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

HRID 1463527Notes

Reaction equation

HRID 1463527 reaction equation
[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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-3f40930c4ba64dcabd4ebee7f3e52a2e
Source dataset
uspto-grants-1994_04
Patent number
US05300668

Reaction notes

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