通过未激活的三级胺直接转化烯胺聚合物的多样化
Lucca Trachsel1, Debabrata Konar1, Jason D Hillman1
1George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, PO Box 117200, Gainesville, Florida 32611-7200, United States.
Journal of the American Chemical Society
|January 8, 2024
概括
研究人员开发了一种用于修改多,N-二甲基胺 (PDMA) 的新型直接转化方法. 这种技术使超高分子量聚合物的前所未有的后聚合修饰成为可能,从而创造出多样化的宏分子结构.
科学领域:
- 聚合物化学
- 大分子科学
- 有机合成
背景情况:
- 在复杂的宏分子中,聚合后的修饰是关键.
- 由于稳定的胺结合,像PDMA这样的烯胺聚合物很难被修改.
研究的目的:
- 为PDMA开发一种新型的直接转法.
- 为了使超高分子量 (UHMW) PDMA 的后聚合修饰.
- 制造出独特的多样化烯合物.
主要方法:
- 在未激活的三级胺的转中取得的进展.
- 用于UHMW PDMA的光化聚合物.
- 设计的烯胺共聚物具有不同的胺反应性.
主要成果:
- 实现PDMA的直接转化,包括UHMW聚合物 (> 10^6 g/mol).
- 在共聚物上展示了顺序性,化学选择性转基因.
- 合成独特多样化的烯合物.
结论:
- 开创了用于聚合物修饰的未激活胺的直接转.
- 建立了一个强大的平台来设计复杂的宏分子,特别是UHMW聚合物.
更多相关视频
相关概念视频
Amines to Amides: Acylation of Amines
2.5K
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary...
2.5K
Preparation of Amines: Alkylation of Ammonia and Amines
3.4K
Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines along with a quaternary ammonium salt through successive SN2 reactions. This process of making the quaternary salt through the direct alkylation method is called exhaustive alkylation.
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering...
3.4K
Preparation of Amides
3.0K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
3.0K
Acid Halides to Amides: Aminolysis
2.8K
Aminolysis is a nucleophilic acyl substitution reaction, where ammonia or amines act as nucleophiles to give the substitution product. Acid halides react with ammonia, primary amines, and secondary amines to yield primary, secondary, and tertiary amides, respectively.
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
In the first step of the aminolysis mechanism, the amine attacks the carbonyl carbon of the acyl chloride to form a tetrahedral intermediate. In the second step, the carbonyl group is re-formed with the elimination of a chloride...
2.8K
Preparation of 1° Amines: Gabriel Synthesis
3.6K
Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...
3.6K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
1.9K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
1.9K


