Page 170 - 《精细化工》2020年第11期

·2316· 精细化工 FINE CHEMICALS 第 37 卷

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(d, J=7.6 Hz, 2H, C 25—H, C 29—H),7.50 (s, 1H, C 22—H), 固体，产率 65.2%，m.p. 132.6~133.2 ℃。 HNMR
7.40 (d, J=7.6 Hz, 2H, C 26 —H, C 28 —H), 7.28 (s, 1H, (400 MHz, C 5 D 5 N), δ: 8.33 (d, J=8.8 Hz, 2H, C 13 —H,
C 10 — H), 3.28~3.16 (m, 2H, C 1 — H, C 3 — H), C 15 —H), 8.12 (d, J=8.6 Hz, 2H, C 12 —H, C 16 —H),
2.80~2.75 (m, 1H, C 4 —H), 2.46 (m, 2H, C 2 —H), 2.37 7.87 (s, 1H, C 22 —H), 7.71 (d, J=8.5 Hz, 2H, C 25 —H,
(m, 1H, C 4 —H ), 1.56 (s, 3H, C 8 —H), 1.17 (s, 3H, C 29 —H), 7.32 (d, J=8.5 Hz, 2H, C 26 —H, C 28 —H),
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C 9 —H); CNMR (100 MHz, C 5 D 5 N), δ: 171.60 (C 19 ), 7.17 (s, 1H, C 10—H), 3.03~2.93 (m, 2H, C 1—H, C 3—H),
159.44 (C 27 ), 155.70 (C 6 ), 152.60 (C 21 ), 138.44 (C 5 ), 2.88 (m, 1H, C 4 —H), 2.54 (m, 2H, C 2 —H), 2.12 (m,
133.34 (C 11 ), 130.88 (C 10 ), 129.51 (C 25 , C 29 ), 128.56 1H, C 4—H ), 1.27 (s, 3H, C 8—H), 0.89 (s, 3H, C 9—H);
(C 12 , C 16 ), 128.12 (C 13 , C 15 ), 128.01 (C 24 ), 117.09 (C 26 , 13 CNMR (100 MHz, C 5 D 5 N), δ: 170.93 (C 19 ), 159.13
C 28 ), 101.57 (C 22 ), 43.53 (C 1 ), 41.85 (C 3 ), 40.44 (C 7 ) ,
32.89 (C 4 ), 29.05 (C 2 ), 21.59 (C 8 ), 22.16 (C 9 ); HRMS (C 27 ), 154.70 (C 6 ), 152.20 (C 21 ), 146.58 (C 14 ), 144.48
(C 11 ), 137.56 (C 5 ), 130.83 (C 10 ), 128.20 (C 12 , C 16 ),
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(ESI), m/Z: C 25 H 26 N 3 OS [M+H] 理论值 416.1788, 127.63 (C 25 , C 29 ), 125.24 (C 13 , C 15 , C 24 ), 116.72 (C 26 ,
测试值 416.1776。 C 28 ), 101.23 (C 22 ), 43.23 (C 1 ), 41.38 (C 3 ), 39.93 (C 7 ),
2-[6,6- 二甲 基 -3-(4- 硝基亚苄 基 ) 双环 [3.1.1] 32.72 (C 4 ), 28.80 (C 2 ), 22.10 (C 8 ), 21.76 (C 9 ); HRMS
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庚-2-亚基]肼基-4-苯基噻唑（Ⅲd）：黄色固体，产 (ESI), m/Z: C 25 H 25 N 4 O 3 S [M+H] 理论值 461.1642,
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率 80.4%，m.p. 206.1~207.9 ℃。 HNMR (400 MHz, 测试值 461.1642。
CDCl 3), δ: 12.73 (s, 1H, N—H), 8.23 (d, J=8.8 Hz, 2H, 2-{2-[3-(4- 氟 亚苄基 )-6,6- 二甲基双环 [3.1.1]
C 13 —H, C 15 —H), 7.75 (d, J=6.6 Hz, 2H, C 25 —H, 庚-2-亚基]肼基}-4-苯基噻唑（Ⅲg）：黄色固体，产
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C 29 —H), 7.64 (d, J=8.9 Hz, 2H, C 12 —H, C 16 —H), 率 74.7%，m.p. 194.8~195.6 ℃。 HNMR (400 MHz,
7.55 (s, 1H, C 22 —H), 7.45(dd, J=10.5、6.6 Hz, 3H, CDCl 3), δ: 12.56 (s, 1H, N—H), 7.68 (d, J=6.9 Hz, 2H,
C 26 —H, C 27 —H, C 28 —H), 6.78 (s, 1H, C 10 —H), C 12 —H, C 16 —H), 7.47~7.35 (m, 6H, C 13 —H, C 15 —H,
3.01~2.88 (m, 2H, C 1 —H, C 3—H), 2.65 (m, 1H, C 4—H), C 25 —H, C 29 —H, C 28 —H, C 22 —H), 7.34 (d, J=8.5 Hz,
2.27 (m, 2H, C 2—H), 1.54 (m, 1H, C 4—H), 0.94 (s, 6H, 2H, C 26 —H, C 28 —H), 6.76 (s, 1H, C 10 —H), 3.11~2.98
C 8 — H, C 9 — H); 13 CNMR (100 MHz, CDCl 3 ), δ: (m, 2H, C 1 —H, C 3 —H), 2.85 (m, 1H, C 4 —H), 2.60 (m,
169.89 (C 19 ), 165.12 (C 6 ), 146.67 (C 21 ), 143.09 (C 14 ), 2H, C 2 —H), 1.39 (m, 1H, C 4 —H), 0.91 (s, 6H, C 8 —H,
