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Updated: May 16, 2026

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Synthesis of Esters Via a Greener Steglich Esterification in Acetonitrile
Published on: October 30, 2018
在水相中的乙烯乙烯的Ni催化裂变
Jiayue He1, Chen Zhao, Johannes A Lercher
1Department of Chemistry and Catalysis Research Center, Technische Universität München, 85747 Garching, Germany.
Journal of the American Chemical Society
|November 30, 2012
概括
这项研究引入了一种新的催化剂,用于分解由素衍生的芳香乙烯. 该过程选择性地在120°C的水中切割以太键和化中间体.
科学领域:
- 催化剂是一种催化剂.
- 绿色化学 绿色化学
- 生物质转换生物质转换
背景情况:
- 质素的价值化对于可持续的化学品生产至关重要.
- 在素衍生物中选择性地切割以太键是具有挑战性的.
- 水相处理为环境带来了好处.
研究的目的:
- 开发一种新的Ni/SiO(2) 催化方法,用于在素衍生的芳香乙烯中进行选择性以太键裂解.
- 为了研究含氧中间体的化.
- 了解反应机制和动力学.
主要方法:
- 使用Ni/SiO(2) 催化剂进行解和化反应.
- 在120°C和6bar H的水相中进行反应.
- 分析了α-O-4,β-O-4和4-O-5链接的反应途径.
主要成果:
- 通过解,选择性地切割α-O-4和β-O-4以太键.
- 观察到对4-O-5连接的并行解和水解.
- 显而易见的激活能与键解离能相关.
- 对于β-O-4和4-O-5链接,C-O键裂变是决定速率的.
- 气压力会影响反应速率和产品脱落.
结论:
- Ni/SiO(2) 催化剂能够有效地选择性地分解由素衍生的芳乙烯.
- 反应机制根据以太链接的类型而异.
- 了解动力学和压的作用是过程优化的关键.
相关概念视频
Ethers to Alkyl Halides: Acidic Cleavage
Ethers are generally unreactive and unsuitable for direct nucleophilic substitution reactions since the alkoxy groups are strong bases and, therefore, poor leaving groups. However, ethers readily undergo acidic-cleavage reactions. Ethers can be converted to alkyl halides when heated with strong acids such as HBr and HI in a sequence of two substitution reactions.
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...
Acid Halides to Esters: Alcoholysis
Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
C–C Bond Cleavage: Retro-Aldol Reaction
The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
E2 Reaction: Kinetics and Mechanism
SN2 substitutions and E2 eliminations of alkyl halides proceed via a concerted pathway. While the nucleophile attacks the alpha carbon in SN2 reactions, it functions as a strong base and abstracts a beta hydrogen in the E2 mechanism. The rate-limiting transition state in E2 elimination reactions is characterized by partially broken carbon–hydrogen and carbon–halogen bonds and a partially formed pi bond between the alpha and beta carbons. The beta hydrogen and halide are eliminated...

