反应详情

温度

57.5 °C

A 750 ml, 4-necked glass flask equipped with a mechanical stirrer, a thermometer, a dropping funnel and an argon inlet was charged under argon with 41.0 g (100 mmol) of tributylammonium hydroxy-(4-hydroxy-benzo[b]thiophen-7-yl)-acetate, 60.5 g (115 mmol) of iron(III) sulfate and a mixture prepared from 60 ml of dry ethanol and 300 ml of 0.4 N sulfuric acid aqueous solution. Then stirring was started and the reaction mixture was heated to 55-60° C. for 5 h. After cooling to room temperature, 300 ml of isopropyl acetate and 100 ml of water were added under stirring, then the organic phase was separated and transferred into a 500 ml glass flask equipped with a pH meter. After addition of 150 ml of water (pH was 3.0), ca. 58 ml of a 2 N sodium hydroxide aqueous solution were added dropwise at 20° C. until a pH of 12-12.5 was reached. The organic phase was removed and to the aqueous phase were added at 10-15° C. dropwise ca. 54 ml of a 2 N aqueous solution of sulfuric acid until a pH of 4-4.5 was reached. The product precipitated during the addition. The suspension was stirred over night at room temperature, 1.2 h in an ice bath and then filtered. The filter cake was washed with water and dried at 60° C./15 mbar to afford 17.23 g (94%) of 4-hydroxy-benzo[b]thiophene-7-carboxaldehyde as white crystals with m.p. of 204° C.

1. customA 750 ml, 4-necked glass flask equipped with a mechanical stirrer
2. temperatureAfter cooling to room temperature
3. stirringunder stirring
4. customthe organic phase was separated
5. customtransferred into a 500 ml glass flask
6. customequipped with a pH meter
7. additionAfter addition of 150 ml of water (pH was 3.0), ca. 58 ml of a 2 N sodium hydroxide aqueous solution
8. additionwere added dropwise at 20° C. until a pH of 12-12.5
9. customThe organic phase was removed and to the aqueous phase
10. additionwere added at 10-15° C. dropwise ca. 54 ml of a 2 N aqueous solution of sulfuric acid until a pH of 4-4.5
11. customThe product precipitated during the addition
12. stirringThe suspension was stirred over night at room temperature, 1.2 h in an ice bath
13. filtrationfiltered
14. washThe filter cake was washed with water
15. customdried at 60° C./15 mbar