Methanesulfonic Acid → 6-Benzyl4-trifluoromethylchromen-2-one

HRID 11799

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HRID 11799 반응식
[CH2:1]([C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:15]([C:19]([CH2:21][C:22](OCC)=[O:23])=O)([F:18])([F:17])[F:16].CS(O)(=O)=O>>[CH2:1]([C:8]1[CH:13]=[C:12]2[C:11](=[CH:10][CH:9]=1)[O:14][C:22](=[O:23])[CH:21]=[C:19]2[C:15]([F:18])([F:17])[F:16])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

참가 물질

4

반응물 3

HCID 6395Methanesulfonic AcidHCID 75634-BenzylphenolHCID 67793Ethyl 4,4,4-trifluoroacetoacetate

생성물 1

HCID 219767876-Benzyl4-trifluoromethylchromen-2-one수율 44.3%

반응 조건

온도
65 °C

실험 절차

A stirred suspension of 4-benzylphenol (4.67 g, 25.4 mmol), CF3COCH2CO2Et (7.00 g, 38.0 mmol), & MeSO3H (8.5 mL, 130.9 mmol) was heated at 65° C. for 9 h. On cooling, the mixture was partitioned between Et2O (200 mL) & H2O (50 mL), then the aqueous phase was basicified with 2 M NaOH. The organic layer was separated & washed with H2O & brine, before being dried (MgSO4). Filtration, solvent evaporation, & column chromatography (4:1 PE-Et2O) furnished 6-benzyl4-trifluoromethylchromen-2-one (3.42 g, 44%): δH (CDCl3)=4.10 (s, 2H), 6.85 (s, 1H), 7.20–7.40 (m, 5H), 7.45 (dd, 1H), 7.60 (d, 1H). This compound (2.00 g, 6.6 mmol) was dissolved in H2SO4 (20 mL), then the whole was stirred for 15 min. The mixture was carefully treated with crushed ice (80 g), then the resulting white precipitate was collected by filtration. The precipitate was air-dried, before being treated with hot THF (100 mL). After filtration, the filtrate was concentrated to yield 4-(2-oxo-4-trifluoromethyl-2H-chromen-6-ylmethyl)benzenesulfonic acid (2.20 g, 87%): δH ((CD3)2SO)=4.05 (s, 2H), 7.00 (s, 1H), 7.20 (d, 2H), 7.45 (d, 1H), 7.50–7.60 (m, 4H). This compound was reacted with (COCl)2, as described above in Preparation 1, to give a solid which was dissolved in EtOAc, before being filtered & concentrated to produce the title compound (2.30 g, 87%): Rf (2:1 PE-EtOAc)=0.60.

후처리

  1. temperatureOn cooling
  2. customthe mixture was partitioned between Et2O (200 mL) & H2O (50 mL)
  3. customThe organic layer was separated
  4. washwashed with H2O & brine
  5. dry with materialbefore being dried (MgSO4)
  6. filtrationFiltration, solvent evaporation, & column chromatography (4:1 PE-Et2O)

출처 및 근거

ORD 기록
ord-6250fc794fad4744874872c3b677d7df
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07098340B2

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