【摘要】 以间氨基苯甲醚为原料,在浓HCl、NaNO2作用下,反应温度5℃以下,加入40%的氟硼酸,加热,经Schiemann反应生成间氟苯甲醚,产率36.6%。然后在60℃水浴中缓慢滴加65%~68%的发烟硝酸、冰乙酸和醋酐的混合液(间氟苯甲醚与浓硝酸的摩尔比为0.0624∶0.0721、冰乙酸与醋酐的体积比为10.6∶7.6),苯环上4-位硝化1 h后得3-氟-4-硝基苯甲醚,产率48.7%,沸点151.2℃。在ZnCl2和浓HCl作用下反应12 h,再还原成3-氟-4-氨基苯甲醚,产率84.1%,熔点240~241℃。加入NaNO2、浓H2SO4和KI,在5℃下重氮化,经Sandmeyer反应碘代合成3-氟-4-碘苯甲醚,产率72.0%,熔点123~123.5℃。通过沸点、熔点、IR、1HNMR、MS和元素分析对产物进行了表征。更多还原

【Abstract】 3-aminoanisole was diazotized with conc.HCl and NaNO₂ below 5 ℃ and treated with fluoroboric acid 4%（Schiemann reaction）to give 3-fluoroanisole in 36.6% yield.Then,the mixture of 65%～68% nitric acid,glacial acetic acid and acetic anhydride was dropped slowly to 3-fluoroanisole at 60℃ for 1h（3-fluoroanisole and nitric acid molar ratio 0.0624∶0.0721,glacial acetic acid and acetic anhydride volume ratio 10.6∶7.6） on water bath to produce 3-fluoro-4-nitroanisole in 48.7% yield（bp 151.2 ℃）.3-Fluoro-4-nitroanisole was reduced by ZnCl₂ and HCl for 12h to form 3-fluoro-4-aminoanisole in 84.1% yield（mp 240～241 ℃）.Finally,3-fluoro-4-iodoanisole was obtainde in 72.0% yield（mp 123～123.5 ℃）by diazotization of 3-fluoro-4-aminoanisole at 5 ℃ in NaNO₂ and H₂SO₄ and addition of KI（Sandmeyer reaction）.The product was characterized by boiling point,melting point,melting point IR,（）¹H NMR,MS and elemental analysis.更多还原