Diiodomethane → 4-Bromo-2-chloro-1-cyclopropoxybenzene

Temperature

0 °C

To an ice-cooled solution of diethylzinc solution (1.0 M in hexanes) (8.25 mL, 8.25 mmol, 2.75 eq.) in DCM (15 mL), trifluoroacetic acid (0.6 mL, 7.80 mmol, 2.60 eq.) was added slowly (gas evolution). Upon addition completion, the mixture was stirred at 0° C. for 10 min. Methyleniodid (0.7 mL, 8.70 mmol, 2.90 eq.) was added dropwise and the mixture was stirred at 0° C. for 10 min. A solution of 4-bromo-2-chloro-1-vinyloxy-benzene (700 mg, 3.00 mmol, 1.00 eq.) in DCM (5 mL) was added dropwise. The reaction mixture was stirred at 0° C. for 30 min and further at r.t. for 1 hour, then quenched with 2N aq. HCl soln. (15 mL) and water (5 mL). The layers were separated. The aq. layer was extracted with DCM (1×25 mL). The comb. org. phases were dried over MgSO4 and concentrated in vacuo. The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane to Heptane+5% AcOEt) to yield 4-bromo-2-chloro-1-cyclopropoxy-benzene as a colorless oil.

1. additionwas added slowly (gas evolution)
2. additionUpon addition completion
3. stirringthe mixture was stirred at 0° C. for 10 min
4. stirringThe reaction mixture was stirred at 0° C. for 30 min and further at r.t. for 1 hour
5. customquenched with 2N aq. HCl soln
6. customThe layers were separated
7. extractionThe aq. layer was extracted with DCM (1×25 mL)
8. dry with materialphases were dried over MgSO4
9. concentrationconcentrated in vacuo
10. customThe residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane to Heptane+5% AcOEt)

ORD record

ord-5f2bbf756c5f4ad7b73b518e16fcd923

Source dataset

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09255090B2