4-Bromo-2-chloro-1-cyclopropoxybenzene → Tert-butyl 2-(3-chloro-4-cyclopropoxyphenyl)acetate

HRID 1773972Notes

Reaction equation

HRID 1773972 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:11][CH2:10]2)=[C:4]([Cl:12])[CH:3]=1.[Cl-].[C:14]([O:18][C:19](=[O:22])[CH2:20][Zn+])([CH3:17])([CH3:16])[CH3:15]>O1CCOCC1.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:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:11][CH2:10]2)=[C:4]([Cl:12])[CH:3]=1)([CH3:17])([CH3:16])[CH3:15]

Participants

5

Reactant 2

HCID 575946584-Bromo-2-chloro-1-cyclopropoxybenzeneHCID 178451183HCID 178451183, compound

Product 1

HCID 89649373Tert-butyl 2-(3-chloro-4-cyclopropoxyphenyl)acetate

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 4-bromo-2-chloro-1-cyclopropoxy-benzene (610 mg, 2.46 mmol, 1.00 eq.) in dioxane (20 mL), bis(tri-t-butylphosphine)palladium (0) (193 mg, 0.37 mmol, 0.15 eq.) and 2-tert-butoxy-2-oxoethylzinc chloride (0.5M in diethyl ether) (8.9 mL, 4.44 mmol, 1.80 eq.) were added in sequence. The resulting mixture was stirred at r.t. for 18 hours and further at 60° C. for 4 hours. The mixture was allowed to cool down to r.t. and filtered through Celite. The filtrate was concentrated in vacuo. The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 40 fractions of 45 mL, Heptane to Heptane+5% AcOEt) to yield the title compound as a white solid.

Workup

  1. temperatureto cool down to r.t.
  2. filtrationfiltered through Celite
  3. concentrationThe filtrate was concentrated in vacuo
  4. customThe residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 40 fractions of 45 mL, Heptane to Heptane+5% AcOEt)

Sources & evidence

ORD record
ord-f19b22be283240fe8b52cd77b05a1b92
Source dataset
uspto-grants-2016_02
Patent number
US09255090B2

Reaction notes

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