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Synthesis and Application of Versatile Monofluoro Building Blocks by Manipulation of the Multifunctional Carbon Compounds.

通过操纵多官能碳化合物合成和应用多功能单氟砌块。

基本信息

批准号：
62570934
负责人：
TAKEUCHI Yoshio
金额：
$ 1.09万
依托单位：
Toyama Medical & Pharmaceutical University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

Development of versatile and practical building blocks for aliphatic monofluoro compounds was attempted in light of recent increasing interest and demand for both new materials and bioactive molecules. Our synthetic approach involves the utilization of the multifunctional carbon compounds and the convenient direct fluorination method which were recently developed in our laboratory. Results are summarized as follows;1. Alkylation follwed by selective fluorination of commercially available nitroacetates produced 2-fluoro-2-nitroalkanoic esters(5), the first fluorine-containing building blocks. The usefulness of 1 was demonstrated by converting into various monofluoro derivatives. Selective denitration of 1 gave 2-fluoroalkanoic esters(2)m which were further converted into the corresponding 2-fluoroalkanoic acids and 2-fluoroalkanols. On the other hand, dealkoxycarbonylation of 1 yielde fluoronitroalkanes, into which the second alkyl groups were introduced to give the di-alkylated fluoron … More itromethanes(3). denitration of 3 afforded successfully fluoroalkanes and fluoroalkenes, which have aingle fluorine atom on the alkyl chains dependent on the choice of teh two alkyl groups.2. Denitrative introduction of the third alkyl groups into 3 was attempted to produce the tertiary alkyl fluorides although in low yields, which are the most difficult structures to prepare among the various organofluorine compounds. On the other hand, denitrative alkylation of 1 gave the target compounds in high yields. We have thus developed versatile building blocks equivalent to the synthon of monofluoromethylene dicarbanion.3. 1-Benzenesulfonyl-1-fluoro-1-nitroalkanes(4), 2-benzenesulfonyl-2-fluoroalkanoic esters(5), and 1-benzenesulfonyl-1-fluorophoalkylphosphonates(6) were also prepared from the corresponding difunctional carbon compounds. Removal of the functional groups of 4 and 5 failed. However, reaction of 6 with various carbonyl compounds produced fluorovinylsulfone derivatives(7). Which were further transformed into various monofluoro compounds via michael addition, diels-alder reaction, and 1,3-dipolar cycloaddition. Less

鉴于最近对新材料和生物活性分子日益增长的兴趣和需求，人们试图开发多用途和实用的脂肪族单氟化合物的构建块。我们的合成方法包括利用我们实验室最近开发的多官能碳化合物和方便的直接氟化法。主要研究结果如下：1.商品硝酸乙酸酯的选择氟化反应生成的2-氟-2-硝基烷酸酯(5)，是第一个含氟的构筑块。通过转化成各种单氟衍生物，证明了1的用途。1经选择性脱硝制得2-氟烷酸酯(2)m，再转化为相应的2-氟烷酸和2-氟烷醇。另一方面，1-亚氟硝基的脱烷氧羰化反应，在其中引入了第二烷基，得到了二烷基化氟…较多的二甲基甲烷(3)。3的脱氮反应成功地生成了氟烷烃和氟烯烃，它们的烷基链上只有一个氟原子，这取决于两个烷基的选择。尝试在3中反硝化引入第三烷基，以生成叔烷基氟化物，但产率较低，这是各种有机氟化合物中最难制备的结构。另一方面，1的反硝化烷基化得到了高产率的目标化合物。因此，我们开发了相当于单氟亚甲基二碳离子合成子的多功能构建块。由相应的双功能碳化合物还合成了1-苯磺酰基-1-氟-1-硝基-烷烃(4)、2-苯磺酰基-2-氟烷酸酯(5)和1-benzenesulfonyl-1-fluorophoalkylphosphonates(6)。4和5的官能团移除失败。然而，6与各种羰基化合物反应生成了氟乙烯基砜衍生物(7)。通过Michael加成、Diels-Alder反应和1，3-偶极环加成反应进一步转化为各种单氟化合物。较少