Electric Literature of 106896-49-5, A common heterocyclic compound, 106896-49-5, name is Methyl 4-amino-3-bromobenzoate, molecular formula is C8H8BrNO2, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.
Example 1c Preparation of 3-Bromo-4-cyano-benzoic acid methyl ester A solution of 4-Amino-3-bromo-benzoic acid methyl ester (1.00 g, 4.35 mmol) in dichloromethane (20 mL) is cooled to -10 C. and treated dropwise with 90% tert-butyl nitrite (0.58 g, 0.67 mL, 5.08 mmol) followed by boron trifluoride diethyl etherate (0.94 g, 0.81 mL, 6.62 mmol). The suspension is allowed to warm to room temperature and stirred for 4 h. Diethyl ether (20 mL) is added, and the off-white solid is collected by filtration, washed with diethyl ether and dried briefly under high vacuum. The solid is then suspended in toluene (15 mL) and cooled to 0 C. A solution of copper (I) cyanide (0.52 g, 5.8 mmol) and sodium cyanide (0.71 g, 14.5 mmol) in water (10 mL) is added dropwise over 10 min. The mixture is stirred at 0 C. for 30 min, allowed to warm to room temperature, and then heated to 60 C. After 1 h, the solids are completely dissolved. The mixture is allowed to cool to room temperature, and ethyl acetate (20 mL) and water (20 mL) are added. The aqueous layer is separated and extracted with ethyl acetate (2*20 mL). The organic layers are combined, washed with water (2*10 mL) and brine, dried over Na2SO4, filtered and concentrated at reduced pressure. The solid residue obtained is recrystallized from hexanes/ethyl acetate to afford 3-Bromo-4-cyano-benzoic acid methyl ester (0.42 g, 39%) as a tan solid. The recrystallization mother liquor is concentrated and chromatographed (Biotage, 95:5 to 85:15 hexanes/ethyl acetate) to afford an additional portion of 3-Bromo-4-cyano-benzoic acid methyl ester (0.34 g, total yield: 0.76 g, 73%).
The synthetic route of 106896-49-5 has been constantly updated, and we look forward to future research findings.
Reference:
Patent; SERENEX, INC.; US2008/119457; (2008); A1;,
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