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1、成都理工大学硕士学位论文（S）-5-羟甲基二氢呋喃-2-酮的合成与表征姓名：李豪申请学位级别：硕士专业：应用化学指导教师：梁渠;闫书一20100501摘 要 I (S)-5-羟甲基二氢呋喃羟甲基二氢呋喃-2-酮的合成与表征酮的合成与表征 作者简介：李豪，男，1984 年 3 月生，师从成都理工大学梁渠教授，2010年 06 月毕业于成都理工大学应用化学专业，获得工学硕士学位。 摘摘 要要 (S)-5-羟甲基二氢呋喃-2-酮是 -丁内酯类衍生物，是重要的手性合成单元，该类结构单元可广泛地应用于有机合成， 特别是药物合成及具有生物活性的天然产物的合成。本文主要研究(S)-5-羟甲基二氢呋喃-2-酮
2、的合成方法，产物通过旋光度测定、元素分析、IR、MS 以及1H NMR 谱图表征，证明合成物质即为目标产物。 超声波处理法合成中间体(S)-5-氧代四氢呋喃-2-甲酸。在冰盐浴条件下，用L-谷氨酸的盐酸溶液和亚硝酸钠为原料，经重氮化、内酯化，超声波处理制备(S)-5-氧代四氢呋喃-2-甲酸。研究了反应温度，原料用量、滴加速度、溶剂的选择及用量以及超声波条件对产率的影响，得到最佳合成条件，使总产率达到76.2%。通过超声波处理减少了反应时间，本处理方法未见文献报道。 还原(S)-5-氧代四氢呋喃-2-甲酸得到(S)-5-羟甲基二氢呋喃-2-酮的实验方法选择了两种，即直接还原法和分步还原法。 在直
3、接还原法中，通过实验对还原剂的选择及其用量、物料的滴加速度、反应温度等条件对产率的影响，寻找最佳还原剂及反应条件。使用柱层析分离提纯产品。在最佳反应条件下合成产率达到 78.9%。实验证明用 BH3 Me2S 作还原剂具有副反应少，收率高等特点。 分步还原法合成(S)-5-羟甲基二氢呋喃-2-酮，(S)-5-氧代四氢呋喃-2-甲酸经过酯化、硼氢化钠还原分步合成(S)-5-羟甲基二氢呋喃-2-酮。通过实验对原料配比、反应时间、反应温度、pH 值等条件对收率的影响，使用柱层析提纯产品，产率为 58.0%。该路线具有反应条件温和，过程易操作的特点。 本文对两种方法进行对比，直接还原法的总产率为 60
4、.1%，分步还原法的总成都理工大学硕士学位论文 II 产率为 44.2%，直接还原法远高于分步还原法，并且直接还原法的步骤少，副产物较少，因此在实验室可操控条件较好的情况下，优先选择此方法。 关键词：L-谷氨酸 (S)-5-氧代四氢呋喃-2-甲酸 (S)-5-羟甲基二氢呋喃-2-酮 还原法 合成 Abstract III Synthesis and Characterization of (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one Introduction of the author: LiHao, male, was born in March,
5、1984 whose tutor was Professor LiangQu . He graduated from Chengdu University of Technology in Applied Chemistry major and was granted the Master Degree in June, 2010. Abstract (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one is the -butyrolactone derivatives, an important chiral synthesis block, such st
6、ructural units can be widely used in organic synthesis, especially in drug synthesis and bioactive natural products synthesis. This paper mainly discusses the synthetic method of (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one.It is proved by optical rotation, elemental analysis, IR, MS and 1HNMR spectr
7、ometry that synthetic material should be the target product. Under ice-salt bath and magnetic-stirring conditions, Ultrasonic treatment as auxiliary means was used to synthesize (S)-5-oxotetrahydrofuran-2-carboxylic acid through adding sodium nitrate to ,L-glutamic acid in hydrochloric acid solution
8、.and diazotization then lactonization reaction. Experiment was conducted tostudy the influence of reaction temperature, consumption of raw material dropping rate of the stuffs, solvent selection and dosage and ultrasonic conditions on the productivity. while optimizing experimental conditions to bri
9、nging the total yield up to 76.2%. Reduced reaction time and cost were observed by ultrasonic treatment, which bring a huge stride to industrialized application. This approach has not been reported ever before. Reductive (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one to (S)-5-(hydroxymethyl) dihydrofur
10、an-2(3H)-one of the experimental method chose two, namely direct reduction and step-by-step approach. Employing direct reduction method to synthesize (S)-5-(hydroxymethyl) dihydrofuran-2(3H)-one made the reaction realized through reduction reaction initialized by the mixture of intermediate product
11、(S)-5-oxotetrahydrofuran- 2-carboxylic acid and BH3 Me2S.Meanwhile, the choice and the amount of reducta成都理工大学硕士学位论文 IV nts,the way to add reaction substrate and the reaction temperature were further studied to discuss the influence of the factors mentioned aboved on the productivity which in turn d
12、etermine the optimal reaction conditions. Column chromatography separation technique was used to purify products, making the yieldreached 78.9%. The synthetic route has fewer side reactions and higher yield. To realize our aim synthesizing the (S)-5-(hydroxymethyl)dihydrofuran-2 (3H)-one by reductio
13、n reaction step by step, (S) -5 - oxo-tetrahydrofuran -2 - formic acid was used in synthesis processes through esterification, sodium borohydride reduction substeps. Influences of ratio of, the raw material reaction time, reaction temperature, pH, and other conditions on the yield were evaluated.Whi
14、le, the yield was 58.0% using the column chromatography purification techniques. The synthtic route characterized by the mild reaction condition and the simple operation processes. . Two methods were compared in this paper, the total yield of direct reduction and step by step reduction was 60.1% and
15、 44.2% respectivel.It is concludedby the experiment that the total yield of step by step reduction, are much lower than the direct reduction which has less reaction steps, and fewer by-products.So, direct reduction method is preferred under manipulated conditions in the laboratory Keywords: L-glutam
16、ic acid (S)-5-oxotetrahydrofuran-2-carboxylic acid (S)-5-(hydroxymethyl)dihydrofuran-2(3H)-one reduction method Synthesis 独创性声明 本人声明所呈交的学位论文是本人在导师指导下进行的研究工作及取得的研究成果。据我所知，除了文中特别加以标注和致谢的地方外，论文中不包含其他人已经发表或撰写过的研究成果， 也不包含为获得 成都理工大学 或其他教育机构的学位或证书而使用过的材料。 与我一同工作的人员对本研究所做的任何贡献均已在论文中作了明确的说明并表示谢意。 学位论文作者签名： 年 月 日 学位论文版权使用授权书 本学位论文作者完全了解 成都理工大学 有关保留、 使用学位论文的规定，有权保留并向国家有关部门或机构送交论文的复印件和磁盘， 允许论文被查阅和借阅。本人授权 成都理工大学 可以将学位论文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩印或扫描等复制
