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p-Toluenesulfonic acid → 4-(4-Chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6-dihydropyrazolo[3,4-e][1,4]thiazepine

HRID 1748800
ノート
印刷プレビュー

反応式

HRID 1748800 の反応式
[CH3:1][N:2]1[C:6]([NH2:7])=[CH:5][C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)=[N:3]1.[Cl:14][C:15]1[CH:22]=[CH:21][C:18]([CH:19]=O)=[C:17]([CH3:23])[CH:16]=1.[SH:24][CH2:25][C:26](=O)[CH3:27].C1(C)C=CC(S(O)(=O)=O)=CC=1>C(#N)C>[Cl:14][C:15]1[CH:22]=[CH:21][C:18]([CH:19]2[S:24][CH2:25][C:26]([CH3:27])=[N:7][C:6]3[N:2]([CH3:1])[N:3]=[C:4]([C:8]4[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=4)[C:5]2=3)=[C:17]([CH3:23])[CH:16]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 6101p-Toluenesulfonic acidHCID 5201441-Mercapto-2-propanoneHCID 27576584-Chloro-2-methylbenzaldehydeHCID 133248371-Methyl-3-Pyridin-2-Yl-1H-Pyrazol-5-Amine

生成物 1

HCID 867241284-(4-Chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6-dihydropyrazolo[3,4-e][1,4]thiazepine収率 76.4%

試薬・触媒・溶媒 1

HCID 6342
Acetonitrile
溶媒

反応条件

温度
150 °C

実験手順

A mixture of 1-methyl-3-(2-pyridyl)pyrazol-5-amine (0.215 g, 1.23 mmol), 4-chloro-2-methyl-benzaldehyde (0.1906 g, 1.23 mmol, Fluorochem), 1-sulfanylpropan-2-one (0.45 g, 4.93 mmol, Enamine), and p-toluenesulfonic acid (0.070 g, 0.37 mmol) in acetonitrile (3 mL) was heated, in a sealed microwave vessel, for about 30 min, at about 150° C., in a microwave. After cooling to rt the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (70 mL) and methanol (10 mL), and washed with 5% aqueous sodium bicarbonate (20 mL). The aqueous layer was extracted with ethyl acetate (20 mL). The combined organic layers were washed with water (40 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:4) to afford 4-(4-chloro-2-methyl-phenyl)-1,7-dimethyl-3-(2-pyridyl)-4,6-dihydropyrazolo[3,4-e][1,4]thiazepine (0.36 g, 0.94 mmol, 76%), as a yellow oil: LC-MS (Table 1, Method a) Rt=5.41 min, m/z 383 (M+H)+; 1H-NMR (CDCl3, Bruker 400 MHz) δ 2.36 (3H, s) 2.60 (3H, s) 3.16 (1H, d, J=16.3 Hz) 3.29 (1H, dd, J=16.3, 1.5 Hz) 4.03 (3H, s) 6.50 (1H, d, J=8.2 Hz) 6.60 (1H, d, J=1.5 Hz) 6.88 (1H, dd, J=8.2, 2.1 Hz) 7.01 (1H, ddd, J=7.4, 4.9, 1.1 Hz) 7.16 (1H, d, J=2.1 Hz) 7.56 (1H, td, J=7.8, 1.7 Hz) 7.86 (1H, dt, J=8.1, 1.0 Hz) 8.35 (1H, ddd, J=4.8, 1.8, 0.8 Hz).

後処理

  1. temperatureAfter cooling to rt the mixture
  2. concentrationwas concentrated under reduced pressure
  3. dissolutionThe residue was dissolved in ethyl acetate (70 mL)
  4. washmethanol (10 mL), and washed with 5% aqueous sodium bicarbonate (20 mL)
  5. extractionThe aqueous layer was extracted with ethyl acetate (20 mL)
  6. washThe combined organic layers were washed with water (40 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:4)

出典と根拠

ORDレコード
ord-61164e3bd8d241508b8c724eaa0e1b7d
出典データセット
uspto-grants-2015_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09150592B2

反応ノート

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