β-O-4型木质素模型化合物的合成及其在GIF型仿酶降解体系中的变化(Ⅱ)  

SYNTHESIS OF β-O-4 TYPE LIGNIN MODEL COMPOUND AND ITS BIOMIMETIC DEGRADATION WITH GIF SYSTEM(Ⅱ)

作　　者：谢益民[1] 胡周建[2] 伍红[2] 赖燕明[2] 

机构地区：[1]山东轻工业学院制浆造纸工程学科,山东济南250100 [2]华南理工大学制浆造纸工程国家重点实验室,广东广州510640

出　　处：《林产化学与工业》2004年第1期1-6,共6页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(29974011;30170756);霍英东基金资助项目(71066);教育部博士点基金项目(20020561022);教育部重点项目(01137)

摘　　要：　深入研究了β-O-4型木质素模型化合物———愈创木基丙三醇-β-愈创木基醚的合成新路线,并利用红外光谱和核磁共振谱对其化学结构进行了分析。采用由Cu2+/吡啶/过氧化氢组成的GIF(GIF sur YVETTE)型仿酶体系对这一木质素模型物进行了仿酶降解的研究,并采用GC-MS、13CNMR等方法分析了该β-O-4型木质素模型化合物在降解过程中的结构变化,在此基础上对这种仿酶降解的机理进行了探讨。研究结果表明:利用溴化铜对4-乙酰基愈创木酚进行溴化后很容易得到4-(α-溴化乙酰基)-愈创木酚中间体,从而提高了合成愈创木基丙三醇-β-愈创木基醚的效率。GIF仿酶降解体系对β-O-4型木质素模型物有较强的碎解能力,降解后产生一系列含羟基、醛基和羧基的芳香族低分子化合物,根据反应产物的结构可以说明β-O-4型木质素模型化合物的主要降解途径为:β-O-4醚键断裂、Cα—Cβ键断裂、Cβ—Cγ键断裂。本研究为该仿酶降解体系在无污染漂白工业上的应用提供理论依据。A lignin model compound of phenolic β-O-4 type,i.e.guaiacylglycerol-β-guaiacyl ether was synthesized with a modified method.Combination of infrared spectra analysis and ~1H NMR was used to identify chemical structure of the products.Afterwards,the β-O-4 type model compound was treated with a new delignification system using (copper)/pyridine/peroxide(GIF system).High resolution ^(13)C NMR and GC-MS analysis were used to investigate the change of chemical structure of β-O-4 type model compound during the reaction.Mechanism of this biomimetic delignification was also explored.Results showed that 4-(α-bromoacetyl)-guaiacol could be obtained from acetovanillone by bromination with copper(Ⅱ) bromide at high yield.Therefore,guaiacylglycerol-β-guaiacyl ether could be synthesized efficiently.Results also indicated that GIF type biomimetic system had strong ability on degradation of phenolic β-O-4 type model compound.After degradation,a series of low molecular aromatic compounds containing carboxyl,(hydroxyl) and carbonyl groups were produced.From their structures,the following reactions were caused by the GIF system:ether-bond cleavage,alkyl-aryl cleavage and C_β—C_γ cleavage.Consequently,this work provides a comprehensive information on biomimetic delignification system that could be applied to industrial non-pollution bleaching.

关 键 词：β-O-4型木质素模型化合物 合成 GIF型仿酶降解体系 仿酶漂白 纸浆 铜离子/吡啶/过氧化氢 

分 类 号：TS745[轻工技术与工程—制浆造纸工程]