β-甲基萘合成2-甲基-1,4-萘醌绿色氧化反应工艺  

Green oxidation process for synthesis of 2-methyl-1,4-naphthoquinone from β-methylnaphthalene

作　　者：潘瑾雯 杨索和[1] 何广湘[1] 郭晓燕[1] 靳海波[1] 马磊 Jinwen PAN;Suohe YANG;Guangxiang HE;Xiaoyan GUO;Haibo JIN;Lei MA(Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology,College of New Material and Chemical Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院新材料与化工学院,燃料清洁化及高效催化减排技术北京市重点实验室,北京102617

出　　处：《过程工程学报》2022年第12期1702-1709,共8页The Chinese Journal of Process Engineering

基　　金：国家自然科学基金资助项目(编号:91634101);北京市属高校高水平教师队伍建设支持计划-高水平创新团队建设计划项目(编号:IDHT20180508)。

摘　　要：2-甲基-1,4-萘醌(2-MNQ)是K族维生素的重要中间体,广泛应用于医药、农药、饲料添加剂等领域。本工作以2-甲基萘(2-MN)为原料,(NH_(4))_(2)S_(2)O_(8)为引发剂,用30%H_(2)O_(2)与冰醋酸在硫酸催化下制备过氧乙酸并滴加至反应液中,氧化合成2-甲基-1,4-萘醌(2-MNQ),通过ICIR,GC-MS,LCMS对其结构进行表征,并验证氧化反应机理及中间产物。考察了催化剂、反应温度、反应时间、氧化剂与引发剂用量对产品2-MNQ收率、转化率的影响,采用HPLC (外标法)测定产品2-MNQ的转化率和收率,得到最佳工艺条件为反应温度65℃、反应时间5 h、n(H_(2)O_(2)):n(2-MN)=26:1,此时,2-甲基萘的转化率为99%,产品收率为34%。本工作的创新点是使用原位红外技术验证反应机理和中间过程,即原料2-甲基萘经过氧乙酸氧化,发生环氧化反应生成中间体,之后重排生成2-甲基羟醌,继续氧化生成目标产物2-甲基-1,4-萘醌。该工艺具有简单环保、操作条件温和、原料易得等特点。2-methyl-1,4-naphthoquinone (2-MNQ) is an important intermediate of K vitamins,which is widely used in medicine,pesticides,feed additives and other fields.However,this vitamin does not exist in nature,and artificial synthesis is the only way to produce 2-MNQ.In industry,vitamin K3 is prepared using 2-methylnaphthalene (2-MN)as raw material and chromic anhydride as an oxidant.This process produces a large amount of waste residue and wastewater containing chromium,causing irreversible pollution to the environment,and trace amounts of chromium in the product pose a threat to human health.Therefore,a new type of the green oxidation process was used for hydrogen peroxide oxidation.The process used 2-methylnaphthalene (2-MN) as raw material,(NH_(4))_(2)S_(2)O_(8) as initiator to prepare peroxygen with 30% H_(2)O_(2) and glacial acetic acid under the catalysis of sulfuric acid.Acetic acid was added dropwise to the reaction solution to synthesize 2-methyl-1,4-naphthoquinone (2-MNQ) by oxidation,and its structure was characterized by ICIR,GC-MS,and LCMS,and the oxidation reaction mechanism and the type and content of byproducts were verified.The main impurities were isomer 6-methyl-1,4-naphthoquinone and its by-products phthalic anhydride and 4-methylphthalic anhydride produced by excessive oxidation.The effects of catalyst,reaction temperature,reaction time,dosage of oxidizer and initiator on the yield and conversion of 2-MNQ were investigated.The conversion rate and yield of 2-MNQ were determined by HPLC (external standard method).The optimum reaction conditions were reaction temperature of 65℃,reaction time of 5 h,n(H_(2)O_(2)):n(2-MN)=26:1.The conversion rate of 2-methylnaphthalene was 99%,and the product yield was 34%.The innovation point of this work was to verify the reaction mechanism and the intermediate process in detail using the original external infrared,that was,the raw material 2-methylnaphthalene was oxidized by peracetic acid,the epoxidation reaction generated the intermediate,and then rearranged to gen

关 键 词：2-甲基萘 2-甲基-1 4-萘醌 氧化反应 绿色合成 

分 类 号：TQ244.62[化学工程—有机化工]