3,4-dihydro-2H-pyran → Methyl 4-bromo-3-(tetrahydropyran-2-yloxy)benzoate

HRID 1685657

反応式

HRID 1685657 の反応式
[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[OH:12].[O:13]1[CH:18]=[CH:17][CH2:16][CH2:15][CH2:14]1>C(Cl)Cl.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Br:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[O:12][CH:14]1[CH2:15][CH2:16][CH2:17][CH2:18][O:13]1

参加物

5

反応物 2

HCID 80803,4-dihydro-2H-pyranHCID 6425184Methyl 4-Bromo-3-hydroxybenzoate

生成物 1

HCID 16747841Methyl 4-bromo-3-(tetrahydropyran-2-yloxy)benzoate収率 76%

試薬・触媒・溶媒 2

HCID 6101p-Toluenesulfonic acid触媒HCID 6344Dichloromethane溶媒

実験手順

The title compound was prepared by adapting the method reported by Kita et al.[Kita, 1994] To a solution of methyl 4-bromo-3-hydroxybenzoate (4.0 g, 17.31 mmol) in anhydrous CH2Cl2 (30 mL) was added 3,4-dihydro-2H-pyran (3.95 mL, 43.28 mmol) and p-toluenesulfonic acid (0.01 g, 0.17 mmol) at 0° C. The mixture was stirred at this temperature for 90 min, warmed to room temperature and quenched with saturated NaHCO3 solution (50 mL). The organic layer was separated, dried (Na2SO4) and concentrated in vacuo. The pale yellow residue was purified by flash column chromatography [SiO2, Et2O/n-hexane (4:6)] affording a colourless oil. The oil solidified on standing at room temperature to give methyl 4-bromo-3-(tetrahydropyran-2-yloxy)benzoate as colourless needles (4.12 g, 76%); δH (270 MHz, CDCl3) 1.59-1.77 (m, 3H), 1.86-2.13 (m, 3H), 3.6-3.64 (m, 1H), 3.8-3.85 (m, 1H), 3.88 (s, 3H), 5.6-5.62 (m, 1H), 7.52 (dd, J=8.2, 1.7, 1H), 7.59 (d, J=8.4, 1H), 7.76 (d, J=2.0, 1H); LRMS (FAB+) m/z (rel. intensity) 316.9 (30, [C13H1581BrO4+H]), 314.9 (47, [C13H1579BrO4+H]; LC-MS (APCI+):tR=1.48 min, m/z 334.13 (C13H1581BrO4+H3O+), 332.11 (C13H1579BrO4+H3O+); HPLC: tR=3.21 min (98%); HRMS (FAB+) Found 317.02290; C13H1681BrO4 requires 317.02115.

後処理

  1. customThe title compound was prepared
  2. customquenched with saturated NaHCO3 solution (50 mL)
  3. customThe organic layer was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThe pale yellow residue was purified by flash column chromatography [SiO2, Et2O/n-hexane (4:6)]
  7. customaffording a colourless oil
  8. customon standing at room temperature

出典と根拠

ORDレコード
ord-3cf3969f6612445f939ea33d45dd3a37
出典データセット
uspto-grants-2012_04
特許番号
US08148415B2

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