Potassium Carbonate → Tert-butyl 3-(4,6-bistrifluoromethylpyridin-2-yl)propylcarbamate

HRID 444793

反応式

HRID 444793 の反応式
[CH2:1]([NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[CH:2]=[CH2:3].C12BC(CCC1)CCC2.Br[C:22]1[CH:27]=[C:26]([C:28]([F:31])([F:30])[F:29])[CH:25]=[C:24]([C:32]([F:35])([F:34])[F:33])[N:23]=1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].O>[F:31][C:28]([F:29])([F:30])[C:26]1[CH:25]=[C:24]([C:32]([F:33])([F:34])[F:35])[N:23]=[C:22]([CH2:3][CH2:2][CH2:1][NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[CH:27]=1

参加物

10

反応物 4

HCID 11430Potassium CarbonateHCID 789669-Borabicyclo(3.3.1)nonaneHCID 4067274tert-butyl N-(prop-2-en-1-yl)carbamateHCID 85875928Pyridine, 2-bromo-4,6-bis(trifluoromethyl)-

生成物 1

HCID 86650694Tert-butyl 3-(4,6-bistrifluoromethylpyridin-2-yl)propylcarbamate収率 74%

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of tert-butyl allylcarbamate (1.95 g, 12.4 mmol) in THF (12 mL), 0.5 mol/L 9-borabicyclo[3.3.1]nonane (29.8 mL, 14.9 mmol) was added under argon atmosphere at room temperature. After stirred at room temperature for 4 h, a solution of 2-bromo-4,6-bistrifluoromethylpyridine (3.65 g, 12.4 mmol) in DMF (12 mL), Pd(OAc)2 (278 mg, 1.24 mmol), DPPF (859 mg, 1.55 mmol) and K2CO3 (2.92 g, 21.1 mmol) were added to the reaction mixture and stirred at room temperature for 7 h. To the reaction mixture, water was added and the crude product was extracted with EtOAc, washed with brine, dried over NaSO4 and the solvent was removed in vacuo. The crude product was purified by column chromatography (Hexane:EtOAc 10:1→2:1) to yield tert-butyl 3-(4,6-bistrifluoromethylpyridin-2-yl)propylcarbamate (3.41 g, 74%) as a colorless solid. 1H NMR (CDCl3, 400 MHz) δ 1.44 (9H, s), 1.96-2.03 (2H, m), 2.98-3.02 (2H, m), 3.20-3.25 (2H, m), 4.71 (1H, brs), 7.59 (1H, s), 7.72 (1H, s). CIMS (+) 373 [M+H]+.

後処理

  1. stirringstirred at room temperature for 7 h
  2. extractionthe crude product was extracted with EtOAc
  3. washwashed with brine
  4. dry with materialdried over NaSO4
  5. customthe solvent was removed in vacuo
  6. customThe crude product was purified by column chromatography (Hexane:EtOAc 10:1→2:1)

出典と根拠

ORDレコード
ord-a2417668deaa487fb23f75a774839b97
出典データセット
uspto-grants-2013_07
特許番号
US08476261B2

関連ノート

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