반응 #420034

반응 방정식

sodium bisulfite

hydrogen peroxide

3-bromo-6-methoxy-2-(4-methoxyphenyl)-benzo[b]thiophene

trifluoroacetic acid

→

3-bromo-6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene 1-oxide

수율 88.0%

용매

water

DCM

반응 조건

후처리

1. 1
   workup.ADDITIONUpon addition the resulting mixture
2. 2
   workup.STIRRINGThe resulting suspension was stirred vigorously for 15 min
3. 3
   농축concentrated in vacuo
4. 4
   기타to remove DCM
5. 5
   기타The residue was partitioned between DCM (40 mL) and sat. aq. NaHCO3 solution (40 mL)
6. 6
   기타separated
7. 7
   기타The organic layer was collected (phase separator)
8. 8
   농축concentrated in vacuo
9. 9
   기타to afford the crude product, which
10. 10
    기타was purified by column chromatography (SiO2, 1-40% EtOAc/Heptane)

실험 절차

To a solution of 3-bromo-6-methoxy-2-(4-methoxyphenyl)-benzo[b]thiophene (4 g, 11.45 mmol) in DCM (20.02 mL) at room temperature was added trifluoroacetic acid (20.02 mL) dropwise, the reaction went from orange to dark brown in color. Upon addition the resulting mixture was stirred at room temp for 10 min and then hydrogen peroxide (30% wt. aq) (1.583 mL, 16.47 mmol) was added dropwise. After 90 min at room temperature the reaction mixture was quenched with sodium bisulfite (1.714 g, 16.47 mmol) (vigorous bubbling was observed) followed by 3.0 mL of water. The resulting suspension was stirred vigorously for 15 min and then concentrated in vacuo to remove DCM and most of the TFA. The residue was partitioned between DCM (40 mL) and sat. aq. NaHCO3 solution (40 mL) and separated. The organic layer was collected (phase separator) and concentrated in vacuo to afford the crude product, which was purified by column chromatography (SiO2, 1-40% EtOAc/Heptane) to afford 3-bromo-6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene 1-oxide (4.6 g, 10.08 mmol, 88% yield) as an orange solid. 1H NMR (400 MHz, CD3OD) δ ppm=7.51-7.65 (m, 2H), 7.37-7.51 (m, 2H), 7.08 (dd, J=2.27, 8.34 Hz, 1H), 6.79-6.96 (m, 2H), 3.74 (s, 3H), 3.68 (s, 3H).

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