Thiophene → Methyl 5,5-dimethyl-5,6-dihydro-8-(2-thienyl)-2-naphthalenecarboxylate

HRID 1391

反応式

HRID 1391 の反応式
[S:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.C([Li])CCC.[CH3:11][C:12]1([CH3:34])[CH2:21][CH:20]=[C:19](OS(C(F)(F)F)(=O)=O)[C:18]2[CH:17]=[C:16]([C:30]([O:32][CH3:33])=[O:31])[CH:15]=[CH:14][C:13]1=2>C1COCC1.[Cl-].[Cl-].[Zn+2]>[CH3:11][C:12]1([CH3:34])[CH2:21][CH:20]=[C:19]([C:2]2[S:1][CH:5]=[CH:4][CH:3]=2)[C:18]2[CH:17]=[C:16]([C:30]([O:32][CH3:33])=[O:31])[CH:15]=[CH:14][C:13]1=2

参加物

6

反応物 3

HCID 8030ThiopheneHCID 10570750Methyl 5,5-dimethyl-5,6-dihydro-8-(trifluoromethylsulfonyl)oxy-naphthalene-2-carboxylate2 回HCID 178418339Butyllithium

生成物 1

HCID 10494326Methyl 5,5-dimethyl-5,6-dihydro-8-(2-thienyl)-2-naphthalenecarboxylate

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

(Compound E5) To a solution of 329.0 mg (3.93 mmol) of thiophene in 2.0 mL THF at 0° C. was added 251.8 mg (3.93 mmol, 1.56 mL of 2.5M solution in hexanes) of n-butyllithium. After stirring for 3 h at 0° C., a solution of 845.0 mg (6.28 mmol) of ZnCl2 in 5.0 mL THF was added and the resulting solution stirred for 30 minutes. This solution was added to a second flask containing 570.0 mg (1.57 mmol) of methyl 5,5-dimethyl-5,6-dihydro-8-(trifluoromethylsulfonyl)oxy-naphthalene-2-carboxylate (Compound E4) and 76.0 mg (0.063 mmol) of tetrakis(triphenyphosphine)palladium(0) in 4.0 mL THF, and the resulting solution was heated to 50° C. for 3 h. Upon cooling to room temperature the reaction was quenched by the addition of saturated aqueous NH4Cl. Extraction with EtOAc was followed by washing of the combined organic layers with H2O and saturated aqueous NaCl, and drying over MgSO4. The dry solution was concentrated under reduced pressure and the title compound was isolated from the residue as a yellow oil by column chromatography (5-10% EtOAc/hexanes).

後処理

  1. stirringthe resulting solution stirred for 30 minutes
  2. additionThis solution was added to a second flask
  3. temperaturethe resulting solution was heated to 50° C. for 3 h
  4. temperatureUpon cooling to room temperature the reaction
  5. customwas quenched by the addition of saturated aqueous NH4Cl
  6. extractionExtraction with EtOAc
  7. washby washing of the combined organic layers with H2O and saturated aqueous NaCl
  8. dry with materialdrying over MgSO4
  9. concentrationThe dry solution was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-d9c61c395e2c4475a549c72777a848f0
出典データセット
uspto-grants-1998_03
特許番号
US05723666

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