合成双酚AF的新方法

New Method for Synthesis of Bisphenol AF

由六氟丙酮三水合物和苯胺,经缩合、重氮化、水解、Friedel-Crafts烷基化4步反应常压下合成了双酚AF。以五氧化二铌为催化剂,在n（HFA.3H2O）∶n（an iline）∶n（Nb2O5）=2∶1∶0.1,回流6 h条件下,合成出中间体（Ⅰ）,收率高达96.3%。重氮化温度为-2-2℃、H2SO4质量分数为14.7%、n（Ⅰ）∶n（H2SO4）∶n（NaNO2）=1∶4.1∶1.1、及水解时H2SO4质量分数为50%、n（H2SO4）∶n（Ⅰ）=11.0∶1、108-112℃反应1.5-2 h的优化条件下,化合物Ⅰ经重氮化、水解后以92.7%的高收率得到中间体2-（4-羟基苯）六氟异丙醇（Ⅱ）;再在甲磺酸存在下,化合物Ⅱ与苯酚经Friedel-Crafts烷基化反应以72.4%的收率合成了目标产物双酚AF（Ⅲ）,总收率为64.6%（以苯胺为基准计算）。

Bisphenol AF was prepared from HFA·3H2O and aniline under atmospheric pressure in 4 steps：condensation, diazotization, hydrolysis and Friedel-Crafts alkylation.Firstly,2-（4-aminophenyl）-1,1,1,3,3,3-hexafluoropropan-2-ol（Ⅰ） was obtained in a yield of 96.3% from HFA·3H2O and aniline under optimal conditions with Nb2O5 as catalyst at an n（HFA·3H2O）∶n（aniline）∶n（Nb2O5） ratio of 2∶1∶0.1 under reflux for 6 h.Then 2-（4-hydroxy phenyl）-1,1,1,3,3,3-hexafluoropropan-2-ol（Ⅱ） was synthesized from compound（Ⅰ） via diazotization,hydrolysis.The optimum reaction conditions were as follows：during diazotization,n（Ⅰ）∶n（H2SO4）∶n（NaNO2） was 1∶4.1∶1.1,the mass fraction of H2SO4 was 14.7% and reaction temperature-2～2 ℃;during hydrolysis,the mass fraction of H2SO4 was 50%,n（H2SO4）∶n（Ⅰ） is 11∶1.Under these conditions,the yield was 92.7%.Subsequently,in the presence of methanesulfonic acid,the Friedel-Crafts alkylation of compound Ⅱ with phenol yielded target compound bisphenol AF（Ⅲ）in a yield of 72.4%.The total yield was 64.6% based on aniline.