Formaldehyde → Ethyl 4-methyl-2-methylenepentanoate

HRID 1109403Notes

Reaction equation

HRID 1109403 reaction equation
[Cl-].[Li+].C(OP([CH:11]([CH2:17][CH:18]([CH3:20])[CH3:19])[C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[CH2:21]1CCN2C(=NCCC2)CC1.C=O>C1COCC1.C(OCC)(=O)C>[CH2:17]([C:11](=[CH2:21])[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:18]([CH3:19])[CH3:20]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 433294Lithium ChlorideHCID 15234297Ethyl 2-diethylphosphono-4-methylpentanoate

Product 1

HCID 10909818Ethyl 4-methyl-2-methylenepentanoateYield 62.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

333 mg of lithium chloride was suspended in 14 ml of dry THF. Then, 2.0 g of ethyl 2-diethylphosphono-4-methylpentanoate was added thereto under stirring. Then, 1.41 g of DBU was added thereto in the form of a dry THF solution. Then, a suspension of 348 mg of paraformaldehyde in dry THF was added thereto. The mixture was stirred at room temperature overnight. The reaction solution was subjected to filtration, and the collected substance was washed with a small amount of benzene. The filtrate and the washing solution were put together and concentrated under reduced pressure. The syrup thereby obtained was dissolved in 60 ml of ethyl acetate. The ethyl acetate layer was washed with water and with a saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then, solvent was distilled off to obtain 700 mg of ethyl 2-isobutyl-2-propenoate as colorless oily substance.

Workup

  1. additionwas added
  2. stirringThe mixture was stirred at room temperature overnight
  3. filtrationThe reaction solution was subjected to filtration
  4. washthe collected substance was washed with a small amount of benzene
  5. concentrationconcentrated under reduced pressure
  6. customThe syrup thereby obtained
  7. washThe ethyl acetate layer was washed with water and with a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationThen, solvent was distilled off

Sources & evidence

ORD record
ord-fec9d60cf72a4a2e9540da5ea038f0b8
Source dataset
uspto-grants-1994_06
Patent number
US05319082

Reaction notes

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