Potassium Carbonate → (2S)-3,3-dimethyl-1-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-2-butanol

HRID 1182302ノート

反応式

HRID 1182302 の反応式
[C:1]([C@H:5]1[CH2:9]OS(=O)(=O)[O:6]1)([CH3:4])([CH3:3])[CH3:2].[F:12][C:13]([F:20])([F:19])[C:14]1[CH:18]=[CH:17][NH:16][N:15]=1.C(=O)([O-])[O-].[K+].[K+].C(Cl)(=O)C.CO.C(=O)(O)[O-].[Na+]>CN(C)C=O>[CH3:2][C:1]([CH3:4])([CH3:3])[C@H:5]([OH:6])[CH2:9][N:16]1[CH:17]=[CH:18][C:14]([C:13]([F:20])([F:19])[F:12])=[N:15]1

参加物

7

反応物 5

HCID 11430Potassium CarbonateHCID 516892Sodium BicarbonateHCID 18070343-(Trifluoromethyl)pyrazoleHCID 22256297Acetyl chloride methanolHCID 58981698(4S)-4-tert-butyl-1,3,2-dioxathiolane 2,2-dioxide

生成物 1

HCID 69513260(2S)-3,3-dimethyl-1-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-2-butanol収率 56.2%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

To 999.9 mg (5.55 mmol) of (4S)-4-tert-butyl-1,3,2-dioxathiolane 2,2-dioxide in 18 mL of N,N-dimethylformamide was added 755.0 mg (5.55 mmol) of 3-(trifluoromethyl)-1H-pyrazole. Then, 805.2 mg (5.83 mmol) of potassium carbonate was added, and the mixture was heated at 100° C. for 22 h. The resulting solution was cooled and 20 mL of acetyl chloride:methanol (1:9) were added. The reaction mixture was stirred for 2 h, and then saturated aqueous sodium bicarbonate was added. The mixture was extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography eluting with an ethyl acetate:hexanes solution (1:4) to give 736.5 mg (56%) of (2S)-3,3-dimethyl-1-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-2-butanol and a small amount of the other regioisomer. Rf=0.23 (1:4 ethyl acetate:hexanes); 1H-NMR (300 MHz, DMSO-d6): δ 7.90 (s, 1H), 6.65 (d, J=2 Hz, 1H), 4.93 (br s, 1H), 4.30 (dd, J=14 Hz, J=2 Hz, 1H), 3.96 (dd, J=14 Hz, 10 Hz, 1H), 3.45 (d, J=10 Hz, 1H), 0.90 (s, 9H); ES-LCMS m/z 237 (M+H).

後処理

  1. temperatureThe resulting solution was cooled
  2. extractionThe mixture was extracted with ethyl acetate
  3. dry with materialthe extract was dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography
  7. washeluting with an ethyl acetate

出典と根拠

ORDレコード
ord-ac66a574e65b4126bb07754291f2a97d
出典データセット
uspto-grants-2007_10
特許番号
US07288541B2

反応ノート

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