芳基乙酸酯的 合成.pdfVIP

经验交流 由芳卤制备芳基乙酸酯的方法 由芳卤制备芳基乙酸酯的方法由芳卤制备芳基乙酸酯的方法 由芳卤制备芳基乙酸酯的方法由芳卤制备芳基乙酸酯的方法 丁明平，丁明平，张维娜张维娜 丁明平丁明平，，张维娜张维娜 芳基乙酸酯类化合物广泛用于医药，农药，香料及燃料等领域，其制备合成方法很 多。本文在查阅文献的基础上结合本课题组的项目进展，重点介绍了由芳卤制备芳基乙 酸酯的方法。 1、通过钯催化反应、通过钯催化反应制成芳基乙酸制成芳基乙酸酯酯 、、通过钯催化反应通过钯催化反应制成芳基乙酸制成芳基乙酸酯酯 1.1 经经Stille反应制得芳基乙酸酯反应制得芳基乙酸酯[1] 经经 反应制得芳基乙酸酯反应制得芳基乙酸酯 反应操作如下： Zinc bromide (1.56 g, 6.92 mmol) in a dry flask was heated at 140oC for 1 h under high vacuum. Then a mixture of compound 1 (1.93 g, 4.94 mmol), ethyl 2-(tri butylstannyl)acetate (2.61 g, 6.92 mmol), and PdCl (P-(o-tol) ) (310 mg, 0.395 mmol) in dry DMF (10 mL) was 2 3 2 o added to the flask and heated at 80 C for 14 h under argon. The black reaction mixture was diluted with water (10 mL) and extracted with Et O (3×10 mL). The combined organic layers 2 were washed with brine, dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The crude residue was further purified by flash chromatography on silica gel (15:1, hexanes-EtOAc) to give compound 2 (1.41 g, 3.58 mmol, 72%) as a pale yellow oil. 1H-NMR (CDCl , 300 MHz): δ 7.23 (s, 1H, H ), 6.67 (s, 1H, H ), 5.16 (s, 2H, ArOCH OCH=), 4.68 (d, 3 6 3 2 2H, J = 3.9 Hz, ArCH OTBS), 4.14 (q, 2H, J = 7.2 Hz, OCH CH ), 3.79 (s, 1H, ArOMe), 3.58 2 2 3 (s, H, ArCH COOEt), 3.49 (s, 3H, ArOCH OCH ), 1.24 (t, 3H, J = 7.2 Hz, OCH CH ), 0.94 2 2 2 3 2 3 [(s, 9H, SiC(CH3)=]. 通过Stille反应引入碳链是