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Synthesis of Esters Via a Greener Steglich Esterification in Acetonitrile
Published on: October 30, 2018
甲基对二甲基酸盐在乙醇中的反应性,聚合和聚合结构的影响
Wolfram Henze1, Armand Vyater, Norbert Krause
1Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrichs-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany.
Journal of the American Chemical Society
|December 8, 2005
概括
添加到吉尔曼酸盐中的四氨酸 (THF) 会以不同的方式影响反应性. THF通过分解盐来增强二甲基酸盐 (1.LiI) 的反应性,同时通过分解寡合体来降低基尔曼酸盐 (1.LiCN) 的反应性.
科学领域:
- 有机金属化学 有机金属化学
- 合成有机化学 合成有机化学
- 物理有机化学 有机化学
背景情况:
- 人们对有机酸盐的反应性知之甚少,这阻碍了合理的控制.
- 聚合状态和结构显著影响有机酸盐的反应性.
- 了解这些因素对于优化合成应用至关重要.
研究的目的:
- 为了研究四基 (THF) 对吉尔曼酸盐的反应性和聚合物结构的影响.
- 阐明分离在调节有机酸盐反应中的作用.
- 为了提供直接的实验证据来证明蓝色-吉尔曼酸盐的结构.
主要方法:
- 动力测量以确定反应速率.
- 核磁共振 (NMR) 谱学,包括扩散测量, (1) H - 7) Li HOE 和 (1) H - 1) H NOE.
- 使用的模型系统是Me(2)CuLi.LiI (1.LiI) 和Me(2)CuLi.LiCN (1.LiCN) 在乙烯 (DEE) 中.
- 研究了对4,4-二甲基环合二烯的1,4-添加反应.
主要成果:
- 添加四氨酸 (THF) 加快了1.LiI的反应性,但降低了1.LiCN的反应性.
- 核磁共振研究显示,THF从1.LiI聚合物中分解盐,同时分解1.LiCN寡合物,同时保持盐的附着.
- 直接的实验证据证实,CN(-) 组附着在岩-吉尔曼酸盐中的酸盐部分.
结论:
- 二基酸盐的活性可以通过对THF或盐的控制添加来微调.
- 通过THF分解有机酸的寡合物,导致蓝-吉尔曼酸的反应性降低.
- 少量THF可以提高合成应用中的二基酸盐的反应性.
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