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摘要： 含偕二氟基团化合物因为其特殊的化学性质在新的药物分子结构开发中引起了广泛的关注，含氟砌块与不饱和化合物的自由基加成反应是引入偕二氟基团的途径之一。本文我们用课题组已开发的α,α,α-碘二氟苯乙酮类化合物作为含氟砌块，研究了其与4-戊烯-1-醇的加成反应。首先，分别对反应体系的参数例如引发剂、溶剂、碱、反应温度和反应时间及反应投料比进行了筛选，并最终得到了制备环合产物偕二氟取代的四氢呋喃类似物的最优反应条件。具体为在偶氮二异丁腈的引发下，α,α,α-碘二氟苯乙酮类化合物与4-戊烯-1-醇在2,6-二甲基吡啶碱的作用下，在80 °C温度条件下反应得到环化加成产物。在最优反应条件下，对含碘代α-二氟苯乙酮类二氟砌块进行底物扩展，并最终合成了五个偕二氟取代的四氢呋喃类似物，所有的目标产物均经氢谱、碳谱和氟谱核磁谱图以及高分辨质谱的确证。实验结果表示，含供电子基团取代的α,α,α-碘二氟苯乙酮类化合物含氟砌块参与的反应的收率最高。42874
毕业论文关键词：碘代α-二氟苯乙酮类化合物，4-戊烯-1-醇，自由基反应，偕二氟取代的四氢呋喃类似物
The radical addition of iododifluoromethyl ketones to pent-4-en-1-ol
Abstract: Compounds containing gem-difluoromethylene group has attracted widespread attention in the molecular structure of new drug development because of their special properties. Fluorine building blocks and their free radical addition reaction of unsaturated compounds is one of the ways to introduce gem-difluoromethyl group into molecules. In this paper, we used the iododifluoromethyl ketones, which have been developed in our lab, as fluorine building blocks, to react with unsaturated alcohol in the radical reaction. First of all, the reaction condition, such as initiator, solvent, base, reaction temperature and reaction time was screened and optimized. Under the optimal reaction conditions, the generality and scope of this radical cyclization reaction was explored by expanding the iododifluoromethyl ketones building blocks. Finally, five target gem-difluoromethylenated containing tetrahydrofuran derivatives were synthesized and verified by 1H, 13C, 19F NMR and HRMS spectra. The results showed that the substitution groups in the benzene ring was found crucial as the reaction with electron-donating groups substituted 2,2-difluoro-2-iodo-1-phenylethanone led to higher yield of the corresponding tetrahydrofuran derivatives.
Keywords: iododifluoromethyl ketones, pent-4-en-1-ol, the radical addition, gem-difluoromethylenated tetrahydronfuran derivatives
目录
1. 课题背景 1
1.1 有机氟化学的介绍 1
1.2 氟原子的引入 3
1.2.1 直接氟化法 3
1.2.2 含氟砌块法 5
1.3 自由基氟代反应 6
1.4 氟代碘代烷烃及其在合成含氟化合物中的应用 8
1.5 α-二氟苯乙酮类化合物的合成 9
1.6 四氢呋喃化合物 10
1.7 烯醇的氟烷基化反应 11
1.8 课题的目的与意义 13
1.8.1 反应体系的筛选 13
1.8.2 反应底物的扩展 14
2 实验部分 14
2.1 仪器与试剂 14