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Synthesis of Heterocylic Compounds Bearing Trifluoromethyl Group

含三氟甲基杂环化合物的合成

基本信息

批准号：
62550632
负责人：
HOJO Masaru
金额：
$ 1.28万
依托单位：
Kobe 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

Reaction of acetals of methyl ketones with trifluoroacetic anhydride occurred cleanly at room temperature to give -substituted -trifluoroacetylvinyl ethers . Likewise orthoacetates gave -trifluoroacetylketene acetals. On treatment of with allyl alcohols in the presence of a small amount of silica gel nucleophilic oxygen-oxygen exchange reaction proceeded easily to afford -substituted -trifluoroacetylvinyl allyl ethers in high yields. When these allyl ethers were heated with silica gel there occurred Claisen rearrangement to give 3-allyl-1,1,1-trifluoro-acetone . These -diketones were then derived to various heterocycles bearing trifluoromethyl and allyl groups by treatment of them with bifunctional nucleophilic reagents such as hydrazines and hydroxylamine. Nucleophilic aromatic nitrogen-nitrogen exchange reaction was successfully performed with the use of N,N-dimethyl-2.4-bistrifluoroacetylnaphthylamine with various amines. The compound was found to undergo interesting cyclization to give fluorine containing naphtho-oxazine in almost quantitative yields by adsorbing on silica gel and keeping it at 78 C for 24 hours without solvent. Reactions of with amino acids, hydrazines and hydroxylamine gave benzindoles, naphthopyrazoles and naphthoisooxazoles, respectively. Assays of these fluorine-containing compounds for physiological activities are now in progress.

甲基酮的缩醛与三氟乙酸酐在室温下完全发生反应，得到取代的三氟乙酰乙烯基醚。同样，原乙酸酯得到β-三氟乙酰基乙烯酮缩醛。在少量硅胶存在下用烯丙醇处理时，亲核氧-氧交换反应容易进行，以高产率提供-取代的-三氟乙酰基乙烯基烯丙基醚。当这些烯丙基醚与硅胶一起加热时，发生克莱森重排，得到3-烯丙基-1,1,1-三氟丙酮。然后，通过用双功能亲核试剂例如肼和羟胺处理这些β-二酮，衍生出带有三氟甲基和烯丙基的各种杂环。 N,N-二甲基-2.4-双三氟乙酰基萘胺与多种胺成功进行了亲核芳香族氮-氮交换反应。发现该化合物通过吸附在硅胶上并在没有溶剂的情况下在78℃下保持24小时，经历有趣的环化，以几乎定量的收率得到含氟萘并恶嗪。与氨基酸、肼和羟胺反应分别生成苯并吲哚、萘并吡唑和萘并异恶唑。这些含氟化合物的生理活性测定正在进行中。