Butyl vinyl ether → 1-(4-Chloro-2-methoxyphenyl)ethan-1-one

HRID 272678Notes

Reaction equation

HRID 272678 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[C:4]([O:9][CH3:10])[CH:3]=1.C(N(CC)CC)C.[CH:18]([O:20]CCCC)=[CH2:19]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:18](=[O:20])[CH3:19])=[C:4]([O:9][CH3:10])[CH:3]=1

Participants

7

Reactant 3

HCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 160792304-Chloro-1-iodo-2-methoxybenzene

Product 1

HCID 194294681-(4-Chloro-2-methoxyphenyl)ethan-1-oneYield 65%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A solution of Example 59A (2.68 g, 10 mmol) in DMF (40 mL) was treated with triethylamine (1.53 mL, 11 mmol), n-butyl vinyl ether (6.5 mL, 50 mmol), DPPF (554 mg, 1 mmol) and Pd(OAc)2 (112 mg, 0.5 mmol), purged with nitrogen, heated to 80° C. for 6 hours, cooled to room temperature, and partitioned between ethyl acetate and water. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with water and brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate to provide 1.20 g (65%) of the desired product. MS (ESI) m/e 185 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 7.60 (d, J=8.14 Hz, 1H), 7.27 (d, J=1.70 Hz, 1H), 7.09 (dd, J=8.31, 1.86 Hz, 1H), 3.92 (s, 3H).

Workup

  1. custompurged with nitrogen
  2. temperaturecooled to room temperature
  3. custompartitioned between ethyl acetate and water
  4. extractionThe aqueous layer was extracted with ethyl acetate
  5. washthe combined organic layers were washed with water and brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-e8602a0c38a644c68b43f7f62fb8f50e
Source dataset
uspto-grants-2008_11
Patent number
US07456169B2

Reaction notes

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