Toluene → 6-chloro-4-hydroxy-3-methyl-2H-chromen-2-one

HRID 495139

반응식

HRID 495139 반응식
C(O[C:4](=[O:8])[O:5][CH2:6][CH3:7])C.[H-].[Na+].[Cl:11][C:12]1[CH:13]=CC(O)=[C:16](C(=O)CC)[CH:17]=1.[OH-:23].[Na+].[C:25]1([CH3:31])C=CC=C[CH:26]=1>>[Cl:11][C:12]1[CH:17]=[CH:16][C:6]2[O:5][C:4](=[O:8])[C:25]([CH3:31])=[C:26]([OH:23])[C:7]=2[CH:13]=1

참가 물질

6

반응물 5

HCID 1140Toluene2회HCID 7766Diethyl CarbonateHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 2921145'-Chloro-2'-hydroxypropiophenone

생성물 1

HCID 546855586-chloro-4-hydroxy-3-methyl-2H-chromen-2-one수율 37%

실험 절차

Diethylcarbonate (27.2 mmol, 3.3 mL) is dissolved in 30 mL toluene, and NaH (16.3 mmol, 0.65 g of 60% dispersion) is added in portions. 5′-chloro-2′-hydroxy-propiophenone (5.4 mmol, 1.0 g) in 10 mL is dissolved in toluene and is added dropwise via an addition funnel to the above solution. The cloudy yellow-green mixture is heated to near reflux for 20 hrs then is cooled to ambient temperature. 1N NaOH (50 mL) is added and the mixture stirred at ambient temperature for 60 hrs. The layers are separated and the organic layer is washed with H2O. The combined aqueous layers are washed with Et2O and the aqueous layer then acidified to pH 2 with conc. HCl. The resulting off-white precipitate is filtered, is washed with Et2O, and is dried to afford the title compound (0.417 g, 37%). A second crop is obtained by refrigerating the filtrate (0.442 g, 39%). 1H NMR (DMSO-d6, 300 MHz) δ 11.50 (1H, br s), 7.88 (1H, d, J=2.5 Hz), 7.61 (1H, dd, J=2.62, 8.87 Hz), 7.40 (1H, d, J=8.87 Hz), 2.00 (3H, s); MS (ESI, Pos.) calcd for C10H7ClO3 ml/z [M+H]=211.0, found 210.9.

후처리

  1. additionis added dropwise via an addition funnel to the above solution
  2. temperatureThe cloudy yellow-green mixture is heated
  3. temperatureto near reflux for 20 hrs
  4. customThe layers are separated
  5. washthe organic layer is washed with H2O
  6. washThe combined aqueous layers are washed with Et2O
  7. filtrationThe resulting off-white precipitate is filtered
  8. washis washed with Et2O
  9. customis dried

출처 및 근거

ORD 기록
ord-43ec0c66bc6f4ebcb684363eb2b9220b
출처 데이터셋
uspto-grants-2009_05
특허 번호
US07538233B2

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