摘 要 本文探索了伯醇在硫酰氟气体（SO₂F₂）作用下与甲基酮化合物构建α,β-不饱和羰基化合物的新方法。研究内容分为三个部分。 参考相关文献在硫酰氟气体（SO₂F₂）作用下由伯醇制备醛。 制备的醛直接与事先用L-脯氨酸活化过的丙酮发生反应得到α,β-不饱和羰基化合物。 对反应条件进行筛选优化，减少消除副反应，提高产率。选取代表性底物验证该方法的适普性。 研究结果初步验证了伯醇在硫酰氟气体（SO₂F₂）作用下被氧化成醛，再进一步与丙酮发生反应得到α,β-不饱和羰基化合物的方法是可行的。 本文的主要亮点是在于用伯醇直接制备得到α,β-不饱和羰基化合物，原料便宜易得，操作简单，产率较高。 关键词 ：伯醇; 硫酰氟气体; L-脯氨酸; 一锅法; α,β-不饱和羰基化合物 Abstract This article explored a new method for the prPVaration of α,β-unsaturated carbonyl compounds from primary alcohols with methyl ketone compounds under the action of sulfuryl fluoride gas (SO2F2). The research content is divided into three parts. The prPVaration of aldehydes from primary alcohols under the action of sulfuryl fluoride gas (SO2F2) is referred to related literature. The prPVared aldehyde reacts directly with acetone previously activated with L-valine to obtain α,β-unsaturated carbonyl compounds. The reaction conditions were optimized for screening, reducing the elimination of side reactions and increasing the yield. A rPVresentative substrate was selected to verify the suitability of the method. The results preliminarily verified that primary alcohols are oxidized to aldehydes under the action of sulfuryl fluoride gas (SO2F2), and further reaction with acetone to obtain α, β-unsaturated carbonyl compounds is feasible. The main highlights of this paper are the direct prPVaration of α,β-unsaturated carbonyl compounds from primary alcohols. The raw materials are cheap and easy to obtain, the operation is simple, and the yield is high. Key words : primary alcohol; sulfuryl fluoride gas; L-proline; one-pot method; α,β-unsaturated carbonyl compound 目录 第1章 绪论...................................................................................................................1 1.1 硫酰氟气体的简介.........................................................................................1 1.2 α，β-不饱和酮的简介................................................................................1 1.3 研究背景现状与意义.....................................................................................1 1.3.1 α，β-不饱和酮的应用.......................................................................1 1.3.2 α，β-不饱和酮的合成方法...............................................................3 1.3.3 研究意义..............................................................................................5 1.4 研究内容与预期目标.....................................................................................5

1. 硫酰氟气体作用下由伯醇制备醛..................................................................6

2.1 主要实验试剂与仪器.....................................................................................6 2.2 实验步骤.........................................................................................................6 2.3 结果讨论.........................................................................................................6

1. α,β-不饱和羰基化合物的合成.......................................................................8

3.1 主要实验试剂与仪器.....................................................................................8 3.2 方法的探索.....................................................................................................8 3.3 条件优化.......................................................................................................11 3.4 底物拓展.......................................................................................................14 3.4.1 对甲氧基甲醇....................................................................................15 3.4.2 联苯甲醇............................................................................................16 3.4.3 对溴苯甲醇........................................................................................18

1. 总结................................................................................................................20

4.1 实验结果汇总...............................................................................................20 4.2 总结...............................................................................................................24 参考文献......................................................................................................................25 附录..............................................................................................................................27 致谢..............................................................................................................................31

1. 绪论

1.1 硫酰氟气体的简介 硫酰氟气体（SO₂F₂）是一种新型的硫氟交换的点击化学的试剂，以它为原料可以合成多种含有磺酰氟基团的分子，在药物分子、探针等的设计与合成中有着重要的应用前景。 硫酰氟化学性质稳定，并且便宜易得。尽管其对环境和人体健康有一定的影响，由于硫酰氟气体独特的化学性质与空间结构，可以与酚类等有机化合物反应，能够利用其进行广泛的化学反应，推动了其在农业和其他产业方面的应用和发展。 1.2 α，β-不饱和酮的简介 α，β-不饱和酮，又称为苯亚甲基丙酮。这类化合物的数目很多，应用特别广泛。由于它具有双键和羰基共轭的结构，所以兼有烯烃、酮和共轭二烯烃的性质，具有良好的反应性，比如可以进行迈克尔加成反应等等^[1]。它不仅是有机合成的重要组成部分，而且也是香料，生物化学，农业，食品化学，聚合物和材料科学等领域的重要化学品^[5]。α，β-不饱和酮广泛的应用于医药领域。比如查耳酮类化合物是合成黄酮类化合物的重要中间体其本身也有重要的药理作用。除此之外，还有α，β-不饱和酮表现出抗肿瘤、抗炎、抗疟疾作用等多种药理作用。因此，这些化合物的合成在学术界和工业界都非常重要。