반응 #69491

ord-b8646e3abb5748fea955e38591076796

반응 방정식

S
H2S
S=C=S
Carbon disulfide
O=S(=O)(O)O
H2SO4
COC(=O)c1cc(Br)c(O)c(C(C)=O)c1
methyl 3-acetyl-5-bromo-4-hydroxybenzoate
C[Si](C)(C)[N-][Si](C)(C)C.[Li+]
lithium bis(trimethylsilyl)amide
COC(=O)c1cc(Br)c2oc(=S)cc(O)c2c1
methyl 8-bromo-4-hydroxy-2-thioxo-2H-chromene-6-carboxylate
수율 63.5%

반응 조건

온도
-5°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    workup.STIRRINGthe mixture was stirred at room temperature overnight
  2. 2
    세척the THF layers was washed with water (2×350 mL)
  3. 3
    온도cooled to 0° C.
  4. 4
    기타equipped with a bleach trap
  5. 5
    기타formed
  6. 6
    workup.STIRRINGThe mixture was stirred at room temperature for 3 h
  7. 7
    workup.STIRRINGwas stirred at room temperature overnight
  8. 8
    추출The aqueous phase was extracted with DCM (2×)
  9. 9
    세척washed with brine
  10. 10
    건조dried over MgSO4
  11. 11
    여과filtered
  12. 12
    기타evaporated
  13. 13
    기타to afford an orange solid
  14. 14
    기타This solid was triturated in diethyl ether
  15. 15
    여과filtered
  16. 16
    기타dried

실험 절차

To a suspension of methyl 3-acetyl-5-bromo-4-hydroxybenzoate (70 g, 243.52 mmol) in THF (700 mL) at −50° C. under nitrogen (flask equipped with a bleach trap) was added lithium bis(trimethylsilyl)amide (828 ml, 828 mmol). The dark solution was allowed to warm to −5° C. and stirred for 2 h. Carbon disulfide (22 mL, 365 mmol) was added in one portion to the solution at −20° C. then the mixture was stirred at room temperature overnight. Water (700 mL) was added, the THF layers was washed with water (2×350 mL). The aqueous phases were combined and cooled to 0° C. and quenched with H2SO4 (108 ml, 1948 mmol) in a vessel equipped with a bleach trap to neutralize the H2S formed. The mixture was stirred at room temperature for 3 h, DCM was added (700 mL) and mixture was stirred at room temperature overnight. The aqueous phase was extracted with DCM (2×). The organic phases were combined, washed with brine, dried over MgSO4, filtered and evaporated to afford an orange solid. This solid was triturated in diethyl ether, filtered and dried to give methyl 8-bromo-4-hydroxy-2-thioxo-2H-chromene-6-carboxylate (48.7 g, 63%) as a yellow/orange solid. Mass Spectrum: m/z [M+H]+=317.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08530470B2uspto-grants-2013_09