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

HRID 1685657

반응식

HRID 1685657 반응식
[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

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 6101p-Toluenesulfonic acid촉매HCID 6344Dichloromethane용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-3cf3969f6612445f939ea33d45dd3a37
출처 데이터셋
uspto-grants-2012_04
특허 번호
US08148415B2

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