تفاعل #1465

ord-833ae973b3214608bac2a8fbd227ff25

معادلة التفاعل

CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
ethyl(E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate
CCOC(=O)c1ccc(/C=C/c2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CCC3(C)C)cc1
ethyl (E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate
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-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-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

ظروف التفاعل

درجة الحرارة
-78°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  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
    درجة الحرارةheated at 50° C. for 1 h
  4. 4
    أخرىThe reaction was quenched by the addition of sat. aqueous NH4Cl
  5. 5
    استخلاصThe mixture was extracted with EtOAc (2×)
  6. 6
    غسيلwashed with brine
  7. 7
    تجفيفThe organic phase was dried over Na2SO4
  8. 8
    تركيزconcentrated in vacuo
  9. 9
    أخرىThe crude material product was purified by flash chromatography (silica, 15% ethyl acetate in hexanes)

الإجراء التجريبي

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, 1.6M 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-yl)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.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US05723666uspto-grants-1998_03