Butylimidazole → 2-[4-(2-chloro-4-fluoro-phenyl)-4H-[1,2,4]triazol-3-yl]-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene-9-carbonitrile

HRID 84639

反応式

HRID 84639 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][C:11]3[CH:10]=[C:9]([C:15]4[N:19]([C:20]5[CH:25]=[CH:24][C:23]([F:26])=[CH:22][C:21]=5[Cl:27])[CH:18]=[N:17][N:16]=4)[S:8][C:7]=3[C:6]=2[CH:28]=1.[CH2:29]([N:33]1C=CN=C1)CCC>[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[K+].[K+].[K+].[K+].[Fe+2].[Cu]I.C1(C)C=CC=CC=1>[Cl:27][C:21]1[CH:22]=[C:23]([F:26])[CH:24]=[CH:25][C:20]=1[N:19]1[CH:18]=[N:17][N:16]=[C:15]1[C:9]1[S:8][C:7]2[C:6]3[CH:28]=[C:2]([C:29]#[N:33])[CH:3]=[CH:4][C:5]=3[O:14][CH2:13][CH2:12][C:11]=2[CH:10]=1

参加物

6

反応物 2

HCID 61347ButylimidazoleHCID 579004223-(9-bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulen-2-yl)-4-(2-chloro-4-fluoro-phenyl)-4H-[1,2,4]triazole

生成物 1

HCID 579003482-[4-(2-chloro-4-fluoro-phenyl)-4H-[1,2,4]triazol-3-yl]-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene-9-carbonitrile収率 30.3%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 9605257Potassium Ferrocyanide触媒HCID 1140Toluene溶媒

反応条件

温度
160 °C

実験手順

A microwave tube was charged with 3-(9-bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulen-2-yl)-4-(2-chloro-4-fluoro-phenyl)-4H-[1,2,4]triazole (0.57 g; 1.2 mmol), K4[Fe(CN)6](101 mg; 0.24 mmol), CuI (23 mg; 0.12 mmol), 1-butylimidazole (0.32 ml; 2.4 mmol) and toluene (5 ml). The mixture was flushed with argon and heated in a microwave at 160° C. for 4 h. LCMS shows approx. 40% conversion so the same amount of K4[Fe(CN)6], CuI and 1-butylimidazole was added again and reaction mixture heated in a microwave at 170° C. for a further 4 h. The reaction mixture was partitioned between CH2Cl2 and water, the organic layer was dried (Na2SO4) and purified by ISCO then prep. LCMS to give 355 as a white solid (154 mg; 30%). δH (400 MHz, CDCl3) 3.19 (t, J=5.2, 2H), 4.36 (t, J=5.2, 2H), 7.08-7.11 (m, 2H), 7.23-7.32 (m, 1H), 7.43-7.52 (m, 3H), 7.81 (d, J=2.0, 1H), 8.23 (s, 1H). [M+H]+: 423

後処理

  1. customThe mixture was flushed with argon
  2. additionwas added again
  3. customreaction mixture
  4. temperatureheated in a microwave at 170° C. for a further 4 h
  5. customThe reaction mixture was partitioned between CH2Cl2 and water
  6. dry with materialthe organic layer was dried (Na2SO4)
  7. custompurified by ISCO

出典と根拠

ORDレコード
ord-26045010ecb44c9fb57f55421d3c6532
出典データセット
uspto-grants-2014_09
特許番号
US08846762B2

関連ノート

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