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.

我们研究了氟化维脒(1,5-二氮杂-1,3-戊二烯鎓)盐的制备和合成利用，该盐具有作为有机合成中氟化和共轭三碳结构单元的潜力。 1．氟化乙烯脒盐的制备：我们通过先前开发的方法制备了在氮上具有各种取代基的β-氟乙烯脒盐(1)。我们还尝试通过N-(2,3,3,4,4,5,5-七氟-1-戊烯基)三甲基碘化铵与二烷基胺的新反应制备另一种氟化维脒盐(2)。利用β-氟乙烯基盐作为合成子的研究：(1) β-氟乙烯基盐(1)与双功能氮亲核试剂(脒、肼)反应容易得到相应的单氟杂环(5-氟嘧啶、4-氟吡唑），收率良好。 (2)1与烯醇化物的反应顺利进行，得到具有氟取代基的多官能化二胺酮衍生物。 (3)虽然确认了上述反应中作为中间体2的存在，但其分离未成功。然而，当反应混合物用水处理时，得到氟化的α，β-不饱和醛和酮。用甲基肼代替水处理产生相应的吡唑。目前的研究表明，氟维脒盐是将氟化C3单元引入底物中的非常有用的合成子。我们还开发了新的简便有效的合成有机氟化合物（例如氟化杂环和二烯胺酮）的方法。

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。”