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

HRID 11799

反応式

HRID 11799 の反応式
[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

参加物

4

反応物 3

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

生成物 1

HCID 219767876-Benzyl4-trifluoromethylchromen-2-one収率 44.3%

反応条件

温度
65 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-6250fc794fad4744874872c3b677d7df
出典データセット
uspto-grants-2006_08
特許番号
US07098340B2

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