Ethyl Acetate → Methyl 4-(2-tert-butoxy-2-oxoethyl)-2-chlorobenzoate

HRID 1469145Notes

Reaction equation

HRID 1469145 reaction equation
[Cl:1][C:2]1[CH:11]=[C:10](I)[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Br-].[C:14]([O:18][C:19](=[O:22])[CH2:20][Zn+])([CH3:17])([CH3:16])[CH3:15].[Cl-].[NH4+].C(OCC)(=O)C>C1COCC1.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[C:14]([O:18][C:19](=[O:22])[CH2:20][C:10]1[CH:9]=[CH:8][C:3]([C:4]([O:6][CH3:7])=[O:5])=[C:2]([Cl:1])[CH:11]=1)([CH3:17])([CH3:16])[CH3:15]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 22619433Methyl 2-chloro-4-iodobenzoateHCID 178451181HCID 178451181, compound

Product 1

HCID 66588010Methyl 4-(2-tert-butoxy-2-oxoethyl)-2-chlorobenzoate

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To methyl 2-chloro-4-iodobenzoate (296 mg) was added a solution (4.5 mL) of 2-tert-butoxy-2-oxoethylzinc bromide in THF, then, bis(tri-tert-butylphosphine)palladium (51 mg) was added, and a reaction was performed at 50 W and 80° C. for 10 minutes using a microwave synthesis apparatus manufactured by CEM Co. The reaction solution was poured into an aqueous saturated ammonium chloride solution, and ethyl acetate was added. Insolubles were filtered off with Celite, and layers were separated. The organic layer was washed with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by medium pressure preparative liquid chromatography W-prep 2XY (column:main column M, inject column S; automatic condition setting: n-hexane:ethyl acetate=4:1, Rf=0.60) to obtain the title compound (94 mg) having following physical property values.

Workup

  1. customa microwave synthesis apparatus
  2. additionwas added
  3. filtrationInsolubles were filtered off with Celite, and layers
  4. customwere separated
  5. washThe organic layer was washed with an aqueous saturated sodium chloride solution
  6. dry with materialdried with anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue was purified by medium pressure preparative liquid chromatography W-prep 2XY (column:main column M, inject column S; automatic condition setting: n-hexane:ethyl acetate=4:1, Rf=0.60)

Sources & evidence

ORD record
ord-d3c37feb6f914e1bafadc875a1efe0cf
Source dataset
uspto-grants-2015_04
Patent number
US09006246B2

Reaction notes

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