Dimethyl Sulfoxide → (5-t-Butylthiophen-2-yl)-ethylene

HRID 1252463Notes

Reaction equation

HRID 1252463 reaction equation
[H-].[Na+].[C:3]([C:7]1[S:11][C:10]([CH:12]=O)=[CH:9][CH:8]=1)([CH3:6])([CH3:5])[CH3:4].O.[CH3:15]S(C)=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:3]([C:7]1[S:11][C:10]([CH:12]=[CH2:15])=[CH:9][CH:8]=1)([CH3:6])([CH3:5])[CH3:4]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 962WaterHCID 24758Sodium hydrideHCID 149549895-(Tert-butyl)thiophene-2-carbaldehyde

Product 1

HCID 20139963(5-t-Butylthiophen-2-yl)-ethyleneYield 25%

Reagents, catalysts & solvents 1

HCID 74505Methyltriphenyliphosphonium bromideCatalyst

Conditions

Temperature
15 °C

Procedure

Sodium hydride (6.05 g-50% suspension in oil, 0.126 mol) was washed with petroleum ether, suspended in dry DMSO (90 ml) and heated with stirring at 60°-70° C. for 2 hours. The reaction mixture was then cooled to 15° C. and methyltriphenylphosphonium bromide (44.5 g, 0.125 mmol) was added portionwise with rapid stirring over a 1/2 hour period. The reaction mixture was stirred at room temperature for a further 1 hour after the addition and 5-t-butyl-2-thiophenecarboxaldehyde (21.01 g, 0.125 mol) was added dropwise over a period of 1 hour. The resultant reaction mixture was stirred at room temperature for 12 hours, poured into water (300 ml) and extracted with ether (4×150 ml). The ethereal extracts were washed with water (4×100 ml) and dried over anhydrous sodium sulphate. Removal of the solvent gave a yellow oil which was purified by column chromatography (silica eluted with hexane) to give (5-t-butylthiophen-2-yl)-ethylene (5.25 g, 25%). Ethyl diazoacetate (4.69 g, 0.041 mol) in dry dichloromethane (80 ml) was added dropwise to a solution of (5-t-butylthiophen-2-yl)-ethylene (5.1 g, 0.031 mol) and anhydrous copper (II) sulphate (0.3 g) in dry dichloromethane (20 ml) at 90° C. by means of a syringe pump over a period of 5 hours. The dichloromethane was distilled over during the addition. After complete addition the remaining dichloromethane was removed in vacuo and the resulting brown oil purified by column chromatography (silica eluted with petroleum ether/ethyl acetate 19:1) to give ethyl 2-(5-t-butylthiophen-2-yl)-cyclopropanecarboxylate (4.72 g, 60%).

Workup

  1. temperatureheated
  2. stirringwith rapid stirring over a 1/2 hour period
  3. stirringThe reaction mixture was stirred at room temperature for a further 1 hour
  4. additionwas added dropwise over a period of 1 hour
  5. customThe resultant reaction mixture
  6. stirringwas stirred at room temperature for 12 hours
  7. extractionextracted with ether (4×150 ml)
  8. washThe ethereal extracts were washed with water (4×100 ml)
  9. dry with materialdried over anhydrous sodium sulphate
  10. customRemoval of the solvent
  11. customgave a yellow oil which
  12. customwas purified by column chromatography (silica eluted with hexane)

Sources & evidence

ORD record
ord-7c30d443474846ada021a5ef0a13720c
Source dataset
uspto-grants-1988_05
Patent number
US04743602

Reaction notes

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