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A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
实验和理论研究的propargyl-allenylindium系统的实验和理论研究
Weishi Miao1, Lung Wa Chung, Yun-Dong Wu
1Department of Chemistry, McGill University, Montreal, Quebec, Canada H3A 2K6.
Journal of the American Chemical Society
|October 14, 2004
概括
使用NMR光谱学识别了过渡性有机中间体,allenylindium (I) 和allenylindium (III) 双化物. 此外,还研究了这些化合物的溶剂和甲基替代效应.
科学领域:
- 有机金属化学 有机金属化学
- 频谱学是一种光谱学.
- 计算化学的计算化学
背景情况:
- 有机化合物是有价值的合成中间体.
- 了解过渡性印物种的结构和反应性对于开发新的合成方法至关重要.
- 甲是有机金属反应中常见的前体.
研究的目的:
- 为了研究由propargyl化物形成的过渡性有机中间体.
- 为了阐明溶剂和甲基替代对甲基-氨基系统的影响.
- 用理论计算来支持实验发现.
主要方法:
- 核磁共振 (NMR) 光谱法被用来识别中间体.
- 反应是在水性介质和四二中进行的.
- 使用B3LYP/6-311+G*方法进行了理论计算.
主要成果:
- 过渡性中间体被确定为艾伦联 (I) 和艾伦联 (III) 二化物.
- 该研究揭示了溶剂极性和甲基替代对有机物种的稳定性和结构的影响.
- 实验数据与理论预测一致.
结论:
- 艾利尼林物种是基化物与的反应中的关键中间体.
- 溶剂和甲基替代物显著调节了甲基-氨基平衡.
- 实验和理论方法的结合提供了对这些有机系统的全面了解.
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Preparation of Alkynes: Alkylation Reaction
Introduction
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.
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.
Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
π Molecular Orbitals of the Allyl Cation and Anion
An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with an...
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
π Molecular Orbitals of the Allyl Radical
Allyl radicals are three-carbon conjugated systems. They are readily formed as intermediates in halogenation reactions of alkenes involving the addition of halogen to the allylic carbon instead of the double bond. As seen in allyl cations and anions, each of the three sp2-hybridized carbon atoms in allyl radicals has an unhybridized p orbital. These orbitals combine to give three π molecular orbitals.
The allyl systems have identical molecular orbitals but differ in the number of π electrons.
The allyl systems have identical molecular orbitals but differ in the number of π electrons.
Extraction: Advanced Methods
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is formed in...

