首页> 外文期刊>The Journal of Organic Chemistry >SYNTHESIS, STRUCTURE, AND CONFORMATIONAL DYNAMICS OF BRIDGEHEAD-SUBSTITUTED NITROSAMINES - DI-1-ADAMANTYLNITROSAMINE AND DI-1-NORBORNYLNITROSAMINE
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SYNTHESIS, STRUCTURE, AND CONFORMATIONAL DYNAMICS OF BRIDGEHEAD-SUBSTITUTED NITROSAMINES - DI-1-ADAMANTYLNITROSAMINE AND DI-1-NORBORNYLNITROSAMINE

机译:桥头取代的亚硝胺-DI-1-金刚氨硝胺和DI-1-降冰片硝胺的合成,结构和构型动力学

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摘要

The synthesis of two bridgehead-substituted nitrosamines, di-1-adamantylnitrosamine (1) and di-1-norbornylnitrosamine (2), is described, and their solid state crystal structures are reported. Large bridgehead substituents increase the NNO angle of the nitrosamine (compared to that found for dimethylnitrosamine) without deconjugating the NNO pi system significantly. This structural change correlates with a red-shifted optical absorption, a diminished N,N rotational barrier, and a greater ease of oxidation of these hindered nitrosamines than is observed for dimethylnitrosamine. The electronic basis of these structure/function correlations is examined. It is concluded that 1 is more strained than N-nitroso-2,2,6,6-tetramethylpiperidine (3) which is more strained than 2 and that a raised (in energy) NO n* orbital is primarily responsible for the extreme properties of the former. [References: 31]
机译:描述了两种桥头取代的亚硝胺,二-1-金刚烷基亚硝胺(1)和二-1-降冰片基亚硝胺(2)的合成,并报道了它们的固态晶体结构。较大的桥头取代基可增加亚硝胺的NNO角(与二甲基亚硝胺的NNO角相比),而不会显着地使NNO pi系统脱结合。与对二甲基亚硝胺相比,这种结构变化与红移的光吸收,减少的N,N旋转势垒以及这些受阻亚硝胺的氧化更容易相关。检查了这些结构/功能相关性的电子基础。结论是:1比N-亚硝基-2,2,6,6-四甲基哌啶(3)的应变更大,而N-亚硝基-2,2,6,6-四甲基哌啶(2)的应变更大,并且升高的(能量)NO n *轨道主要负责极端性质。前者。 [参考:31]

著录项

  • 来源
    《The Journal of Organic Chemistry》 |1996年第9期|p. 3177-3182|共6页
  • 作者单位

    VANDERBILT UNIV DEPT CHEM NASHVILLE TN 37235 USA;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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