tert-Butyl 4-(2-(2,4-Difluorophenyl)acetyl)piperazine-1-carboxylate → tert-Butyl 4-(2,4-Difluorophenethyl)piperazine-1-carboxylate

HRID 56355

反応式

HRID 56355 の反応式
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH2:9][C:10]([N:12]1[CH2:17][CH2:16][N:15]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:13]1)=O>C1COCC1>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH2:9][CH2:10][N:12]1[CH2:13][CH2:14][N:15]([C:18]([O:20][C:21]([CH3:23])([CH3:24])[CH3:22])=[O:19])[CH2:16][CH2:17]1

参加物

3

反応物 1

HCID 46901912tert-Butyl 4-(2-(2,4-Difluorophenyl)acetyl)piperazine-1-carboxylate

生成物 1

HCID 46901913tert-Butyl 4-(2,4-Difluorophenethyl)piperazine-1-carboxylate収率 100.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
66 °C

実験手順

tert-Butyl 4-(2-(2,4-difluorophenyl)acetyl)piperazine-1-carboxylate (1.12 g, 3.30 mmol) was dissolved in THF (8.5 mL) and borane-tetrahydrofuran complex (1.0 M, 15.8 mL, 15.8 mmol) was added. The reaction was refluxed at 66° C. The reaction was quenched slowly with methanol (0.4 mL) dropwise. Then, 0.5 M HCl (10.0 mL) was added, and the mixture was extracted with EtOAc (2×100 mL). The organic extracts were dried over Na2SO4, filtered, and concentrated to give a residue that was purified by RP-HPLC. The best fractions were added to NaHCO3 (20 mL) and extracted with EtOAc (2×100 mL). The organic extracts were dried over Na2SO4, filtered, and concentrated to yield the title compound (1.08 g) as a white solid. 1H NMR (DMSO-d6, 400 MHz) δ 1.41 (s 9H), 2.80-2.96 (m, 6H), 3.10-3.03 (m, 2H), 3.50-3.60 (m, 4H), 7.06 (dt, J=2.6, 8.5 Hz, 1H), 7.22 (dt, J=2.6, 9.6 Hz, 1H), 7.38-7.46 (m, 1H). Exact mass calculated for C17H24F2N2O2: 326.2. Found: LCMS m/z=327.1 (M+H+).

後処理

  1. additionborane-tetrahydrofuran complex (1.0 M, 15.8 mL, 15.8 mmol) was added
  2. customThe reaction was quenched slowly with methanol (0.4 mL) dropwise
  3. additionThen, 0.5 M HCl (10.0 mL) was added
  4. extractionthe mixture was extracted with EtOAc (2×100 mL)
  5. dry with materialThe organic extracts were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a residue that
  9. customwas purified by RP-HPLC
  10. additionThe best fractions were added to NaHCO3 (20 mL)
  11. extractionextracted with EtOAc (2×100 mL)
  12. dry with materialThe organic extracts were dried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated

出典と根拠

ORDレコード
ord-df19997cd0e341599ca2a58275ad3f0a
出典データセット
uspto-grants-2016_09
特許番号
US09434692B2

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