Page 218 - 《精细化工》2021年第7期

第 38 卷第 7 期 精 细 化 工 Vol.38, No.7
202 1 年 7 月 FINE CHEMICALS July 2021

精细化工中间体
4-溴-5-硝基-1,8-萘酐的合成工艺改进

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胡艳雄，吴爱斌 ，师春甜，刘 叶，舒文明，余维初
（长江大学 化学与环境工程学院，湖北 荆州 434023）

摘要：以苊为原料、NaBr/CeCl 3 •7H 2 O/H 2 O 2 为溴化试剂，得到 5-溴苊，再用 Al(NO 3 ) 3 •9H 2 O/CH 3 COOH 硝
化，得到 4-溴-5-硝基苊，进一步以醋酸钴/醋酸锰/N-羟基邻苯二甲酰亚胺/氧气为氧化剂，制备得到萘酰亚
胺类荧光染料的重要中间体 4-溴-5-硝基-1,8-萘酐。考察了原料配比、反应温度、时间以及溶剂对收率的影
响，优选的最佳反应条件为：溴化反应温度 25 ℃，反应时间 3 h，n（苊）∶n（CeCl 3 •7H 2 O）∶n（NaBr）= 2∶1∶
2.4，收率 86.4%；硝化反应温度 45 ℃，反应时间 8 h，n（5-溴苊）∶n〔Al(NO 3 ) 3 •9H 2 O〕= 1∶1.2，收率 88.4%；
氧化反应温度 110 ℃，反应时间 5 h，n（醋酸钴）∶n（醋酸锰）∶n（N-羟基邻苯二甲酰亚胺）∶n（4-溴-5-
硝基苊）= 1.2∶0.5∶1.2∶10，收率 72.3%。进行了初步放大实验，结果表明，反应扩大 5~20 倍后仍具有较
好的收率。
关键词：苊；溴化；硝化；氧化；4-溴-5-硝基-1,8-萘酐；精细化工中间体
中图分类号：TQ241.5 文献标识码：A 文章编号：1003-5214 (2021) 07-1500-05

Improvement of synthesis process of
4-bromo-5-nitro-1,8-naphthalene anhydride

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HU Yanxiong, WU Aibin , SHI Chuntian, LIU Ye, SHU Wenming, YU Weichu
（College of Chemistry & Environmental Engineering, Yangtze University, Jingzhou 434023, Hubei, China）

Abstract: 5-Bromoacenaphthene was obtained from acenaphthene using NaBr/CeCl 3 ·7H 2O/H 2O 2 as
bromination reagent. Then, nitration reaction of 5-bromoacenaphthene with Al(NO 3) 3·9H 2O/CH 3COOH to
synthesize 4-bromo-5-nitroacenaphthene. Finally, 4-bromo-5-nitro-1,8-naphthalene anhydride, important
intermediate of naphthalimide fluorescent dyes was prepared using cobalt acetate/manganese acetate/N-
hydroxyphthalimide (NHPI)/oxygen as oxidant. The effects of raw material ratio, reaction temperature,
reaction time, and solvent on the yield of the product were investigated. The optimal reaction conditions
were obtained. For the bromination reaction, the yield of 5-bromoacenaphthene was 86.4% under the
conditions of temperature 25 ℃, reaction time 3 h, n(acenaphthene)∶n(CeCl 3•7H 2O)∶n(NaBr)=2∶1∶
2.4, Under the conditions of temperature 45 ℃ , reaction time 8 h, n(5-bromoacenaphthene) ∶
n[Al(NO 3) 3•9H 2O]=1∶1.2, the yield of 4-bromo-5-nitroacenaphthene was 88.4%. For the oxidation
reaction, when the temperature was 110 ℃, reaction time was 5 h, n(cobalt acetate)∶n(manganese
acetate)∶n(NHPI)∶n(4-bromo-5-nitroacenaphthene) was 1.2∶0.5∶1.2∶10, the yield of 4-bromo-5-
nitro-1,8-naphthalene anhydride was 72.3%. A preliminary scale-up experiment was conducted by using
this method. The product yield was still high after the reaction was expanded by 5~20 times.
Key words: acenaphthene; bromination; nitration; oxidation; 4-bromo-5-nitro-1,8-naphthalene
anhydride; ;fine chemical intermediates

1,8-萘酰亚胺类化合物是一类非常重要的功能 材料，吸引了人们的广泛关注。该类材料色泽鲜艳、

收稿日期：2021-02-05; 定用日期：2021-02-19; DOI: 10.13550/j.jxhg.20210138
基金项目：国家自然科学基金项目（21801022）
作者简介：胡艳雄（1994—），男，硕士生。联系人：吴爱斌（1973—），男，博士，副教授，E-mail：abwu@yangtzeu.edu.cn；余维
初（1965—），男，博士，教授，E-mail：yuweichu@126.com。