苯并咪唑类化合物的合成及防腐性能研究
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摘要
苯并咪唑类化合物具有很好的杀菌、防霉活性及其他性能。为探索具有高活性的有机木材防腐剂，本论文以4-取代邻苯二胺为原料，经酰化、环合等步骤合成了7种5-取代苯并咪唑类衍生物，其结构经熔点、MS、1H NMR及元素分析确证。用滤纸片法研究目标化合物对白腐菌[彩绒革盖菌（Coriolus versicolor）]、褐腐菌[密粘褶菌（Gloeophyllum trabeum）]、霉菌[黑曲霉（Aspergillus niger）、绿色木霉（Trichoderma viride）]的抑制效果。然后，本文通过室内防霉实验、抗流失性能实验对其进行测试和评价，并与传统的防霉剂相比，具有鲜明的优点。具体研究内容及成果如下：
1.以4-取代邻苯二胺为原料，经酰化、环合等步骤合成了7种5-取代苯并咪唑类衍生物，其中有2个化合物未见文献报道。以上合成方法具有条件温和、操作简便、易纯化等优点，具有一定的实际应用价值。
2.采用滤纸片法对目标化合物进行抑菌实验，结果显示：合成的7种化合物对木材腐朽菌中的腐朽菌均没有活性，但部分化合物对木材腐朽菌中的霉菌有明显的抑制效果，且活性高于对照试剂。
3.配制不同浓度的目标化合物溶液，通过室内防霉实验检测其对木材的防霉性能，结果表明，化合物4a在质量浓度为0.5%时防霉等级达到0级，化合物4b在质量浓度为1.5%时防霉等级达到0级，优于五氯酚钠。
4.配制1.0%、1.5%浓度的目标化合物溶液和五氯酚钠溶液，通过室内抗流失试验对其流失性进行测定，结果表明，相同实验条件下，目标化合物4b的流失率最低，在质量浓度为1.5%时其流失率仅为8.31%，优于化合物4a（多菌灵）及五氯酚钠。
Benzimidazole derivatives have good bactericidal activity, mould resistanceactivity and possess a variety of other characters. To find new hyperactivitybroad-spectrum organic wood preservative, seven5-substituted benzimidazolecompounds were synthesized from4-substituted o-phenylenediamine throughmulti-step reactions including acylation, cyclization and so on. All the structureswere confirmed by melting points, MS,1H NMR and elemental analysis. The targetcompounds were screened for antimicrobial activity by agar-well diffusion methodagainst white-rot fungus (Coriolus versicolor), brown-rot fungus (Gloeophyllumtrabeum) and moulds (Aspergillus niger and Trichoderma viride). Then, this paperstudies on them laboratory anti-mould performance and leaching resistanceevaluation, they have the distinct advantages compared with the traditionalanti-mould. The contents and the primary contributions of the research aresummarized as follows:
1. Seven5-substituted benzimidazole compounds were synthesized from4-substituted o-phenylenediamine through multi-step reactions including acylation,cyclization and so on, and in which two have never been reported by now, the salientfeatures of the above mentioned methods include a simple procedure, mildconditions and easy purification.
2. The antibacterial properties of fungi of the target compounds were testthrough the zone of inhibition. Results show that: all compounds showed their nofungicidal activities, but some showed their anti-mould activities, and even somebetter than the contrast.
3. Laboratory anti-mould performance was carried on to evaluate mouldresistance using the concentration of different target compounds solution, the resultsshow that0.5%4a and1.5%4b could obtain grade0anti-mould, better thanpentachlorophenol sodium.
4. Laboratory leaching performance was carried on to evaluate leaching rate of1.0%,1.5%concentration of target compounds and pentachlorophenol sodium, theresults show that the leaching rate of target compounds4b is the lowest in the sameexperimental conditions, which1.5%4b is only to8.31%, better than4a(carbendazim) and pentachlorophenol sodium.
