Potassium Carbonate → ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

HRID 2214858ノート

反応式

HRID 2214858 の反応式
[CH:1]([C:3]1[CH:10]=[C:7]([CH:8]=O)[C:6]([OH:11])=[CH:5][CH:4]=1)=[O:2].[F:12][C:13]([F:22])([F:21])/[CH:14]=[CH:15]/[C:16]([O:18][CH2:19][CH3:20])=[O:17].C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[CH:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][CH:14]([C:13]([F:12])([F:22])[F:21])[C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:8][C:7]=2[CH:10]=1)=[O:2]

参加物

5

反応物 3

HCID 11430Potassium CarbonateHCID 1651064-HydroxyisophthalaldehydeHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoate2 回

生成物 1

HCID 21883688ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
60 °C

実験手順

A 50 mL round bottom flask was charged with 5-formylsalicylaldehyde (3.21 g, 21.39 mmol), ethyl 4,4,4-trifluorocrotonate (3.50 mL, 3.96 g, 23.53 mmol), dimethylformamide (15 mL) and potassium carbonate (2.95 g, 21.39 mmol) and heated to 60° C. for 12 hours. Additional ethyl 4,4,4-trifluorocrotonate (3.50 mL, 3.96 g, 23.53 mmol) was added and the reaction heated for 16 hours at 75° C. After cooling to room temperature, the reaction was partitioned between H2O and diethyl ether. The organic phase was washed with saturated NaHCO3 solution, KHSO4 solution (0.25 M), brine, treated with decolorizing carbon (warmed gently). The resulting black suspension was dried over MgSO4, vacuum filtered through diatomaceous earth, and concentrated in vacuo yielding an orange crystalline mass. This material was recrystallized from hot hexanes yielding the ester (1.51 g, 24%) as orange crystals: mp 84.3–86.2° C. 1H NMR (acetone-d6/300 MHz) 9.96 (s, 1H), 8.06 (d, 1H, J=2 Hz), 8.02 (s, 1H), 7.99 (dd, 1H, J=8.5, 2.0 Hz), 7.24 (d, 1H, J=8.5 Hz), 5.99 (q, 1H, J=7.1 Hz), 4.43–4.25 (m, 2H), 1.34 (t, 3H, J=7.3 Hz). FABLRMS m/z 301 (M+H). EIHRMS m/z 300.0605 (M+, Calc'd 300.0609). Anal. Calc'd for C14H11F3O4: C, 56.01; H, 3.69. Found: C, 56.11; H, 3.73.

後処理

  1. temperaturethe reaction heated for 16 hours at 75° C
  2. temperatureAfter cooling to room temperature
  3. customthe reaction was partitioned between H2O and diethyl ether
  4. washThe organic phase was washed with saturated NaHCO3 solution, KHSO4 solution (0.25 M), brine
  5. additiontreated with decolorizing carbon (
  6. temperaturewarmed gently)
  7. dry with materialThe resulting black suspension was dried over MgSO4, vacuum
  8. filtrationfiltered through diatomaceous earth
  9. concentrationconcentrated in vacuo
  10. customyielding an orange crystalline mass
  11. customThis material was recrystallized from hot hexanes yielding the ester (1.51 g, 24%) as orange crystals

出典と根拠

ORDレコード
ord-45524fabf623455e8f21f5978696aa42
出典データセット
uspto-grants-2006_09
特許番号
US07109211B2

反応ノート

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