Isopropenyl acetate → HCID 20134188, compound

HRID 1295408Notes

Reaction equation

HRID 1295408 reaction equation
C[O-].C([Sn+](CCCC)CCCC)CCC.Br[C:17]1[CH:18]=[C:19]([CH:24]=[CH:25][CH:26]=1)[C:20]([O:22][CH3:23])=[O:21].C([O:30][C:31]([CH3:33])=[CH2:32])(=O)C.[F-].[K+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[CH3:23][O:22][C:20](=[O:21])[C:19]1[CH:24]=[CH:25][CH:26]=[C:17]([CH2:32][C:31](=[O:30])[CH3:33])[CH:18]=1

Participants

8

Reactant 4

HCID 7916Isopropenyl acetateHCID 12070Methyl 3-bromobenzoateHCID 522689Potassium FluorideHCID 11964040Methoxytri-n-butylstannane

Product 1

HCID 20134188HCID 20134188, compoundYield 94.6%

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent2×

Procedure

Tributyltin methoxide (80.3 mL, 279 mmol), methyl 3-bromobenzoate (53.5 g, 249 mmol), isopropenyl acetate (39.4 ml, 358 mmol), palladium(II)acetate (2.6 g, 11.6 mmol) and tri-ortho-tolylphosphine (7.1 g, 23.2 mmol) were stirred together in toluene (350 mL) at 100° C. under nitrogen for 18 hours. After cooling, the reaction was treated with potassium fluoride solution (4M, 560 ml) and stirred for 2 hours. The resulting mixture was diluted with further toluene (200 mL) and filtered through Celite®, washing the filter pad with ethyl acetate. The organic phase was separated, dried (sodium sulfate) and reduced in vacuo. The residue was purified by chromatography eluting with ethylacetate: pentane 10:90 to 20:80 to give the title compound (45.3 g) as an orange oil. 1H NMR (400 MHz, CDCl3) δ: 2.18 (3H, s), 3.75 (2H, s), 3.91 (3H, s), 7.43–7.37 (2H, m), 7.87 (1H, s), 7.95–7.93 (1H, d); LRMS ESI m/z 215 [M+Na]+, 191 [M−H]−.

Workup

  1. temperatureAfter cooling
  2. filtrationfiltered through Celite®
  3. washwashing the filter pad with ethyl acetate
  4. customThe organic phase was separated
  5. dry with materialdried (sodium sulfate)
  6. customThe residue was purified by chromatography
  7. washeluting with ethylacetate: pentane 10:90 to 20:80

Sources & evidence

ORD record
ord-d77a0c26faba43578b4fcc896e1979b6
Source dataset
uspto-grants-2007_07
Patent number
US07241810B2

Reaction notes

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