反应详情

A 1000 mL, three-necked, round bottomed flask equipped with a magnetic stirrer, thermometer, addition funnel, and argon inlet was charged with 2-chloro-6-methylbenzaldehyde (71.31 g, 461 mmol, crude obtained from the above experiment) and 750 mL of acetonitrile. To this suspension, a solution of monobasic sodium phosphate (115 mmol, 15.9 g) in water 240 mL) was added followed by hydrogen peroxide (50 mL, 30%) at room temperature. Then, a solution of sodium chlorite (73.5 g, 811 mmol) in water (700 mL) was added dropwise at 0° C. while maintaining the temperature below 3° C. After the addition was complete, the yellow suspension was stirred for 15 h at 0° C. to room temperature. TLC analysis of the mixture indicated the absence of starting material. A solution of sodium bisulfite (73 g, 701 mmol) in water (200 mL) was added dropwise at 0° C. until the yellow color disappeared (KI-paper positive). Cooling was maintained throughout to control the exothermic reaction. The solvent was removed under vacuum to afford a colorless solid. The solid was collected by filtration and the filtrate was extracted with diethyl ether (200 mL). The above solid was dissolved in the combined diethyl ether extracts which were then washed with 10% NaOH solution (2×200 mL). The combined aqueous washings were acidified with 10% HCl to pH 1. The resulting colorless precipitate was collected by filtration and air-dried to afford 54.88 g (65%, overall in two steps) of 2-chloro-6-methylbenzoic acid as a colorless solid.

1. customA 1000 mL, three-necked, round bottomed flask equipped with a magnetic stirrer
2. additionthermometer, addition funnel, and argon inlet
3. temperaturewhile maintaining the temperature below 3° C
4. additionAfter the addition
5. temperatureCooling
6. temperaturewas maintained throughout
7. customthe exothermic reaction
8. customThe solvent was removed under vacuum
9. customto afford a colorless solid
10. filtrationThe solid was collected by filtration
11. extractionthe filtrate was extracted with diethyl ether (200 mL)
12. dissolutionThe above solid was dissolved in the combined diethyl ether extracts which
13. washwere then washed with 10% NaOH solution (2×200 mL)
14. filtrationThe resulting colorless precipitate was collected by filtration
15. customair-dried