| 分子内氮原子上亲核取代反应生成三元氮杂环的理论研究 |
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| 引用本文： | 曾义,唐丽,王欧平,廖玉龙,郭齐香,林波,冯灏. 分子内氮原子上亲核取代反应生成三元氮杂环的理论研究[J]. 西华大学学报(自然科学版), 2014, 33(4): 49-54. DOI: 10.3969/j.issn.1673-159X.2014.04.012 |
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| 作者姓名： | 曾义 唐丽 王欧平 廖玉龙 郭齐香 林波 冯灏 |
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| 作者单位： | 西华大学物理与化学学院先进计算研究中心 |
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| 基金项目： | 四川省教育厅自然科学青年项目(10ZB149);西华大学校级重点项目(Z0913308);西华大学西华杯项目;西华大学物理与化学学院《结构化学》教改项目 |
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| 摘 要： | 采用密度泛函方法M062X在6-31+G**基组水平上以-CH(CHO)-CH2-NFR(R=H, CH3)为计算模型，考察分子内可能发生的2种竞争反应路径——氮原子上的亲核取代反应和消去反应。R=H的亲核取代反应能垒为49.7 kJ/mol，而R=CH3亲核取代的反应能垒为68.6 kJ/mol，表明CH3的空间位阻明显提高了反应能垒。R=CH3的优势路径是亲核取代，产物为三元氮杂环，而消去历程的能垒为151.7 kJ/mol，得到的是开链副产物。计算结果表明，分子内氮原子上亲核取代反应生成三元氮杂环比较容易发生，且对其竞争路径消去反应有着明显的优势。
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| 关 键 词： | 亲核取代 消去反应 理论研究 密度泛函 |
Theoretical Study of Intramolecular Nucleophilic Substitution on Nitrogen to Three-Membered N-Heterocycle |
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| ZENG Yi;TANG Li;WANG Ou-ping;LIAO Yu-long;GUO Qi-xiang;FENG Hao. Theoretical Study of Intramolecular Nucleophilic Substitution on Nitrogen to Three-Membered N-Heterocycle[J]. Journal of Xihua University(Natural Science Edition), 2014, 33(4): 49-54. DOI: 10.3969/j.issn.1673-159X.2014.04.012 |
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| Authors: | ZENG Yi TANG Li WANG Ou-ping LIAO Yu-long GUO Qi-xiang FENG Hao |
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| Affiliation: | ZENG Yi;TANG Li;WANG Ou-ping;LIAO Yu-long;GUO Qi-xiang;FENG Hao;Research Center for Advanced Computation,School of Physics and Chemistry,Xihua Universtiy; |
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| Abstract: | Using- CH（CHO） -CH2-NFR（ R = H, CH3 ） as the computational model, two possible intramolecular reactions, nucleo- philic substitution on nitrogen and elimination reaction, were investigated by adopting a popular density functional theory-M062X with the 6-31 ＋ G＊ ＊ basis set. The energy barrier of nucleophilic substitution was predicted to be 49.7 kJ/mol for R = H, while it was 68.6 kJ/mol for R = CHz , showing the steric hindrance of CH3 significantly increases the energy barrier. For R = CH3 , the nucleophil- ic substitution with a three-membered N-heterocycle as product was the favorable pathway, while its elimination reaction has a higher energy barrier, 151.7 kJ/mol, with the chain compound as product. These theoretical prediction suggests the nucleophilic substitution on nitrogen for three-membered N-heterocycle can occur easily, and takes some advantage over the corresponding elimination reaction. Therefore, the nucleophilic substitution on nitrogen has certain potential for future experiment. |
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| Keywords: | nucleophilic substitution elimination reaction theoretical study density functional theory |
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