Hydrochloric Acid → ethyl 4-pivaloylbenzoate

HRID 1025797Notes

Reaction equation

[I-].[CH2:2]([O:4][C:5]([C:7]1[CH:12]=[CH:11][C:10]([Zn+])=[CH:9][CH:8]=1)=[O:6])[CH3:3].[CH3:14][C:15]([CH3:20])([CH3:19])[C:16](Cl)=[O:17].Cl>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:14][C:15]([CH3:20])([CH3:19])[C:16]([C:10]1[CH:11]=[CH:12][C:7]([C:5]([O:4][CH2:2][CH3:3])=[O:6])=[CH:8][CH:9]=1)=[O:17]

Participants

Conditions

Temperature: 0 °C

Procedure

4-(Ethoxycarbonyl)phenyl-zinc iodide (50.0 mL of a 0.5 M solution in THF, 25.0 mmol) was added slowly via cannula to a stirred solution of dichlorobis(triphenylphosphine)palladium(II) (484 mg, 0.690 mmol) in THF (50 mL) at 0° C. After 15 min, trimethylacetyl chloride (2.80 mL, 22.7 mmol) was added and the resulting mixture was stirred at 0° C. for 1.5 h. The reaction mixture was poured into 1 N HCl and extracted three times with EtOAc. The combined organic extracts were washed with water, brine, dried (MgSO4) and concentrated in vacuo. Purification of the crude residue by flash chromatography on silica gel (gradient elution; 0-10% EtOAc/hexanes as eluent) afforded the title compound i-1a. 1HNMR (500 MHz, CDCl3): δ 8.08 (d, 2H, J=8.5 Hz), 7.67 (d, 2H, J=8.5 Hz), 4.42 (q, 2H, J=7.2 Hz), 1.42 (t, 3H, J=7.2 Hz), 1.36 (s, 9H).

Workup

extractionextracted three times with EtOAc
washThe combined organic extracts were washed with water, brine
dry with materialdried (MgSO4)
concentrationconcentrated in vacuo
customPurification of the crude residue by flash chromatography on silica gel (gradient elution; 0-10% EtOAc/hexanes as eluent)

Sources & evidence

ORD record: ord-f921ef57b1c848568072f8f72f3c2e48
Source dataset: uspto-grants-2014_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08729104B2

Reaction notes

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