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1,4-Dichloro-cis-2-butene → Methyl 1-(4'-t-butyldimethylsilyloxymethylphenyl)-2-vinylcyclopropane-1-carboxylate

HRID 1463527
ノート
印刷プレビュー

反応式

HRID 1463527 の反応式
[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][C:17]([O:19][CH3:20])=[O:18])=[CH:12][CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CC(C)([O-])C.[K+].Cl[CH2:28]/[CH:29]=[CH:30]\[CH2:31]Cl>C1COCC1>[Si:1]([O:8][CH2:9][C:10]1[CH:11]=[CH:12][C:13]([C:16]2([C:17]([O:19][CH3:20])=[O:18])[CH2:31][CH:30]2[CH:29]=[CH2:28])=[CH:14][CH:15]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 64321151,4-Dichloro-cis-2-buteneHCID 19090692Methyl[4-({[tert-butyl(dimethyl)silyl]oxy}methyl)phenyl]acetateHCID 23665647Potassium tert-butoxide2 回

生成物 1

HCID 19090698Methyl 1-(4'-t-butyldimethylsilyloxymethylphenyl)-2-vinylcyclopropane-1-carboxylate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a solution of the product of Step 1, above, (1.0 g, 3.4 mmol) in 10 ml THF at -20° C. was added a 1M solution of potassium t-butoxide in THF (3.73 ml, 3.73 mmol) over 15 minutes. After 30 minutes at -20° C., cis-1,4-dichlorobut-2-ene (0.393 ml, 3.73 mmol) was added dropwise and the reaction was warmed to room temperature. After 20 minutes the reaction was cooled to -20° C. and treated with potassium t-butoxide in THF (3.73 ml, 3.73 mmol). The reaction was allowed to warm to room temperature, then was heated at 50° C. for 30 minutes and quenched with saturated ammonium chloride solution. The solvents were removed in vacuo and the residue was taken up in ethyl acetate and washed with water. The organic layer was washed with saturated sodium chloride solution and dried over magnesium sulfate. After filtration, evaporation and gravity silica gel chromatography (SGC) with 2% ethyl acetate in petroleum ether as eluant, a mixture of the title compound and methyl 1-(4'-t-butyldimethylsilyloxymethylphenyl)-2-vinylcyclopropane-1-carboxylate (7:1 ratio, total 708 mg) was obtained as an oil. Since the two compounds were inseparable, the mixture was taken on.

後処理

  1. temperatureAfter 20 minutes the reaction was cooled to -20° C.
  2. temperatureto warm to room temperature
  3. temperaturewas heated at 50° C. for 30 minutes
  4. customquenched with saturated ammonium chloride solution
  5. customThe solvents were removed in vacuo
  6. washwashed with water
  7. washThe organic layer was washed with saturated sodium chloride solution
  8. dry with materialdried over magnesium sulfate
  9. filtrationAfter filtration, evaporation and gravity silica gel chromatography (SGC) with 2% ethyl acetate in petroleum ether as eluant
  10. additiona mixture of the title compound

出典と根拠

ORDレコード
ord-3f40930c4ba64dcabd4ebee7f3e52a2e
出典データセット
uspto-grants-1994_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05300668

反応ノート

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