Study on green synthesis process for 2-methyl-1,4-naphthoquinone
QIAO Qiong-qing1, WANG Po-hui1, WU Jin-ting1, DONG Ming-fu2, LI Hong-bo1
1. School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China; 2. Sichuan Yinhe Chemical Co., Ltd., Mianyang 622656, China
Abstract: Crude 2-methyl-1,4-naphthoquinone (2-MNQ) is prepared by using 2-methylnaphthalene (2-MN) as raw material,glacial acetic acid as solvent,30% H2O2 as oxidant and (NH4)2S2O8 as initiator.Its structure is confirmed by IR,NMR and MS spectra.The purity of crude product,and the type and content of impurities contained therein are determined by HPLC (area normalization method).The optimum process conditions are obtained through investigating the effects of reaction temperature,reaction time,amounts of solvent and oxidant on the yield,purity and conversion of crude 2-MNQ.The optimum reaction temperature is 85℃,the optimum reaction time is 3 h,and the optimum n(CH3COOH):n(H2O2):n(2-MN) is 50:11:1.Under the optimum conditions,crude product yield can reach 61.1%,the conversion is 99.7%,and the purity is 87.7%.Through HPLC determination,crude 2-MNQ contains main impurities including phthalic anhydride and 6-methyl-1,4-naphthoquinone (6-MNQ).Pure 2-MNQ with a purity of 97.7% can be obtained by processing crude 2-MNQ with NaHCO3 and NaHSO3 aqueous solutions in turn,the total yield is 56.2%.
乔琼清, 王珀会, 吴金婷, 董明甫, 李鸿波. 2-甲基-1,4-萘醌的绿色合成工艺研究[J]. 现代化工, 2020, 40(8): 158-161.
QIAO Qiong-qing, WANG Po-hui, WU Jin-ting, DONG Ming-fu, LI Hong-bo. Study on green synthesis process for 2-methyl-1,4-naphthoquinone. Modern Chemical Industry, 2020, 40(8): 158-161.
[1] 刘兴泉,唐毅,林晓静,等.K系维生素中间体β-甲基萘醌合成的研究进展[J].化工科技,2003,11(2):49-54. [2] 逯秀玲,张昶,张斌,等.双香豆素类鼠药致维生素K依赖性凝血因子缺乏患者的观察护理[J].护士进修杂志,2006,21(11):1017-1018. [3] Plaza S M.The anticancer effects of vitamin K[J].Alternative Medicine Review,2003,8(3):303-318. [4] 陈本懋.维生素C和K3的抗癌作用[J].生命的化学,1991(4):27-27. [5] 彭莉.维生素K3的合成及应用[J].中国兽药杂志,2003,37(10):50-52. [6] Schmid R,Goebel F,Warnecke A,et al.Synthesis and redox potentials of methylated vitamin K derivatives[J].Journal of the Chemical Society Perkin Transactions,1999,6(6):1199-1202. [7] 张华蜂,张华强,陈天华,等.维生素K生产工艺进展[J].饲料工业,2004,25(1):19-21. [8] 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):323-330. [9] Arnold R T,Larson R.Quinones by the peroxide oxidation of aromatic compounds[J].J Org Chem,1940,5(3):250-252. [10] Bohle A,Schubert A,Yu S,et al.A new metal-free access to Vitamin K3[J].Advanced Synthesis & Catalysis,2010,348(9):1011-1015. [11] Olga V Z,Vasiliy Y E,Gennadii M M,et al.Selective oxidation of pseudocumene and 2-methylnaphthalene with aqueous hydrogen peroxide catalyzed by γ-Keggin divanadium-substituted polyoxotungstate[J].Journal of Organometallic Chemistry,2015,793:210-216. [12] Feng S,Man K T,Beller M.A novel and convenient process for the selective oxidation of naphthalenes with hydrogen peroxide[J].Advanced Synthesis & Catalysis,2007,38(22):303-308.