高附加值萘二酚类中间体的合成与应用进展

doi:10.16085/j.issn.1000-6613.2018-1353

化工进展 ›› 2019, Vol. 38 ›› Issue (04): 1903-1912.DOI: 10.16085/j.issn.1000-6613.2018-1353

高附加值萘二酚类中间体的合成与应用进展

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

1. 天津大学化工学院，天津市应用催化科学与工程重点实验室，天津 300354
2. 天津市功能精细化学品技术工程中心，天津 300354
3. 天津化学化工协同创新中心，天津 300072

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:
国家重点研发计划(2017YFB0404701)

Progress in synthesis and application of naphthalenediol intermediates with high value-added

Bin LI^1,²,Xue WANG¹,Shuang JIANG^1,²(),Tianyong ZHANG^1,³(),Jingyi YANG¹,Jingchao WANG¹,Xiao SHAO¹,Xiaoyuan MA¹

1. Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300354, China
2. Tianjin Engineering Research Center of Functional Fine Chemicals, Tianjin 300354, China
3. Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China

Received:2018-07-02 Revised:2018-11-13 Online:2019-04-05 Published:2019-04-05
Contact: Shuang JIANG,Tianyong ZHANG

摘要/Abstract

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。

关键词: 萘二酚, 1,6-二羟基萘, 生物转化法, 催化羟基化法

Abstract:

The traditional synthetic process of naphthalenediol intermediates has the advantages of simple operation and high degree of industrialization, but there are problems such as large amount of waste acid emission, complicated post-treatment process, high cost, and serious environmental pollution. In recent years, it has been gradually replaced by green synthetic technology. In this paper, the traditional synthetic methods based on sulfonation alkali fusion and nitration reduction methods was reviewed. The biotransformation method that employs microalgae microorganisms, recombinant yeast and various structures of oxygenase metabolism, and the emerging green synthesis process that uses direct acid catalyzed hydroxylation with strong acids, biological enzymes and organometallic complexes as catalysts were briefly described. The synthesis progress of 1,6-dihydroxynaphthalene was highlighted. In particular, in the presence of hydrogen peroxide, the catalytic hydroxylation reaction was carried out directly with an acid catalyst like the use of strong acid hydrofluoric acid and antimony pentafluoride and the use of fluoroanthracenesulfonic acid, boron trifluoride and hydrofluoric acid. At the same time, the typical applications of naphthalenediols in dyes, medicines, catalysis and batteries were also reviewed. Finally, the improvement direction of the biotransformation method and the catalytic hydroxylation method for the preparation of naphthalenediol is to improve the yield of the reaction and the conversion rate of naphthalene to satisfy the demand of large-scale industrial production. In addition, the development of the application field of naphthalene diphenol intermediates is towards the development of refined, high value-added medicines and materials.

Key words: naphthalenediol, 1,6-dihydroxynaphthalene, biotransformation, catalytic hydroxylation

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.

图/表 19

图1 磺化反应工艺流程

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

图2 硝化还原工艺流程

图3 多种单加氧酶催化萘氧化反应

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3对应）
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

图4 催化羟基化法制备萘二酚

图5 萘直接催化羟基化合成萘酚及萘二酚

图6 羟基自由基参与的萘羟基化反应

图7 CYP101B1酶催化萘系底物羟基化反应

图8 酸性媒介黑P2B染料合成工艺

图9 酸性媒介黑PV染料合成工艺

图10 萘二酚的聚合物作二次电池电极材料

图11 二次电池充放电机理

图12 1,6-DHN催化苯甲醛氧化成苯甲酸

图13 萘二酚酯类液晶化合物合成路线

图14 B-1催化光氧化反应

表3 萘二酚光催化氧化反应

序号	反应物4结构	产品5结构	收率/%
1			74
2			73
3			80

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

图15 BODIPY衍生物三重态光敏剂催化反应机理

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高附加值萘二酚类中间体的合成与应用进展

Progress in synthesis and application of naphthalenediol intermediates with high value-added

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