2-甲基-1,4-萘醌的合成研究
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摘要
以2-甲基萘为原料,通过溴化、甲氧基化反应合成1-甲氧基-2-甲基萘,以酞菁铁为催化剂,双氧水为氧化剂,1-甲氧基-2-甲基萘氧化制得目标产物2-甲基-1,4-萘醌。文中考察了反应温度、催化剂种类及催化剂用量、物料配比对氧化反应的影响,确定了最佳反应条件:冰醋酸做溶剂,酞菁铁5.5%,双氧水与1-甲氧基-2-甲基萘的物质的量比为3∶1,55℃反应4h。在此条件下,2-甲基萘醌的收率为64.7%,纯度为99.0%(HPLC面积归一化法)。产品结构经熔点、~1H-NMR和MS表征。
1-methoxyl-2-methylnaphthalene was synthesized by bromination and methoxylation.The target product 2-methyl-1,4-naphthalenedione was synthesized by oxidation in glacial acetic acid with iron phthalocyanine as catalyst and hydrogen peroxide as oxidant.This paper mainly investigates the reaction temperature,catalyst type,material ratio,catalyst dosage effect on the oxidation reaction,the optimum reaction conditions were determined: glacial acetic acid solvent,iron phthalocyanine catalyst,hydrogen peroxide and 1-methoxy-2-methyl naphthalene mole ratio of 3∶1,4 h reaction time,reaction temperature of 55℃.Under these conditions,the yield of 2-methyl-1,4-naphthoquinone was 64.7%,and the purity was 99.0%(HPLC area normalization method).The product structure was characterized by MP.1 H-NMR and MS.
1-methoxyl-2-methylnaphthalene was synthesized by bromination and methoxylation.The target product 2-methyl-1,4-naphthalenedione was synthesized by oxidation in glacial acetic acid with iron phthalocyanine as catalyst and hydrogen peroxide as oxidant.This paper mainly investigates the reaction temperature,catalyst type,material ratio,catalyst dosage effect on the oxidation reaction,the optimum reaction conditions were determined: glacial acetic acid solvent,iron phthalocyanine catalyst,hydrogen peroxide and 1-methoxy-2-methyl naphthalene mole ratio of 3∶1,4 h reaction time,reaction temperature of 55℃.Under these conditions,the yield of 2-methyl-1,4-naphthoquinone was 64.7%,and the purity was 99.0%(HPLC area normalization method).The product structure was characterized by MP.1 H-NMR and MS.
引文
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[2] 张天永,刘晓思,李彬,等.β- 甲基萘催化氧化合成维生素K3的研究进展[J].化工进展,2017,36(1):316-322.
[3] YALCIN S,CANDEMIR M,KORLU Z,et al.Process for industrial production of 2-methyl-1,4-naphthaquinone:US13/820359[P].2010-9-3.
[4] 王德胜,闫亮,王晓来.杂多酸催化剂研究进展[J].分子催化,2012,26(4):366-375.
[5] 靳会杰,韩志慧,廉红蕾,等.H4PMo11VO40催化氧化2-甲基萘制备甲萘醌[J].河南师范大学学报:自然科学版,2010,38(6):95-97.
[6] 黑晓明.一种2-甲基-1,4-萘醌的新合成方法:CN,201410091125.X[P].2014-06-04.
[7] Notari B.Titanium silicalites[J].Catal Today,1993,18:163-172.
[8] 王祥生.钛硅沸石的研究现状及工业化前景[J].精细化工,1996,13(1):30-34.
[9] 刘兴泉,唐毅,林晓静.K系维生素中间体β-甲基萘醌的合成研究进展[J].化工科技,2003(11):49.
[10] 李东军,岳莉,赖世全.WO3/HMS催化氧化β-甲基萘合成β-甲基萘醌研究[J].化学工业与工程,2011,28(2):63-67.
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[12] 孙兵,焦斌,王守凯,等.1- 甲氧基 -2- 甲基萘的合成研究[J].精细化工中间体,2009,39(1):39-41.