摘要
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.
出处
《应用化学》
CAS
CSCD
北大核心
2009年第11期1292-1296,共5页
Chinese Journal of Applied Chemistry