐4‐methylpyridazine (23):
white crystals; 28%; mp 163 °C. IR (KBr): νmax = 3087, 3070,
3041, 2927, 1597, 1587, 1490, 1451, 1092, 1006, 789 cm–1. 1H
NMR (300 MHz, CDCl3) δ 2.44 (s, 3H), 7.53–7.47 (m, 5H), 7.62
(d, 2H, J = 8.4), 7.73 (s, 1H), 8.13 (d, 2H, J = 6.3). 13C NMR (75
MHz, CDCl3) δ 19.9, 124.6, 126.0, 127.5, 128.8, 129.7, 129.8,
130.1, 131.6, 135.0, 136.0, 157.6, 159.4. Anal. found, C, 72.77; H,
4.69; N, 10.17. C17H13ClN2 requires C, 72.73; H, 4.67; N, 9.98.
3‐(4‐Chlorophenyl)‐6‐(4‐bromophenyl)‐4‐methylpyridazine
(24): white crystals; 67%; mp 174 °C. IR (KBr): νmax = 3090,
3055, 3035, 2960, 2925, 1592, 1486, 1404, 1091, 1004, 824
cm–1. 1H NMR (300 MHz, CDCl3) δ 2.45 (s, 3H), 7.50 (d, 2H, J =
8.4), 7.57–7.69 (m, 4H), 7.72 (s, 1H), 8.02 (d, 2H, J = 8.4). 13C
NMR (75 MHz, CDCl3) δ 20.0, 124.6, 126.0, 127.6, 128.1, 129.8,
129.3, 131.5, 132.9, 135.2, 136.2, 156.5, 159.7. Anal. found, C,
56.81; H, 3.35; N, 7.95. C17H12BrClN2 requires C, 56.77; H, 3.36;
N, 7.79.
3‐(4‐Chlorophenyl)‐6‐(3,4‐dimethoxyphenyl)‐4‐methylpyri‐
dazine (30): white crystals; 78%; mp 182 °C. IR (KBr): νmax
=
3086, 3061, 3001, 2966, 2942, 2902, 2842, 2882, 1587, 1464,
1240, 1091, 1023, 838 cm–1. 1H NMR (300 MHz, CDCl3) δ 2.42
(s, 3H), 3.95 (s, 3H), 4.00 (s, 3H), 6.98 (d, 1H, J = 8.4), 7.47 (d,
2H, J = 7.8), 7.51–7.64 (m, 3H), 7.69 (s, 1H), 7.93 (s, 1H). 13
C
NMR (75 MHz, CDCl3) δ 20.0, 55.3, 56.6, 108.8, 109.1, 109.8,
110.7, 111.3, 111.7, 125.6, 127.7, 128.6, 131.3, 135.5, 135.9,
156.9, 158.9. Anal. found, C, 66.99; H, 5.04; N, 8.31.
C17H17ClN2O2 requires C, 66.96; H, 5.03; N, 8.22.
3‐(4‐Chlorophenyl)‐6‐(3,4‐methylenedioxyphenyl)‐4‐methyl‐
pyridazine (31): yellow crystals, 80%, mp 166 °C. IR (KBr): νmax
= 3081, 3046, 3006, 2966, 2897, 2787, 1592, 1505, 1452, 1108,
1001, 819 cm–1. 1H NMR (300 MHz, CDCl3) δ 2.42 (s, 3H), 6.05
(s, 2H), 6.94 (d, J = 8.1, 1H), 7.48 (d, J = 8.1, 2H), 7.66–7.54 (m,
4H), 7.71 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 19.9, 101.5, 106.6,
107.4, 108.8, 109.3, 125.7, 127.5, 129.7, 130.3, 131.3, 135.5,
135.9, 148.5, 157.0, 159.0. Anal. found, C, 66.59; H, 4.04; N, 8.81.
C18H13ClN2O2 requires C, 66.57; H, 4.03; N, 8.63.
3‐(4‐Chlorophenyl)‐6‐(4‐hydroxy‐3‐methoxyphenyl)‐4‐
methylpyridazine (32): white crystals; 78%; mp 150 °C. IR
(KBr): νmax = 3529, 3078, 3049, 2939, 1596, 1510, 1489, 1270,
1029, 824, 789 cm–1. 1H NMR (300 MHz, CDCl3) δ 2.44 (s, 3H),
4.01 (s, 3H), 6.01 (s, 1H), 7.05 (d, 1H, J = 8.1), 7.51–7.47 (m, 3H),
7.62 (d, 2H, J = 8.1), 7.70 (s, 1H), 7.99 (s, 1H). 13C NMR (75 MHz,
CDCl3) δ 55.2, 56.9, 108.5, 110.4, 113.5, 115.6, 118.9, 120.8,
121.1, 123.9, 125.7, 127.4, 129.4, 129.7, 131.5, 135.9. Anal.
found, C, 66.17; H, 4.61; N, 8.76. C18H15ClN2O2 requires C, 66.16;
H, 4.63; N, 8.57.
