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Green oxidation process for synthesis of 2-methyl-1,4-naphthoquinone from β-methylnaphthalene
Jinwen PAN Suohe YANG Guangxiang HE Xiaoyan GUO Haibo JIN Lei MA
The Chinese Journal of Process Engineering
2022, 22 (12):
1702-1709.
DOI: 10.12034/j.issn.1009-606X.221426
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, (NH4)2S2O8 as initiator to prepare peroxygen with 30% H2O2 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 by-products 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(H2O2):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 generate 2-methylhydroxyquinone, and the oxidation continued to generate the target product 2-methyl-1,4-naphthalene quinone. The process has the characteristics of environment friendly, simple technology, mild operating conditions and easy availability of raw materials.The process uses 2-methylnaphthalene (2-MN) as raw material, (NH4)2S2O8 as initiator to prepare peroxygen with 30% H2O2 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 by-products 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 obtained reaction temperature 65℃, reaction time 5h, n(CH3COOOH):n(2-MN) = 26:1. The conversion rate of 2-methylnaphthalene was 98%, and the product yield was 35%. The innovation point of this paper is to verify the reaction mechanism and the intermediate process in detail using the original external infrared, that is, the raw material 2-methylnaphthalene is oxidized by oxyacetic acid, the epoxidation reaction generates the intermediate, and then the rearranges to generates 2-methylhydroxyquinone, and the oxidation continues to generate the target product 2-methyl-1, 4-naphthalene quinone. The process has the characteristics of environment friendly, simple technology, mild operating conditions and easy availability of raw materials.
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