Hydrochloric Acid → 2-Bromo-7,9-dihydroxy-10,11-dihydrodibenz[b,f]oxepin-10-one

HRID 48007

반응식

HRID 48007 반응식
[Br:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](O)=[O:7])=[C:4](Cl)[CH:3]=1.C[O:13][C:14]1[CH:15]=[C:16]([OH:22])[CH:17]=[C:18]([O:20][CH3:21])[CH:19]=1.C(=O)([O-])[O-].[K+].[K+].Cl>[Cu].[Cu]I.C(OCC)(=O)C.C1C=CC=CC=1.CN1CCCC1=O>[Br:1][C:2]1[CH:10]=[CH:9][C:21]2[O:20][C:18]3[CH:19]=[C:14]([OH:13])[CH:15]=[C:16]([OH:22])[C:17]=3[C:6](=[O:7])[CH2:5][C:4]=2[CH:3]=1

참가 물질

10

반응물 4

HCID 313Hydrochloric AcidHCID 103833,5-DimethoxyphenolHCID 11430Potassium CarbonateHCID 1088294-Bromo-2-chlorobenzoic acid

생성물 1

HCID 234318462-Bromo-7,9-dihydroxy-10,11-dihydrodibenz[b,f]oxepin-10-one수율 62.6%

시약·촉매·용매 5

HCID 23978Copper촉매HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 241Benzene용매HCID 8857Ethyl Acetate용매HCID 13387N-methyl-2-pyrrolidone용매

반응 조건

온도
120 °C

실험 절차

To a mixture of 88.3 g (F.W. 235.46, 375 mmol) of 4-bromo-2-chlorobenzoic acid (3), 57.8 g (F.W. 154.165, 375 mmol) of 3,5-dimethoxyphenol (13), 93.2 g (F.W. 138.21, 670 mmol) of potassium carbonate and 400 mL of N-methyl-2-pyrrolidone was added benzene (200 mL), and the resulting solution was dried by a Dean-Stark water separator (140-170° C.) for three hours and then, 6.0 g (F.W. 63.55, 93.7 mmol) of copper (powder) and 17.8 g (F.W. 190.45, 93.7 mmol) of copper (I) iodide were added thereto and stirred at 120° C. for 30 minutes. This reaction mixture was cooled by standing and ice water and ethyl acetate were added thereto and then, the obtained solution was made pH 2 with concentrated hydrochloric acid and filtered. The organic layer was separated and then, thoroughly washed with water and subjected to salting out with a saturated sodium chloride aqueous solution. The resulting solution was dried with anhydrous magnesium sulfate and concentrated and the residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:hexane=1:3) and recrystallized from ethyl acetate-hexane to obtain 75.4 g (57%) a desired compound (20). (TLC; ethyl acetate:hexane=1:2 or 1:1).

후처리

  1. dry with materialthe resulting solution was dried by a Dean-Stark water separator (140-170° C.) for three hours
  2. temperatureThis reaction mixture was cooled
  3. filtrationfiltered
  4. customThe organic layer was separated
  5. washthoroughly washed with water
  6. dry with materialThe resulting solution was dried with anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customthe residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:hexane=1:3)
  9. customrecrystallized from ethyl acetate-hexane

출처 및 근거

ORD 기록
ord-a5b93d68da6448919b73cc4727d101dc
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06700013B2

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