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

HRID 1252469Notes

Reaction equation

HRID 1252469 reaction equation
[H-].[Na+].[C:3]([C:7]1[O: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[O: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 136961955-tert-Butylfuran-2-carbaldehyde

Product 1

HCID 20139961(5-t-Butylfuran-2-yl)-ethyleneYield 50%

Reagents, catalysts & solvents 1

HCID 74505Methyltriphenyliphosphonium bromideCatalyst

Conditions

Temperature
15 °C

Procedure

Sodium hydride (7.09 g-50% suspension in oil, 0.148 mol) was washed with petroleum ether, suspended in dry DMSO (100 ml) and heated with stirring at 60°-70° C. for 2 hours. The reaction mixture was then cooled to 15° C. and methyltriphenylphosphonium bromide (52.74 g, 0.136 mol) 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-furancarboxaldehyde (22.46 g, 0.148 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 petroleum ether) to give (5-t-butylfuran-2-yl)-ethylene (11.03 g, 50%). Ethyl diazoacetate (4.45 g, 0.039 mol) in dry dichloromethane (70 ml) was added dropwise to a solution of (5-t-butylfuran-2-yl)-ethylene (5.85 g, 0.039 mol) and anhydrous copper (II) sulphate (0.3 g) in dry dichloromethane (30 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 9:1) to give ethyl 2-(5-t-butylfuran-2-yl)-cyclopropanecarboxylate (2.1 g, 23%).

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 petroleum ether)

Sources & evidence

ORD record
ord-ebfb908823b74ee4ab75d46ac1f37dd7
Source dataset
uspto-grants-1988_05
Patent number
US04743602

Reaction notes

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