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Theoretical Study of Intramolecular Nucleophilic Substitution on Nitrogen
Zeng Yi, Ren Yi*
College of Chemistry, Sichuan University, Chengdu 610064
Abstract:
Using the -CHR-(CH2)3-NFCH3(R=H, CH3, CH2CF3, CHO, COCH3) as the computational model, the two possible intramolecular reactions, nucleophilic substitution on nitrogen and elimination reaction, were studied at the theoretical level of MP2(full)/6-31+G(d,p). The results indicate that the elimination mechanism, when the -CHR radical is more basic (R=H, CH3, CH2CF3) leading to linear products R-CH2-(CH2)3N=CH2 is preferred. In contrast, electro-withdrawing groups CHO and COCH3 on the attacking site will favor the intramolecular nucleophilic substitution of nitrogen and form 5-membered heterocyclic compounds. These theoretical predictions agree with the available experiments.
Key words:  Intramolecular nucleophilic substitution, Elimination, Theoretical calculation
FundProject:
分子内氮原子上亲核取代反应的理论研究
曾义, 任译*
四川大学化学学院,成都,610064
摘要:
在MP2(full)/6-31+G(d,p) 理论水平上,以-CHR-(CH2)3-NFCH3 (R=H, CH3, CH2CF3, CHO, COCH3) 为计算模型,对分子内可能发生的两条反应路径-氮原子上的亲核取代反应及消去反应进行了理论研究.结果表明,当进攻基团-CHR为碱性较强的基团,即R=H、 CH3、 CH2CF3 时,有利于发生消去反应而生成直链化合物R-CH2-(CH2)3N=CH2;而当R为吸电子基团 -CHO、-COCH3时,主要发生分子内氮原子上的亲核取代反应, 产物为含氮的五员杂
关键词:  分子内亲核取代  消去反应  理论计算
DOI:10.1088/1674-0068/18/6/918-924
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