反应详情

Oxallyl chloride (95 mg, 0.75 mmol) was added to a chloroform (1 ml) solution of 9-bromononanoic acid (119 mg, 0.5 mmols) and a drop of DMF and the resulting mixture was stirred for 40 minutes at room temperature. The reaction mixture and toluene were azeotroped, and then a chloroform (1 ml) solution of the condensed residue was dropped in to a chloroform (0.5 ml) solution of 2,4,6-trifluoroaniline (74 mg, 0.5 mmols) and triethylamine (76 mg, 0.75 mmols) cooling in ice bath, and stirred for 90 minutes at room temperature. The resulting mixture was concentrated, and the resulting residue was diluted with ethyl accetate. The organic layer was washed with 0.5N-HCl, an aqueous saturated solution of sodium hydrogencarbonate, water, and saturated saline in that order, and dried with anhydrous sodium sulfate, and the solvent was evaporated. Then, the residue was purified through silica gel chromatography (silica gel 20 g, developer; hexane:acetone=20:3). And the resulting crystals were recrystallized from acetone-hexane, and 9-bromo-N-(2,4,6-trifluorophenyl) nonanamide 137 mg (yield: 75%) as colorless needle-like crystals (m.p. 65-66° C.). Potassium carbonate (69 mg, 0.45 mmols) and 18-crown-6 (8 mg, 0.03 mmols) were added to a DMF (1 ml) solution of the resulting anilide (110 mg, 0.3 mmols) and 2-mercaptbenzoxzole (45 mg, 0.3 mmol), and stirred for 3 hours at 80° C. The mixture was diluted with water, and extracted with ethyl accetate. The organic layer was washed with water and saturated saline in that order, and dried with anhydrous sodium sulfate, and the solvent was evaporated. And the resulting residue was purified through silica gel chromatography (silica gel 10 g, developer; hexane:acetone=5:2). And the resulting crystals were recrystallized from acetone-hexane, and the intended product 94 mg (yield: 72%) as colorless needle-like crystals.

1. customThe reaction mixture and toluene were azeotroped
2. temperaturecooling in ice bath
3. concentrationThe resulting mixture was concentrated
4. additionthe resulting residue was diluted with ethyl accetate
5. washThe organic layer was washed with 0.5N-HCl
6. dry with materialan aqueous saturated solution of sodium hydrogencarbonate, water, and saturated saline in that order, and dried with anhydrous sodium sulfate
7. customthe solvent was evaporated
8. customThen, the residue was purified through silica gel chromatography (silica gel 20 g, developer; hexane:acetone=20:3)