3,6‐Bis(4‐chlorophenyl)‐4‐methylpyridazine (25): white
crystals; 66%; mp 181 °C. IR (KBr): νmax = 3090, 3060, 3030,
1
1587, 1487, 1376, 1090, 1008, 827 cm–1. H NMR (300 MHz,
CDCl3) δ 2.46 (s, 3H), 7.47–7.56 (m, 4H), 7.62 (d, 2H, J = 8.1),
7.72 (s, 1H), 8.09 (d, 2H, J = 8.4). 13C NMR (75 MHz, CDCl3) δ
20.0, 124.6, 126.0, 127.4, 127.5, 128.1, 129.1, 129.8, 130.4,
131.3, 136.2, 156.5, 159.6. Anal. found, C, 64.80; H, 3.81; N, 9.03.
C17H12Cl2N2 requires C, 64.78; H, 3.84; N, 8.89.
3‐(4‐Chlorophenyl)‐6‐(4‐fluorophenyl)‐4‐methylpyridazine
(26): white crystals; 81%; mp 182 °C. IR (KBr): νmax = 3090,
3080, 2970, 2925, 2855, 1596, 1487, 1389, 1089, 1003, 842
1
cm–1. H NMR (300 MHz, CDCl3) δ 2.45 (s, 3H), 7.16–7.29 (m,
2H), 7.50 (d, 2H, J = 8.4), 7.62 (d, 2H, J = 8.4), 7.70 (s, 1H),
8.08–8.18 (m, 2H). 13C NMR (75 MHz, CDCl3) δ 19.9, 115.2,
115.8, 116.8, 117.1, 124.5, 129.7, 131.3, 136.1, 156.6, 159.4,
162.4, 165.7. Anal. found, C, 68.39; H, 4.07; N, 9.40. C17H12ClFN2
requires C, 68.35; H, 4.05; N, 9.38.
3‐(4‐Chlorophenyl)‐6‐(4‐methoxyphenyl)‐4‐methylpyridazine
(27): white crystals; 78%; mp 150 °C. IR (KBr): νmax = 3070,
3050, 3000, 2970, 2840, 1608, 1585, 1487, 1392, 1091, 1017,
824 cm–1. 1H NMR (300 MHz, CDCl3) δ 2.45 (s, 3H), 3.92 (s, 3H),
7.05 (d, 2H, J = 8.4), 7.49 (d, 2H, J = 8.4), 7.62 (d, 2H, J = 8.4),
7.68 (s, 1H), 8.11 (d, 2H, J = 8.1). 13C NMR (75 MHz, CDCl3) δ
20.0, 56.0, 113.2, 113.8, 114.1, 115.5, 127.5, 129.2, 129.9, 131.3,
135.5, 135.9, 157.1, 158.9. Anal. found, C, 69.59; H, 4.88; N, 9.13.
C18H15ClN2O requires C, 69.57; H, 4.86; N, 9.01.
3‐(4‐Methylphenyl)‐6‐phenyl‐4‐methylpyridazine (33): white
crystals; 70%; mp 133 °C. IR (KBr): νmax = 3055, 2930, 1586,
1490, 1392, 1092, 10018, 839 cm–1. 1H NMR (300 MHz, CDCl3)
δ 2.45 (s, 3H), 2.46 (s, 3H), 7.33 (d, 2H, J = 7.8), 7.45–7.60 (m,
5H), 7.74 (s, 1H), 8.13 (d, 2H, J = 6.3). 13C NMR (75 MHz, CDCl3)
δ 20.0, 20.1, 125.0, 126.2, 126.6, 127.9, 128.1, 129.6, 130.0,
130.5, 136.5, 138.9, 157.2, 160.4. Anal. found, C, 83.07; H, 6.20;
N, 10.91. C18H16N2 requires C, 83.04; H, 6.19; N, 10.76.
3‐(4‐Methylphenyl)‐6‐(4‐bromophenyl)‐4‐methylpyridazine
(34): white crystals; 94%; mp 166 °C. IR (KBr): νmax = 3090,
2922, 2850, 1588, 1486, 1407, 1073, 1003, 821 cm–1. 1H NMR
(300 MHz, CDCl3) δ 2.45 (s, 3H), 2.48 (s, 3H), 7.33 (d, 2H, J =
7.5), 7.57 (d, 2H, J = 7.5), 7.66 (d, 2H, J = 8.1), 7.75 (s, 1H), 8.03
(d, 2H, J = 8.1). 13C NMR (75 MHz, CDCl3) δ 20.1, 21.3, 124.8,
127.7, 128.2, 128.5, 129.5, 129.9, 130.1, 130.4, 131.4, 133.0,
156.2, 160.5. Anal. found, C, 63.78; H, 4.45; N, 8.30. C18H15BrN2
requires C, 63.73; H, 4.46; N, 8.26.
3‐(4‐Chlorophenyl)‐6‐(3‐bromophenyl)‐4‐methylpyridazine
(28): yellow crystals; 71%; mp 132 °C. IR (KBr): νmax = 3091,
3056, 3011, 2971, 2932, 1567, 1487, 1376, 1091, 1001, 843
1
cm–1. H NMR (300 MHz, CDCl3) δ 2.45 (s, 3H), 7.40 (t, 1H, J =
7.8), 7.50 (d, 2H, J = 8.4), 7.57–7.67 (m, 3H), 7.72 (s, 1H), 8.07
(d, 1H, J = 7.8), 8.29 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 20.0,
124.9, 126.3, 127.6, 129.2, 129.5, 130.8, 131.3, 131.8, 133.6,
135.2, 136.3, 138.1, 156.2, 159.8. Anal. found, C, 56.80; H, 3.38;