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

HRID 854927노트

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HRID 854927 반응식
[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]

참가 물질

5

반응물 3

HCID 11430Potassium CarbonateHCID 1651064-HydroxyisophthalaldehydeHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoate2회

생성물 1

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

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

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온도
60 °C

실험 절차

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 (warming 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.

후처리

  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. temperaturewarming 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

출처 및 근거

ORD 기록
ord-ccd8df94bbe2420e85323bab75fd4d4e
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07259266B2

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