1,3-INTERACTION BETWEEN AMIDE NITROGENS------Possibility and Limitation

1,3-酰胺氮之间的相互作用------可能性和局限性

• 批准号: 02640384
• 负责人: TAKEUCHI Yoshito
• 金额: $ 1.34万
• 依托单位: THE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640384/
• 关键词: Amide-type nitrogen; 1,3-Interaction; Amine-type nitrogen; Variable temperature NMR; X-ray crystallographic analysis; Restricted rotation of amides; Nitrogen inversion; 動物NMR; 環の反転障壁; ヘテラピペリジンの反転; ピペリジンの反転; ヘテラインドリジジン; MNDO法; ヘテラキノリジジン; ダイナミ

The purpose of this investigation is to explore the possible 1,3- interaction between amide-type nitrogen atoms. It seems that 1,3,5- tribenzoylperhydro-1,3,5-triazine(A) is the most appropriate system for this purpose.The X-ray crystallographic analysis of (A) revealed that the molecule is symmetric and the nitrogen atoms have approximate trigonal structures. This means that the nitrogen involved is a conventional amide nitrogen, which is in contrast to the tetrahedral nitrogen in 1,2-diacylhydrazine. The results were already published in Acta Cryst.Though no indication of 1,3-interaction between amide nitrogens, we explored variable temperature of C-13 NMR spectra of (A). As the temperature lowered, there was observed a change of line-shape which corresponds to the amide rotation. As the temperature further lowered, there was observed the second chemical exchange. This rate process is most likely due to the nitrogen inversion. Unfortunately the NMR spectrometer in general cannot reach temperature below-100C and hence we failed to finalize our interpretation.In conclusion, it is likely that in (A) the nitrogen atoms have a tetrahedral character to some extent. This might mean that the 1,3-interaction between amide nitrogens do exist. Further study would be required to finalize this conclusion.;C and hence we failed to finalize our interpretation.

本研究的目的是探讨酰胺型氮原子之间可能的1,3-相互作用。看来1,3,5-三苯甲酰过氢-1,3,5-三嗪(A)是最合适的体系。x射线晶体学分析表明(A)分子是对称的，氮原子具有近似的三角结构。这意味着所涉及的氮是传统的酰胺氮，这与1,2-二酰基肼中的四面体氮相反。研究结果已经发表在《晶体学报》上。虽然酰胺氮之间没有1,3相互作用的迹象，但我们探索了(A)的C-13核磁共振变温谱。随着温度的降低，观察到与酰胺旋转相对应的线形变化。随着温度进一步降低，出现了第二次化学交换。这个速率过程很可能是由氮转化引起的。不幸的是，核磁共振光谱仪一般不能达到低于100摄氏度的温度，因此我们未能完成我们的解释。综上所述，(A)中氮原子在一定程度上可能具有四面体特征。这可能意味着酰胺氮之间的1,3相互作用确实存在。需要进一步研究才能最后确定这一结论。C，因此我们未能最终确定我们的解释。

项目成果

K.OGAWA,S.YOSHIMURA,Y.TAKEUCHI et al.: "Structure of 1、3、5-Tribenzoylperhydro-1、3、5-triazine" Acta Crystallographca. C48. 1071-1074 (1992)

K.OGAWA、S.YOSHIMURA、Y.TAKEUCHI 等：“1,3,5-三苯甲酰基全氢-1,3,5-三嗪的结构”Acta Crystallographca 1071-1074 (1992)。

Keiichiro Ogawa, S. Yoshimura, Yoshito Takeuchi, A. Katritizky, and Ramia Murugan: "Structure of 1,3,5-Tribenzoyl-1,3,5-triazine" Acta Crystallographica. C48. 1071-1074 (1992)

Keiichiro Okawa、S. Yoshimura、Yoshito Takeuchi、A. Katritizky 和 ​​Ramia Murugan：“1,3,5-三苯甲酰基-1,3,5-三嗪的结构”晶体学报。

J.B.Lambert and Y.Takeuchi(ed.),Y.Takeuchi: "Cyclic Organonitrogen Stereodynamics“Nuclear Magnetic Resonance Methods"" VCH, 21 (1991)

J.B.Lambert 和 Y.Takeuchi（编辑），Y.Takeuchi：“循环有机氮立体动力学“核磁共振方法””VCH，21 (1991)

K.ogawa,S.Yoshimura,Y.Takeuchi,A.Katritzky,R.Murgen: "Structure of 1,3,5ーTribenzoylperhydroー1,3,5ーtriazine" Acta Crystallographica. (1992)

小川、S.Yoshimura、Y.Takeuchi、A.Katritzky、R.Murgen：“1,3,5-三苯甲酰全氢-1,3,5-三嗪的结构”晶体学报（1992）。

K.Ogawa,S.Yoshimura,Y,Takeuchi et al.: "Structure of 1,3,5ーTribenzoylperhydroー1,3,5ーtriazine" Acta Crystallographica. C48. 1071-1074 (1992)

K. Okawa、S. Yoshimura、Y、Takeuchi 等人：“1,3,5-三苯甲酰全氢-1,3,5-三嗪的结构”《晶体学报》1071-1074 (1992)。