应用化学 ›› 2009, Vol. 26 ›› Issue (11): 1292-1296.

• 研究论文 • 上一篇    下一篇

合成双酚AF的新方法

戴燕,吕春绪*,李斌栋,李晶晶   

  1. (南京理工大学化工学院 南京 210094)
  • 收稿日期:2008-11-03 修回日期:2009-03-19 出版日期:2009-11-10 发布日期:2009-11-10
  • 通讯作者: 吕春绪,男,教授,博士生导师; E-mail:yangzi7310@sina.com; 研究方向:有机氟化学

New Method for Synthesis of Bisphenol AF

DAI Yan, LV Chun-Xu*, LI Bin-Dong, LI Jing-Jing   

  1. (School of Chemical Engineering,Nanjing University of Science & Technology,Nanjing 210094)
  • Received:2008-11-03 Revised:2009-03-19 Published:2009-11-10 Online:2009-11-10

摘要:

由六氟丙酮三水合物和苯胺,经缩合、重氮化、水解、Friedel-Crafts烷基化等4步反应在常压下合成了双酚 AF。首先,以五氧化二铌为催化剂,在 n (HFA•3H2O) : n (aniline) : 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%。然后在重氮化温度为 ﹣2 ~ 2 ℃,硫酸质量分数为 14.7%,n (Ⅰ) : n (H2SO4) : n (NaNO2) = 1 : 4.1 : 1.1,及水解时硫酸质量分数为 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)。

关键词: 双酚AF, 六氟丙酮水合物, 苯胺, Friedel-Crafts烷基化, 重氮化, 水解

Abstract:

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) is 1 : 4.1 : 1.1, the content of H2SO4 is 14.7% and reaction temperature ﹣2 ~ 2 ℃; during hydrolysis, the content of H2SO4 is 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.

Key words: bisphenol AF, hexafluoroacetone hydrate, aniline, Friedel-Crafts alkylation, diazotization, hydrolysis

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