반응 #76285

ord-a5b93d68da6448919b73cc4727d101dc

반응 방정식

O=C(O)c1ccc(Br)cc1Cl
4-bromo-2-chlorobenzoic acid
O=C(O)c1ccc(Br)cc1Cl
4-Bromo-2-chlorobenzoic Acid
COc1cc(O)cc(OC)c1
3,5-dimethoxyphenol
O=C([O-])[O-].[K+].[K+]
potassium carbonate
Cl
hydrochloric acid
O=C1Cc2cc(Br)ccc2Oc2cc(O)cc(O)c21
desired compound ( 20 )
수율 62.6%
O=C1Cc2cc(Br)ccc2Oc2cc(O)cc(O)c21
2-Bromo-7,9-dihydroxy-10,11-dihydrodibenz[b,f]oxepin-10-one
수율 62.6%

반응 조건

온도
120°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    건조the resulting solution was dried by a Dean-Stark water separator (140-170° C.) for three hours
  2. 2
    온도This reaction mixture was cooled
  3. 3
    여과filtered
  4. 4
    기타The organic layer was separated
  5. 5
    세척thoroughly washed with water
  6. 6
    건조The resulting solution was dried with anhydrous magnesium sulfate
  7. 7
    농축concentrated
  8. 8
    기타the residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:hexane=1:3)
  9. 9
    기타recrystallized from ethyl acetate-hexane

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).

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US06700013B2uspto-grants-2004_03