盐酸为氯源“一锅法”绿色高效合成α-氯噻吩

doi:10.16085/j.issn.1000-6613.2020-0049

摘要/Abstract

摘要：

在现有氯碱工业中，以氯气为氯源的氯化反应安全性差且产生过量盐酸，氯的原子经济性较差。针对这些问题，本文以盐酸为唯一氯源，经双氧水氧化得到氯气分子，进而氯化噻吩合成α-氯噻吩（2-氯噻吩和2,5-二氯噻吩）。产物结构经气质联用分析仪（GC-MS）与核磁氢谱（¹H NMR）分析确定。通过对HCl量、H₂O₂量、反应温度和反应时间等工艺条件的考察，获得最佳实验条件为n(噻吩)∶n(HCl)∶n(H₂O₂)=1∶2.7∶2.1，反应温度35℃，反应时间3h，经气相色谱分析得到噻吩的转化率达100%，α-氯噻吩选择性达93%。另外，通过离子色谱对反应前后水相中氯离子浓度检测来确定氯离子的消耗量，并对单程反应后水相重复利用的工艺条件进行了探究。研究结果表明该工艺路线绿色安全，反应条件温和，后处理简单。水相中无其他杂质且可循环回收利用，工艺条件更适合工业化生产，同时也为氯化氢气体的回收利用提供了另外一种可能的途径。

关键词: 盐酸, 噻吩, 氧化氯化, α-氯噻吩, 绿色合成, 回收利用

Abstract:

In the existing chlor-alkali industry, the chlorination reaction using chlorine gas as a chlorine source has poor safety and is prone to produce excessive hydrochloric acid, and the atomic economy of chlorine is poor. In response to these problems, hydrochloric acid was used as the sole source of chlorine in this study. Oxygen peroxide was used to obtain chlorine molecules, and then chlorothiophene was synthesized into α-chlorothiophene (2-chlorothiophene and 2,5-dichlorothiophene). Phase can continue to be recycled. The structure of the product was confirmed by GC-MS and ¹HNMR analysis. By examining the process conditions such as the amount of HCl, the amount of H₂O₂, the reaction temperature, and the reaction time, the optimal experimental conditions are n(thiophene)∶n(HCl)∶n(H₂O₂)=1∶2.7∶2.1, and the reaction temperature is 35℃. With a reaction time of 3h, the conversion of thiophene was 100%, and the selectivity of α-chlorothiophene was 93%. In addition, the chloride ion concentration in the aqueous phase before and after the reaction was measured by ion chromatography to determine the consumption of chloride ions, and the process conditions for the reuse of the aqueous phase after a single-pass reaction were investigated. The research results show that the process route is green and safe, the reaction conditions are mild, and the post-processing is simple. The water phase has no other impurities and can be recycled. The process conditions are more suitable for industrial production, and it also provides another possible way for the recycling of hydrogen chloride gas.

Key words: hydrochloric acid, thiophene, oxychlorination, α-chlorothiophene, green synthesis, recycle

中图分类号:

TQ251.2

孙小康, 冯宇, 李国梅, 刘妙青, 卢建军. 盐酸为氯源“一锅法”绿色高效合成α-氯噻吩[J]. 化工进展, 2020, 39(S2): 305-311.

Xiaokang SUN, Yu FENG, Guomei LI, Miaoqing LIU, Jianjun LU. One-pot method for the green and efficient synthesis of α-chlorothiophene with hydrochloric acid as a chlorine source[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 305-311.

图/表 8

图1 2-氯噻吩和2,5-二氯噻吩的1HNMR谱图

图2 反应结束后有机粗品相的GC-MS分析

图3 反应温度对噻吩转化率和产物选择性的影响

图4 HCl用量对噻吩转化率和产物选择性的影响

图5 H2O2用量对噻吩转化率和产物选择性的影响

图6 反应时间对噻吩转化率和产物选择性的影响

表1 单程反应后氯离子的转化率

起始时Cl^-的量 /mol	终了时Cl^-的量 /mol	单程Cl^-的消耗量 /mol	Cl^-的转化率 /%
0.1694	0.1042	0.0652	38.49

表2 回收水相的实验条件对结果的影响

反应时间 /h	补加物料（α-氯噻吩5g）		转化率/%	收率^③/%	选择性%
反应时间 /h	盐酸^①/mL	双氧水^②/mL	转化率/%	收率^③/%	选择性%
3	5	5	56.56	46.61	78.87
3	8	5	57.91	49.35	78.32
3	8	8	70.44	58.83	83.52
5	5	5	72.36	56.21	77.68
5	8	5	82.51	65.76	77.27
5	8	8	92.29	79.27	85.88
6	8	8	95.53	71.66	75.01

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