Preparation and Synthetic Application of Fluorinated Vinamidinium Salts as Building Unit for Synthesis of Organofluorine Molecules

含氟维脒盐的制备及其作为有机氟分子合成结构单元的应用

• 批准号: 05650855
• 负责人: YAMANAKA Hiroki
• 金额: $ 1.34万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650855/
• 关键词: Fluorinated vinamidinium; Fluorinated ammonium; 1,5-diazapentadienium; Fluorinated heterocycle; 5-Fluoropyrimidine; 4-Fluoropyrazole; Fluorinated dienaminone; 1,5-ジアザペンタジエニウム; 含フッ素合成素子

We investigated the preparation and synthetic utilization of the fluorinated vinamidinium (1,5-diaza-1,3-pentadienium) salts, which have the potential of serving as fluorinated and conjugated three-carbon building blocks in organic synthesis.1. Preparation of fluorinated vinamidinium salts :We Prepared the beta-fluorovinamidinium salt (1) having various substituents on nitrogen by our previously developed method. We also tried the preparation of another fluorinated vinamidinium salt (2) by the new reaction of N- (2,3,3,4,4,5,5-heptafluoro-1-pentenyl) trimethylammonium iodide with dialkylamines.2. Investigation on the utilization of beta-fluorovinamidium salt as synthon :(1) The reactions of beta-fluorovinamidinium salt (1) with bifunctional nitrogen-nucleophiles (amidines, hydrazines) easily gave the corresponding monofluorinated heterocycles (5-fluoro-pyrimidines, 4-fluoropyrazoles) in good yields. (2) The reactions of 1 with enolates proceeded smoothly to afford multifunctionalized dienaminone derivatives having fluoro-substituent. (3) Although the existence of 2 as intermediate in the reaction described above was confirmed, its isolation was unsuccessful. However, when the reaction mixture was treated with water, fluorinated alpha, beta-unsaturated aldehydes and ketones were obtained. The treatment with methylhydrazine instead of water produced the corresponding pyrazole.Present studies showed that fluorovinamidinium salts were very useful synthon to introduce fluorinated C3 unit into substrates. We also developed new facile and efficient method for synthesis of organofluorine compounds such as fluorinated heterocycles and dienaminones.

我们研究了氟化乙烯基丹（1,5-二氮二烷-1,3-苯二烯）盐的制备和合成利用，这些盐具有有机合成中的氟化和共轭的三碳构建块的潜力1。制备氟化乙烯胺盐：我们制备了通过我们先前开发的方法在氮上具有各种取代基的β-氟氨基丙酮盐（1）。我们还尝试通过N-（2,3,3,3,4,4,4,5,5- heptafluoro-1-戊烯基）三甲基铵与二甲胺的新反应来制备另一种氟化的乙烯胺盐（2）。2。 Investigation on the utilization of beta-fluorovinamidium salt as synthon :(1) The reactions of beta-fluorovinamidinium salt (1) with bifunctional nitrogen-nucleophiles (amidines, hydrazines) easily gave the corresponding monofluorinated heterocycles (5-fluoro-pyrimidines, 4-fluoropyrazoles) in good yields. （2）1与烯醇的反应顺利进行，以实现具有氟硫化物的多功能二烯胺衍生物。 （3）尽管在上述反应中存在2个中间体的存在，但其分离却没有成功。但是，当反应混合物用水，氟化α，β-不饱和醛和酮处理时。用甲基羟嗪而不是水的处理产生了相应的吡唑。表明的研究表明，氟丙酰氨基盐盐非常有用，可以将氟化的C3单位引入底物中。我们还开发了新的便捷和有效的方法来合成有机氟的化合物，例如氟化杂环和二烯胺。

项目成果

Xifeng Shi: "Reactions of β-Fluorovinamidinium Salt with Bifunctional Hetero Nucleophiles.A New Synthetic Route to Fluorinated Heterocycles" Tetrahedron Letters. 36. 1527-1530 (1995)

石西峰：“β-氟脒盐与双功能异杂亲核试剂的反应。氟化杂环的新合成路线”Tetrahedron Letters 36。1527-1530 (1995)

Xifeng Shi, Takashi Ishihara, Hiroki Yamanaka, J.T.Gupton: "Reactions of beta-Fluorovinamidinium Salt with Bifunctional Hetero Nucleophiles. A New Synthetic Route to Fluorinated Heterocycles." Tetrahedron Letters. 36. 1527-1530 (1995)

Xifeng Shi、Takashi Ishihara、Hiroki Yamanaka、J.T.Gupton：“β-氟脒盐与双功能杂亲核试剂的反应。氟化杂环的新合成路线。”