钨酸钠/过氧化氢体系对葡甲苷伯羟基的选择催化氧化

doi:10.11944/j.issn.1000-0518.2015.10.150107

摘要/Abstract

摘要：

采用钨酸钠/过氧化氢体系对甲基葡萄糖苷的伯羟基进行选择催化氧化制备葡萄糖醛酸及其内酯,考察了不同催化氧化工艺条件对反应收率的影响,产物用HPLC检测,同时对反应机理进行了初步探讨。结果表明, 该体系对葡甲苷伯羟基的氧化具有较好的催化活性和反应选择性,葡萄糖醛酸及其内酯总收率可达到74.07%。与传统的淀粉硝酸氧化法工艺相比,该方法具有资源节约、环境友好的特点。

关键词: 钨酸钠/过氧化氢体系, 葡甲苷, 葡萄糖醛酸, 选择氧化

Abstract:

Sodium tungstate/hydroperoxide was used for the preparation of glucuronic acid and its lactone by selective oxidation of primary hydroxyl group of methyl glucoside. The effects of different catalytic oxidative conditions on the yield were studied. The products were determined by HPLC. A reaction mechanism was proposed. The catalytic system exhibits high activity and good selectivity on the oxidation of primary hydroxyl of methyl glycoside. Combined yield of glucuronic acid and its lactone is up to 74.07%. Compared with the traditional HNO₃ oxidation of starch, this process is more environmental-friendly and economical.

Key words: sodium tungstate/hydroperoxide system, methyl glucoside, glucuronic acid, selective oxidation

张培,袁华,吴加雄,张华良. 钨酸钠/过氧化氢体系对葡甲苷伯羟基的选择催化氧化[J]. 应用化学, 2015, 32(10): 1159-1163.

ZHANG Pei,YUAN Hua,WU Jiaxiong,ZHANG Hualiang. Selective Oxidation of Primary Hydroxyl of Methyl Glucoside by Sodium Tungstate/Hydroperoxide[J]. Chinese Journal of Applied Chemistry, 2015, 32(10): 1159-1163.

参考文献

[1]	SUN Yinglian,WANG Yingjun,SUI Ming. Research on the Effects of Glucurolactone Granules on Experimental Liver Injury[J]. Spec Wild Econom Animal Res,2009,31(2):45-47(in Chinese). 孙英莲,王英军,隋明. 肝泰乐颗粒对实验性肝损伤的保护作用[J]. 特产研究,2009,31(2):45-47.
[2]	YUAN Hua,DU Zhiping,YAN Zhiguo,et al.Selective Oxidation of Primary Alcohol from Methyl Glucoside over Pd/La0.5Pb0.5Mn0.9Sn0.1O3 Catalyst[J]. Acta Chim Sin,2009,67(4):345-351(in Chinese). 袁华,杜治平,闫志国,等. Pd/La0.5Pb0.5Mn0.9Sn0.1O3对葡甲苷伯羟基的选择催化氧化[J]. 化学学报,2009,67(4):345-351.
[3]	MA Yan,ZHAO Linlin,LIU Huaqing,et al.Progress in the Preparation of Glucuronic Acid by Catalytic Oxidative Methods from Starch and its Derivatives[J]. Appl Chem Ind,2011,40(7):1245-1247(in Chinese). 马彦,赵林林,刘华庆,等. 淀粉及其衍生物催化氧化制备葡萄糖醛酸研究进展[J]. 应用化工,2011,40(7):1245-1247.
[4]	YUAN Hua,SUN Yanbin,WU Mao,et al.Synthesis of Glucuronic Acid by Pd/La0.5Pb0.5MnO3 Catalytic Oxidation from Methyl Glucoside[J]. Chinese J Process Eng,2008,8(3):572-575(in Chinese). 袁华,孙炎彬,邬茂,等. Pd/La0.5Pb0.5MnO3催化氧化甲苷合成葡萄糖醛酸[J]. 过程工程学报,2008,8(3):572-575.
[5]	CHANG Zhenyong,CUI Lianqi. Review on Research and Application of Perovskite Type Structure Metal Oxide Catalysis[J]. Spec Petrochem,2002,5(3):50-53(in Chinese). 常振勇,崔连起. 钙钛矿金属氧化物催化剂的研究与应用综述[J]. 精细石油化工,2002,5(3):50-53.
[6]	Shi M,Feng Y S. Oxidation of Benzyl Chlorides and Bromides to Benzoic Acids with 30% Hydrogen Peroxide in the Presence of Na2WO4, Na2VO4, or Na2MoO4 under Organic Solvent-Free Conditions[J]. J Org Chem,2001,66:3235-3237.
[7]	Takemasa Hida,Hideo Nogusa. Practical and Versatile Oxidation of Alcohol Using Novel Na2WO4 H2O2 System under Neutral Conditions[J]. Tetrahedron,2009,65:270-274.
[8]	MOU Ling. Determination of Glucurolactone by HPLC[S]. Drug Standards of China,2004,5(4):57-58(in Chinese). 牟玲. HPLC法测定葡醛内酯的含量[S]. 中国药品标准,2004,5(4):57-58.
[9]	SU Hao,YANG Chun. Selective Oxidation of Benzyl Alcohol Catalyzed by Polyoxometalates: A Green Recyclable Catalytic System with High Performance[J]. Chinese J Appl Chem,2014,31(8):959-964(in Chinese). 苏浩,杨春. 多金属氧酸盐催化苯甲醇的选择性氧化:一个绿色可循环的高效催化氧化体系[J]. 应用化学,2014,31(8):959-964.
[10]	LI Xiancai,CAO Xiaohua,XU Changlong. Oxidation of Cyclohexanone to Adipic Acid with 30%H2O2 Catalyzed by WO3[J]. Chinese J Appl Chem,2006,23(11):1250-1252(in Chinese). 黎先财,曹小华,徐常龙. WO3催化H2O2氧化环己酮合成己二酸[J]. 应用化学,2006,23(11):1250-1252.
[11]	Schmidt A K C,Stark C B W. TPAP-Catalyzed Direct Oxidation of Primary Alcohols to Carboxylic Acids through Stabilized Aldehyde Hydrates[J]. Org Lett,2011,16(13):4164-4167.
[12]	ZHANG Chengyu. Radical Addition-Coupling Reaction and its Application in Synthesis of Polymers with Different Structure[D]. Hangzhou:Zhejiang University,2013(in Chinese). 张成裕. 自由基加成—偶合反应及其在聚合物合成中的应用[D]. 杭州:浙江大学,2013.
[13]	MaxymV Vasylyev,Ronny Neumann. New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions[J]. J Am Chem Soc,2004,126:884-890.
[14]	WANG Jianmin,YAN Liang,LI Guixian,et al.Mono-Substituted Keggin-Polyoxometalate Complexes as Effective and Recyclable Catalyst for the Oxidation of Alcohols with Hydrogen Peroxide in Biphasic System[J]. Tetrahedron Lett,2005,46(41):7023-7027.