Potassium bis(trimethylsilyl)amide → Ethyl 2-(2,6-dimethoxyphenyl)acrylate

HRID 907463Notes

Reaction equation

HRID 907463 reaction equation
[CH3:1][Si]([N-][Si](C)(C)C)(C)C.[K+].[CH3:11][O:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[C:14]=1[C:21](=O)[C:22]([O:24][CH2:25][CH3:26])=[O:23]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1.C1(C)C=CC=CC=1>[CH3:11][O:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[C:14]=1[C:21](=[CH2:1])[C:22]([O:24][CH2:25][CH3:26])=[O:23]

Participants

6

Reactant 2

HCID 3251421Potassium bis(trimethylsilyl)amideHCID 22560922Ethyl (2,6-dimethoxyphenyl)(oxo)acetate

Product 1

HCID 57659400Ethyl 2-(2,6-dimethoxyphenyl)acrylateYield 81%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of methyltriphenylphosphonium bromide (61.1 g, 1.2 equiv) in THF (350 ml) at 0 C was added potassium bis(trimethylsilyl)amide (260 ml of a 15% solution in toluene, 1.2 equiv) and this mixture was stirred at 0 C for 15 min and at r.t. for 45 min. Then, a solution of the ketoester 16 (33.7 g, 141 mmol) in THF (70 ml) was added at 0 C and stirring was continued at r.t. for 1 h. The reaction was quenched by addition of a saturated solution of NH4Cl and ice. The product was extracted into i-PrOAc and the organics were dried over Na2SO4 and filtered through small pad of silica. Purification of the residue by filtration through a plug of silica (1.5 L) with EtOAc/hexane 10 and 15% yielded 26.92 g (81%) of 17 as a colorless oil.

Workup

  1. stirringstirring
  2. waitwas continued at r.t. for 1 h
  3. customThe reaction was quenched by addition of a saturated solution of NH4Cl and ice
  4. extractionThe product was extracted into i-PrOAc
  5. dry with materialthe organics were dried over Na2SO4
  6. filtrationfiltered through small pad of silica
  7. customPurification of the residue
  8. filtrationby filtration through a plug of silica (1.5 L) with EtOAc/hexane 10 and 15%

Sources & evidence

ORD record
ord-fc298509653040329f9e9dca2832bac6
Source dataset
uspto-grants-2011_09
Patent number
US08013159B2

Reaction notes

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