반응 #52847

ord-4ce7c23667ed4c469af66e055671ecc8

반응 방정식

CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
Compound A9
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
Ethyl (E)-4-[2-(5,6-dihydro-5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-naphthalen-2-yl)ethenyl]-benzoate
c1ccsc1
thiophene
[Li][CH2]CCC
n-butyl lithium
[Li][c]1cccs1
lithiothiophene
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(c2cccs2)=CCC3(C)C)cc1
title compound
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(c2cccs2)=CCC3(C)C)cc1
Ethyl (E)-4-[2-(-5,5-dimethyl-8-(2-thienyl)-5,6-dihydronaphthalen-2-yl)ethenyl]-benzoate

반응 조건

온도
-78°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    workup.STIRRINGThe resulting solution was stirred at −78° C. to room temperature for 1 h
  2. 2
    workup.STIRRINGThe resulting mixture was stirred at room temperature for 10 min
  3. 3
    온도heated at 50° C. for 1 h
  4. 4
    기타The reaction was quenched by the addition of sat. aqueous NH4Cl
  5. 5
    추출The mixture was extracted with EtOAc (2×)
  6. 6
    세척washed with brine
  7. 7
    건조The organic phase was dried over Na2SO4
  8. 8
    농축concentrated in vacuo
  9. 9
    기타The crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes)

실험 절차

A solution of lithiothiophene was prepared by the addition of 0.10 g (0.095 mL, 1.2 mmol) of thiophene to a cold solution (−78° C.) of 0.61 g (0.90 mL, 1.4 mmol, 1.6 M in hexanes) of n-butyl lithium in 2.0 mL of tetrahydrofuran. The solution was stirred at −78° C. for 35 min and then a solution of 0.158 g (1.2 mmol) of zinc chloride in 2.0 mL of tetrahydrofuran was added. The resulting solution was stirred at −78° C. to room temperature for 1 h and then the organozinc was added via cannula to a mixture of 0.212 g (0.44 mmol) of ethyl (E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-l)ethenyl] benzoate (Compound A9) and 18 mg (0.016 mmol) of tetrakis(triphenylphosphine)palladium(0) in 2.0 mL of tetrahydrofuran. The resulting mixture was stirred at room temperature for 10 min and then heated at 50° C. for 1 h. The reaction was quenched by the addition of sat. aqueous NH4Cl. The mixture was extracted with EtOAc (2×), and washed with brine. The organic phase was dried over Na2SO4 and then concentrated in vacuo. The crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes) to afford the title compound as a solid.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US06855832B2uspto-grants-2005_02