Chloroiodomethane → Methyl 3-bromo-4-cyclopropoxybenzoate

Temperature

0 °C

To a solution of methyl 3-bromo-4-vinyloxy-benzoate (1.00 g, 3.89 mmol, 1.00 eq) in DCM (15.00 mL) was added ZnEt2 (960.91 mg, 7.78 mmol, 2.00 eq) at 0° C. under N2 protection. Then the mixture was stirred at 0° C. for 30 min, and ClCH2I (1.72 g, 9.73 mmol, 2.50 eq) was added. The formed mixture was stirred at 25° C. for 16 hrs. The mixture was poured into NH4Cl solution, and extracted with EA, the combined organic layer was dried over Na2SO4, concentrated, the residue was diluted in THF (5.00 mL) and H2O (5.00 mL), NaIO4 (832.00 mg, 3.89 mmol, 1.00 eq) and K2OsO4 (74.01 mg, 389.00 umol, 0.10 eq) was added, the mixture was stirred at 25° C. for 30 min, then the reaction was quenched by saturated Na2SO3, extracted with EA, the combined organic layer was dried over Na2SO4, concentrated, the residue was purified by silica gel chromatography (PE:EA=10:1) to afford product methyl 3-bromo-4-(cyclopropoxy)benzoate (530.00 mg, 1.95 mmol, 50.26% yield) as colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.23 (d, J=2.01 Hz, 1H), 8.00 (dd, J=8.78, 2.01 Hz, 1H), 7.28-7.33 (m, 1H), 3.92 (s, 3H), 3.88 (t, J=4.39 Hz, 1H), 0.76-0.99 (m, 4H).

1. stirringThe formed mixture was stirred at 25° C. for 16 hrs
2. extractionextracted with EA
3. dry with materialthe combined organic layer was dried over Na2SO4
4. concentrationconcentrated
5. additionthe residue was diluted in THF (5.00 mL)
6. stirringthe mixture was stirred at 25° C. for 30 min
7. customthe reaction was quenched by saturated Na2SO3
8. extractionextracted with EA
9. dry with materialthe combined organic layer was dried over Na2SO4
10. concentrationconcentrated
11. customthe residue was purified by silica gel chromatography (PE:EA=10:1)

ORD record

ord-ed7c173fe08e4e4f9e4ba16594167920

Source dataset

uspto-grants-2015_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09181288B2