preparation | step 1: synthesis of 2-amino -4-bromobenzene methanol 60g NaBH4 is added to 300mL tetrahydrofuran (THF) and stirred mechanically. Under the ice water bath, add 100g of 2-amino-4-bromobenzoic acid to the solution, then add 27mL of boron trifluoride ethyl ether solution dropwise, and control the temperature below 20 degrees. After dropping, raise the reaction solution to room temperature and react overnight until the raw material is finished. Add 300ml MeOH dropwise to the reaction solution, add 5N NaOH(200ml) after the dropwise addition, and stir for about half an hour. The organic solvent in the reaction liquid is spin dried and cooled to room temperature, solid is precipitated, filtered, and the crude 2-amino -4-bromobenzene methanol is obtained by about 60g [mass spectrometry (MS)M 1 203]. 98.7% yield. Step 2: Synthesis of 2-amino-4-bromobenzaldehyde Add 60g and 300g of manganese dioxide obtained in step 1 to 1L dichloromethane solvent, mechanically stir, and react overnight. The reaction liquid is passed through diatomite and column (petroleum ether: ethyl acetate = 5: 1) to obtain about 40g of 2-amino -4-bromobenzaldehyde [nuclear magnetic resonance hydrogen spectrum (400MHz,CDCl3):δ6.72-6.75(d,1h),7.23(bs,2h),7.38-7.42(dd, h),7.72-7.73(d,1h),9.77(s,1H)]. 85.2% yield. |