基 ((三甲) 胺:取代剂和溶剂的溶液结构和反应性
Qiulin You1, Yun Ma1, Ryan A Woltornist1
1Department of Chemistry and Chemical Biology Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States.
本研究详述了胺化合物的合成和结构分析,揭示了依赖溶剂的聚合和反应性. 皇冠乙烯影响胺的行为,而15-皇冠-5的效果低于预期.
科学领域:
- 有机金属化学
- 溶液状态化学
- 光谱学和计算化学
背景情况:
- 胺化合物在有机合成中至关重要.
- 了解它们的聚合和溶解是控制反应性的关键.
- 之前的研究通常假定特定的溶解行为.
研究的目的:
- 合成和描述新的胺化合物,包括同位素.
- 研究这些胺在各种溶剂和皇冠以太的聚合和溶解行为.
- 阐明由这些胺基介导的氨解反应中的结构-活性关系.
主要方法:
- 合成异二甲胺 (NaPTA),二甲胺 (NaPETA) 和二甲胺 (NaBTA).
- 使用29Si NMR光谱,连续变异方法和DFT计算的溶液结构研究.
- 对氨解反应和皇冠复合的定量动力学研究.
主要成果:
- 准备了NaPTA,NaPETA和NaBTA以及它们的15N同位素.
- 对于各种溶剂和皇冠乙醇,确定了二元单元平衡和溶解数,显示了替代剂和溶剂依赖性.
- 速率研究揭示了氨解速率的47,000倍变化,在多和THF中基于二元的机制,以及PMDTA和dwglyme溶解物种的独特行为.
结论:
- 溶解和聚合显著影响胺的反应性.
- 皇冠乙烯的功效有所不同,而15-皇冠-5在加速介导反应方面效率低于预期.
- 获得了对氨解反应的详细机制见解,强调了初级和二级溶解的重要性.
更多相关视频
10:42Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
06:35Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
相关概念视频
Preparation and Reactions of Sulfides
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia
When dissolved in liquid ammonia, an alkali metal,...
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
Alkyl Halides
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Conversion of Alcohols to Alkyl Halides