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141.21 (C 11 ), 135.45 (C 5 ), 130.91 (C 10 ), 130.02 (C 24 ), C 9 —H); CNMR (100 MHz, CDCl 3 ), δ: 169.49 (C 19 ),
128.79 (C 12 , C 16 ), 127.74 (C 26 , C 28 ), 126.09 (C 25 , C 29 , 165.52 (C 14 ), 162.41 (C 6 ), 140.71 (C 21 ), 134.48 (C 5 ),
C 27 ), 124.08 (C 13 , C 15 ), 101.23 (C 22 ), 44.90 (C 1 ), 42.73 131.42 (C 24 ), 130.49 (C 10 ), 129.73 (C 11 ), 129.68 (C 12 ,
(C 3 ), 39.57 (C 7 ), 32.25 (C 4 ), 28.24 (C 2 ), 22.32 (C 8 ), C 16 ), 128.82 (C 26 , C 28 ), 127.61 (C 25 , C 29 ), 125.73 (C 27),
22.00 (C 9 ); HRMS (ESI), m/Z: C 25 H 25 N 4 O 2 S [M+H] + 115.6 (C 13, C 15), 101.12 (C 22), 44.59 (C 1), 42.35 (C 3 ),
理论值 445.1701, 测试值 445.1696。 39.47 (C 7 ), 31.87 (C 4 ), 27.99 (C 2 ), 21.87 (C 8 ), 21.15
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2-{2-[6,6- 二甲基 -3-(4- 硝基苯 亚甲 基 ) 二环 (C 9 ); HRMS (ESI), m/Z: C 25 H 25 N 3 FS [M+H] 理论值
[3.1.1]庚-2-亚基]肼基}-4-(4-氟苯基)噻唑（Ⅲe）：黄 418.1751, 测试值 418.1753。
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色固体，产率 73.4%，m.p. 207.8~208.9 ℃。 HNMR 2-{2-[3-(4- 氟 亚苄基 )-6,6- 二甲基双环 [3.1.1]
(400 MHz, CDCl 3 ), δ: 12.60 (s, 1H, N—H), 8.23 (d, 庚-2-亚基]肼基}-4-(4-氟苯基)噻唑（Ⅲh）：黄色固
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J=8.8 Hz, 2H, C 13—H, C 15—H), 7.72 (d, J=8.5 Hz, 2H, 体，产率 71.4%，m.p. 196.2~196.9 ℃。 HNMR
C 25 —H, C 29 —H), 7.63 (d, J=8.8 Hz, 2H, C 12 —H, (400 MHz, CDCl 3 ), δ: 12.25 (s, 1H, N—H), 7.87 (d,
C 16 —H), 7.55 (s, 1H, C 22 —H), 7.15 (d, J=8.5 Hz, 2H, J=8.8 Hz, 2H, C 12 —H, C 16 —H), 7.64 (d, J=7.0 Hz, 2H,
C 26 —H, C 28 —H), 6.74 (s, 1H, C 10 —H), 2.99~2.84 (m, C 25 —H, C 29 —H), 7.51 (s, 1H, C 22 —H), 7.41 (d,
2H, C 1 —H, C 3 —H), 2.63 (m, 1H, C 4 —H), 2.26 (m, J=8.8 Hz, 2H, C 13—H, C 15—H), 7.35 (d, J=7.1 Hz, 2H,
2H, C 2 —H), 1.50 (m, 1H, C 4 —H), 0.93 (s, 6H, C 8 —H, C 26 —H, C 28 —H), 6.89 (s, 1H, C 10 —H), 3.06~2.86 (m,
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C 9 —H); CNMR (100 MHz, CDCl 3 ), δ: 169.86 (C 19 ), 2H, C 1 —H, C 3 —H), 2.78 (m, 1H, C 4 —H), 2.39 (m,
165.23 (C 27 ), 163.34 (C 6 ), 147.86 (C 21 ), 143.09 (C 14 ), 2H, C 2—H), 1.65 (m, 1H, C 4—H), 1.09 (s, 6H, C 8—H,
140.20 (C 11 ), 135.20 (C 5 ), 130.89 (C 10 ), 128.96 (C 25 , C 9 —H); CNMR (100 MHz, CDCl 3 ), δ: 169.74 (C 19 ),
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C 29 ), 128.23 (C 12 , C 16 , C 24 ), 124.09 (C 13 , C 15 ), 117.24
(C 26 , C 28 ), 101.30 (C 22 ), 44.85 (C 1 ), 42.75 (C 3 ), 39.56 166.28 (C 14 ), 164.68 (C 27 ), 162.21 (C 6 ), 140.05 (C 21 ),
(C 7 ), 32.23 (C 4 ), 28.34 (C 2 ), 21.35 (C 8 ), 21.05 (C 9 ); 132.89 (C 5 ), 132.27 (C 10 ), 132.23 (C 11 ), 130.68 (C 25 ,
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HRMS (ESI), m/Z: C 25 H 25 N 4 O 2 FS [M+H] 理论 值 C 29 ), 130.22 (C 12 , C 16 ), 128.17 (C 24 ), 117.28 (C 26 , C 28 ),
115.95 (C 13, C 15 ), 100.78 (C 22), 44.89 (C 1), 42.76 (C 3),
463.1734, 测试值 463.1708。 39.75 (C 7 ), 32.05 (C 4 ), 28.34 (C 2 ), 22.47 (C 8 ), 22.09
4-(2-{2-[6,6-二甲基-3-(4-硝基苯亚甲基)二环 (C 9 ); HRMS (ESI), m/Z: C 25 H 25 N 3 F 2 S [M+H] 理论值
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[3.1.1]庚-2-亚基]肼基}噻唑-4-基)苯酚（Ⅲf）：黄色 436.1661, 测试值 436.1668。