【作者】 韩业晶；

【导师】 曹端林；

【作者基本信息】 中北大学 ， 化学工艺， 2014， 硕士

【摘要】 丙炔酸酯是一类具有酯基的不饱和化合物，酯基的吸电子作用使碳碳三键具有较高的活性，易发生亲核加成反应。近三十年来，通过对丙炔酸酯的结构进行修饰得到的大量丙炔酸酯的衍生物，作为有机合成中间体，广泛应用于医药，香料等化学工业产品中。由于二茂铁问世以来，二茂铁及其衍生物因其本身的特点，如疏水性，生物可氧化性，芳香性，稳定性，低毒性，生物活性等，而被广泛应用于医学，航天等领域。近年来研究表明，二茂铁衍生物具有多种生物活性，如抗肿瘤性，抗贫血，杀菌，杀虫，抗炎等，具有广泛的应用前景。因此，合成含有二茂铁基团的丙炔酸酯具有深远的研究价值和重要的现实意义。本文以二茂铁为原料，经Vilsmeier-Haack反应得二茂铁甲醛；通过二茂铁甲醛与磷叶立德发生Witting反应得到取代烯；取代烯在碱性条件下发生脱卤化得到二茂铁乙炔；以二茂铁乙炔和甲醇为反应底物，合成了一个新型的二茂铁丙炔酸酯化合物。以二茂铁乙炔和甲醇为实验模版，考察了多种因素对实验的影响，对催化剂、催化剂与助催化剂用量和反应中添加的碱，进行了实验条件的优化。通过优化，确定最佳反应条件为：以PdCl₂为催化剂，用量为5mol%时，助催化剂CuI的用量为4mol%，在碱K₂CO₃作用下，回流2h，产率较高。在上述优化好的条件下，研究了8个不同的脂肪醇同CO和二茂铁乙炔的偶联反应。反应产物二茂铁丙炔酸甲酯、二茂铁丙炔酸乙酯、二茂铁丙炔酸正丙酯等6种化合物均为未见文献报道的新化合物。所有产物的结构均通过IR、1HNMR、¹³C NMR和HR-ESI-MS等波谱分析方法进行了鉴定表征。更多还原

【Abstract】 Propiolic acid ester is a kind of ester of unsaturated compounds, ester of electronicabsorption effect on the high activity of carbon carbon triple bond, prone to nucleophilicaddition reaction. Nearly30years, through the structure of propiolic acid ester was modifiedto get plenty of propiolic acid ester derivatives, as an organic synthesis intermediates, arewidely used in pharmaceutical, chemical industrial products such as spices. Because offerrocene since the advent of ferrocene and its derivatives because of its own characteristics,such as hydrophobicity, biological oxidizability, aromaticity, stability, low toxicity, biologicalactivity and so on, and is widely used in medical, aerospace and other fields. In recent years,studies have shown that ferrocene derivatives has many biological activities, such as antitumor, anemia, bactericidal and insecticidal, anti-inflammatory and so on, has wideapplication prospect. erefore, the synthesis of propiolic acid ester containing ferrocene grouphas far-reaching research value and practical significance.This article with ferrocene as raw material, the Vilsmeier Haack reaction of ferroceneformaldehyde; By ferrocene formaldehyde and phosphorous Ye Lide witting reaction to getreplaced material; Replace the ene in alkaline conditions to take off the halide get ferroceneacetylene, so is good for carbonylation reaction of ferrocene acetylene and methanol asreaction substrate, synthesis of a new type of ferrocene propiolic acid ester compounds. Withferrocene acetylene and methanol as the template to the dosage of catalyst, catalyst andcocatalyst and adding alkali, reaction to optimize the experimental conditions. By optimizing,optimum reaction conditions were determined as: PdCl₂as catalyst dosage of5mol%, theamount of cocatalyst CuI4mol%, under the influence of alkali K₂CO₃, reflow2h, the yieldis higher. In the optimized conditions, the above eight different fatty alcohols was studiedwith CO and ferrocene coupling reaction of acetylene. Reaction product Ferrocene propiolicacid methyl ester, ferrocene propiolic acid ethyl ester, ferrocene propiolic acid is acrylic esterof6kinds of compounds no literature reports. The structure was characterized by1H NMR,¹³C NMR, IR and HR-ESI-MS.更多还原