2,2-二氟苯并[d][1,3]二氧代-5-羧酸甲酯用作研究用化合物,主要用于化学合成。
化学合成
路线1:
- 步骤:将5-溴-2,2-二氟苯并[d][1,3]二氧杂环戊烯(3g,12.66mmol)溶于甲醇(30ml),加入Pd(dppf)Cl₂(817mg,1.12mmol)和三乙胺(2.56g,25.4mmol),在CO气氛下100℃搅拌24小时,真空浓缩后经硅胶柱色谱(1%乙酸乙酯的石油醚溶液洗脱)纯化,得到淡黄色油状产物2,2-二氟苯并[d][1,3]二氧杂环戊烯-5-羧酸甲酯。
- 条件:100℃;CO气氛;24小时
- 收率:51%
- 参考文献:[1] Patent: US2012/277224, 2012, A1. Location in patent: Page/Page column 26;[2] Patent: US2007/244159, 2007, A1. Location in patent: Page/Page column 78;[3] Patent: US2008/9524, 2008, A1. Location in patent: Page/Page column 383; 384;[4] Patent: US2009/143381, 2009, A1. Location in patent: Page/Page column 53;[5] Patent: US2009/221597, 2009, A1. Location in patent: Page/Page column 29;[6] Patent: US2009/253736, 2009, A1. Location in patent: Page/Page column 22;[7] Patent: US2009/246137, 2009, A1. Location in patent: Page/Page column 32-33;[8] Patent: WO2005/75435, 2005, A1. Location in patent: Page/Page column 148;[9] Patent: WO2010/53471, 2010, A1. Location in patent: Page/Page column 46;[10] Patent: WO2007/21982, 2007, A2. Location in patent: Page/Page column 63-64;[11] Patent: US2015/231142, 2015, A1. Location in patent: Paragraph 1112; 1350; 1514;[12] Patent: WO2016/109362, 2016, A1. Location in patent: Paragraph 00157;[13] Patent: WO2008/141119, 2008, A2. Location in patent: Page/Page column 69
路线2:
- 步骤:将2,2-二氟胡椒酸(171g)溶于甲醇(1197ml),加入亚硫酰氯(215g),回流反应4小时,冷却至20℃后加入3.8kg水,分离下层有机层,减压蒸馏得产物2,2-二氟苯并[d][1,3]二氧杂环戊烯-5-羧酸甲酯,其中2,2-二氟甲基苯甲酸酯含量为99.9%。
- 条件:回流;4小时
- 收率:94.2%