化工进展 ›› 2019, Vol. 38 ›› Issue (04): 1903-1912.DOI: 10.16085/j.issn.1000-6613.2018-1353
李彬1,2,王雪1,姜爽1,2(),张天永1,3(),杨靓怡1,王景超1,邵笑1,马骁媛1
收稿日期:
2018-07-02
修回日期:
2018-11-13
出版日期:
2019-04-05
发布日期:
2019-04-05
通讯作者:
姜爽,张天永
作者简介:
<named-content content-type="corresp-name">李彬</named-content>(1982—),男,博士,副教授,硕士生导师。|姜爽,讲师,研究方向为精细化学品合成。E-mail:<email>shuangjiang@tju.edu.cn</email>|张天永,教授,博士生导师。E-mail:<email>tyzhang@tju.edu.cn</email>
基金资助:
Bin LI1,2,Xue WANG1,Shuang JIANG1,2(),Tianyong ZHANG1,3(),Jingyi YANG1,Jingchao WANG1,Xiao SHAO1,Xiaoyuan MA1
Received:
2018-07-02
Revised:
2018-11-13
Online:
2019-04-05
Published:
2019-04-05
Contact:
Shuang JIANG,Tianyong ZHANG
摘要:
萘二酚类中间体的传统合成工艺具有操作简单和工业化程度高等优点,但存在废酸排放量大、后处理工艺复杂、成本高和环境污染严重等问题,近年来有被绿色合成工艺逐步替代的趋势。本文回顾了以磺化碱熔法和硝化还原法为主的传统合成方法;简述了用微藻类微生物、重组酵母以及多种结构的加氧酶代谢转化的生物转化法和以强酸、生物酶以及有机金属络合物作为催化剂的直接催化羟基化法等新兴绿色合成工艺。着重介绍了1,6-二羟基萘(又称为1,6-萘二酚)的合成工艺进展,特别是在过氧化氢存在下,采用酸催化剂,如用强酸氢氟酸和五氟化锑催化以及用氟锑磺酸、三氟化硼和氢氟酸等直接进行的催化羟基化反应。同时还综述了萘二酚化合物在染料、医药、催化及电池等领域的典型应用情况。最后指出了生物转化法及催化羟基化法制备萘二酚的改进方向是提高反应的收率及萘的转化率,以达到大规模工业化生产的水平;并对萘二酚类中间体应用领域的拓展进行了展望,指出其向精细化、高附加值的医药及材料方向发展的趋势。
中图分类号:
李彬, 王雪, 姜爽, 张天永, 杨靓怡, 王景超, 邵笑, 马骁媛. 高附加值萘二酚类中间体的合成与应用进展[J]. 化工进展, 2019, 38(04): 1903-1912.
Bin LI, Xue WANG, Shuang JIANG, Tianyong ZHANG, Jingyi YANG, Jingchao WANG, Xiao SHAO, Xiaoyuan MA. Progress in synthesis and application of naphthalenediol intermediates with high value-added[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1903-1912.
磺化剂 | 分子式 | 物理状态 | 副反应 | 活泼性 |
---|---|---|---|---|
三氧化硫 | SO3 | 气态 | 很多 | 活泼 |
液态 | 很多 | 非常活泼 | ||
氯磺酸 | Cl SO3H | 液态 | 多 | 活泼 |
发烟硫酸 | H2SO4 SO3 | 液态 | 较多 | 比较活泼 |
硫酸 | H2SO4 | 液态 | 较多 | 比较活泼 |
氨基磺酸 | NH2SO3H | 固态 | 较少 | 温和 |
表1 常用磺化剂反应特性的比较
磺化剂 | 分子式 | 物理状态 | 副反应 | 活泼性 |
---|---|---|---|---|
三氧化硫 | SO3 | 气态 | 很多 | 活泼 |
液态 | 很多 | 非常活泼 | ||
氯磺酸 | Cl SO3H | 液态 | 多 | 活泼 |
发烟硫酸 | H2SO4 SO3 | 液态 | 较多 | 比较活泼 |
硫酸 | H2SO4 | 液态 | 较多 | 比较活泼 |
氨基磺酸 | NH2SO3H | 固态 | 较少 | 温和 |
酶 | 1-萘酚 选择性/% | 2-萘酚 选择性/% | 反应过程 (与图 |
---|---|---|---|
野生型TOM | 99 | <1 | a、b、c、e |
TOM TmoA3 V106A | 99 | <1 | a |
野生型ToMO | 90 | 10 | b、c、d、e |
野生型TpMO | 63 | 37 | d、e |
野生型T4MO | 52 | 48 | d、e |
TmoA I100A | 8 | 92 | b |
TmoA I100S | 5 | 95 | |
TmoA I100G | 12 | 88 | |
TmoA I100L | 83 | 17 | |
TmoA G103S/A107G | 99 | <1 | a |
表2 不同种加氧酶反应的选择性及适用的反应过程[21,22,23]
酶 | 1-萘酚 选择性/% | 2-萘酚 选择性/% | 反应过程 (与图 |
---|---|---|---|
野生型TOM | 99 | <1 | a、b、c、e |
TOM TmoA3 V106A | 99 | <1 | a |
野生型ToMO | 90 | 10 | b、c、d、e |
野生型TpMO | 63 | 37 | d、e |
野生型T4MO | 52 | 48 | d、e |
TmoA I100A | 8 | 92 | b |
TmoA I100S | 5 | 95 | |
TmoA I100G | 12 | 88 | |
TmoA I100L | 83 | 17 | |
TmoA G103S/A107G | 99 | <1 | a |
序号 | 取代胺结构 | 产品6结构 | 收率/% |
---|---|---|---|
4 | | 79 | |
5 | | 77 | |
6 | | 75 |
表4 1,4-萘醌与苯胺合成反应
序号 | 取代胺结构 | 产品6结构 | 收率/% |
---|---|---|---|
4 | | 79 | |
5 | | 77 | |
6 | | 75 |
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