氧化1,4-丁二醇制备4-羟基丁醛的相关研究
孟庆勇
学位类型硕士
导师吾满江•艾力
2008-06-09
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业有机化学
关键词4-羟基丁醛 1 氧化反应 4-丁二醇 六价铬氧化剂 无机负载氧化剂 微乳液 环化反应 量子化学计算
摘要

有机化学经验指出,4-羟基丁醛易于环化生成2-羟基四氢呋喃。本文首先利用量子化学计算方法对这个环化反应进行了计算研究。采用重铬酸钾硫酸溶液,Jones试剂,PCC氧化剂,PDC氧化剂和Sarett试剂在30 oC条件下氧化1,4-丁二醇得到4-羟基丁醛。为指示4-羟基丁醛的产率,将反应混合物与2,4-二硝基苯肼(DNP)的盐酸溶液作用得到4-羟基丁醛-2,4-二硝基苯腙(DNP derivative)。实验发现,以Jones试剂为氧化剂到达反应终点的时间最短;以PCC试剂为氧化剂n(BDO):n(Cr)=1:1时苯腙收率最高,达到80%。制备得到各种氯铬酸吡啶(PCC)和氯重铬酸吡啶(PDC)无机载体氧化剂,以1,4-丁二醇的选择性氧化成4-羟基丁醛为探针反应。同样,为了计算氧化效率,在氧化结束后向体系加入2,4-二硝基苯肼,得到4-羟基丁醛-2,4-二硝基苯腙。在30 oC下反应60 min,其收率分别为:73.0%(PCC/活性炭),82.0%(PCC/氧化铝),85.0%(PCC/硅胶),80.0%(PCC);62.0%(PDC/活性炭),73.0%(PDC/氧化铝),78.0%(PDC/硅胶),63.0%(PDC)。不同载体的氧化活性顺序为:PCC/活性炭

其他摘要

Very few synthetic operations in organic chemistry match the importance of the oxidation of alcohols to aldehydes and ketones. A quantum chemical direct dynamics study was performed for the pericyclic reaction of 4-hydroxybutanal. 4-Hydroxybutanal were synthesized from 1,4-butanediol by oxidation reaction at 30 oC with potassium dichromate in sulfate, Jones reagent, PCC reagent, PDC reagent and Sarett reagent. For defining the stoichiometry, 4-hydroxybutanal 2,4-dinitrophenylhydrazine (DNP) derivative were prepared. The results show that, the molar ratio of 1,4-butandiol and chromium(VI) 1:1, the yield of DNP derivative is about 80% by PCC reagent; oxidation reaction of 1,4-butandiol with Jones reagent was the fastest. Some typical inorganic carriers were used to support PCC and PDC as oxidants, the activity of the supported oxidants was evaluated in the selective oxidation reaction of 1,4-butanediol to 4-hydroxybutanal. For determining stoichiometry, 4-hydroxybutanal 2,4-dinitrophenylhydrazine (DNP) derivative were prepared. The effects of the kinds of carriers as well as the reaction conditions on the activity of PCC were investigated. The yield was investigated to be 73.0% (PCC/activated carbon), 82.0% (PCC/A12O3), 85.0% (PCC/silica gel), 80.0% (PCC); 62.0% (PDC/activated carbon), 73.0% (PDC/A12O3), 78.0% (PDC/silica ge1), and 63.0% (PDC), when the reaction was carried out with the content of PCC or PDC of 1.8 mmolg-1, and the stirring time of 60 min at room temperture. Silica gel is a good carrier for PCC or PDC. For protecting a hydroxyl of 1,4-butanediol, the 1,4-butanediol single-ester of chloacetate acid, benzoic acid, decane acid, lauric acid, myristic acid, palmitic acid, stearic acid, and diphenyl glycolic acid were synthesized. The 1,4-butanediol single-ether of butyl and benyl were also synthesized. For Oxidation these single-ester and single-ether, the water/Tergitol 7/oil and oil/Tergitol 7/water microemulsions were preparated.

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/3527
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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孟庆勇. 氧化1,4-丁二醇制备4-羟基丁醛的相关研究[D]. 北京. 中国科学院研究生院,2008.
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