1.以4-取代邻苯二胺为原料，经酰化、环合等步骤合成了7种5-取代苯并咪唑类衍生物，其中有2个化合物未见文献报道。以上合成方法具有条件温和、操作简便、易纯化等优点，具有一定的实际应用价值。
2.采用滤纸片法对目标化合物进行抑菌实验，结果显示：合成的7种化合物对木材腐朽菌中的腐朽菌均没有活性，但部分化合物对木材腐朽菌中的霉菌有明显的抑制效果，且活性高于对照试剂。
3.配制不同浓度的目标化合物溶液，通过室内防霉实验检测其对木材的防霉性能，结果表明，化合物4a在质量浓度为0.5%时防霉等级达到0级，化合物4b在质量浓度为1.5%时防霉等级达到0级，优于五氯酚钠。
4.配制1.0%、1.5%浓度的目标化合物溶液和五氯酚钠溶液，通过室内抗流失试验对其流失性进行测定，结果表明，相同实验条件下，目标化合物4b的流失率最低，在质量浓度为1.5%时其流失率仅为8.31%，优于化合物4a（多菌灵）及五氯酚钠。
Benzimidazole derivatives have good bactericidal activity, mould resistanceactivity and possess a variety of other characters. To find new hyperactivitybroad-spectrum organic wood preservative, seven5-substituted benzimidazolecompounds were synthesized from4-substituted o-phenylenediamine throughmulti-step reactions including acylation, cyclization and so on. All the structureswere confirmed by melting points, MS,1H NMR and elemental analysis. The targetcompounds were screened for antimicrobial activity by agar-well diffusion methodagainst white-rot fungus (Coriolus versicolor), brown-rot fungus (Gloeophyllumtrabeum) and moulds (Aspergillus niger and Trichoderma viride). Then, this paperstudies on them laboratory anti-mould performance and leaching resistanceevaluation, they have the distinct advantages compared with the traditionalanti-mould. The contents and the primary contributions of the research aresummarized as follows:
1. Seven5-substituted benzimidazole compounds were synthesized from4-substituted o-phenylenediamine through multi-step reactions including acylation,cyclization and so on, and in which two have never been reported by now, the salientfeatures of the above mentioned methods include a simple procedure, mildconditions and easy purification.
2. The antibacterial properties of fungi of the target compounds were testthrough the zone of inhibition. Results show that: all compounds showed their nofungicidal activities, but some showed their anti-mould activities, and even somebetter than the contrast.
3. Laboratory anti-mould performance was carried on to evaluate mouldresistance using the concentration of different target compounds solution, the resultsshow that0.5%4a and1.5%4b could obtain grade0anti-mould, better thanpentachlorophenol sodium.
4. Laboratory leaching performance was carried on to evaluate leaching rate of1.0%,1.5%concentration of target compounds and pentachlorophenol sodium, theresults show that the leaching rate of target compounds4b is the lowest in the sameexperimental conditions, which1.5%4b is only to8.31%, better than4a(carbendazim) and pentachlorophenol sodium.
引文
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[7]池玉杰.木材腐朽菌的种群结构和木材腐朽菌对木材生物降解的初步研究[R].中国林业科学研究院博士后研究报告,2002.
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[18] Barnes H. M., Murphy R. J.. Wood preservation: the classics and the new age[J]. For. Prod.J.,1995,45(9):16-26.
[19]金重为.世界木材工业的发展.中国林学会木材工业分会论文集(19),2000.11,浙江嘉善.
[20] United States Environmental Protection Agency. Whitman Announees Transition fromConsumer Use of Treated Wood Containing Arsenic[N]. EPA Environmental News,2002,2,12.
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[23]任士学.季铵盐类木材防腐剂的应用研究[D].东北林业大学,2001.
[24]余丽萍.抗流失硼基木材防腐剂配方遴选及优选配方处理材的性能[D].北京林业大学,2009.
[25]李晓文.三唑类木材防腐剂防腐和抗流失性能的研究[D].中国林业科学研究院,2009.
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[28]姜卸宏,曹金珍.季铵盐类化合物(QAC)在木材防腐中的应用[J].林产工业,2007,34(2):3-8.
[29]黄金营.含咪唑杂环的长链烷基双季铵盐的合成及其特性研究[D].华中科技大学,2005.
[30]宋琳,王惠贞.苯并咪唑Schiff碱的合成及其杀菌活性[J].中国药物化学杂志,2000,10(2):92-94.
[31]朱莉,廖展如,龙云飞等.含苯并咪唑锌配合物的合成、表征及晶体结构[J].无机化学学报,2004,20(4):399-402.
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