调查一种与形状相锁定的(Z)-阿齐多克西姆
Alexander H Cleveland1, Jack V Davis1, Gregory H Imler2
1High Explosive Science and Technology, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
The Journal of organic chemistry
|October 11, 2023
概括
由于无法循环,1,2,4-三衍生性亚齐多克西姆是能量材料的不佳候选者. 计算研究揭示了一个高激活能障碍,防止对反应性 (E) 形状的异构化.
科学领域:
- 能量材料是一种能量材料.
- 有机化学 有机化学
- 计算化学是一种计算化学.
背景情况:
- 高化合物在推进剂,爆炸物和制药中至关重要.
- 阿齐多克西姆和1-基醇是高材料的类别.
- 阿齐多克西姆是有活力的,但敏感的,经常循环转化为稳定的异构体.
研究的目的:
- 调查新型1,2,4-三衍生性阿齐多克西姆的意外缺乏反应性.
- 确定这些化合物不能循环的根本原因.
- 探索这些阿齐多克西姆作为能量材料的潜力.
主要方法:
- 新型1,2,4-三衍生性阿齐多克西姆的合成.
- 在既定条件下尝试循环.
- 密度函数理论 (DFT) 的研究.
- 基于晶体学数据的静电电位映射.
主要成果:
- 在标准条件下,即使加热,1,2,4-三衍生性亚齐多克西姆也不会发生循环.
- DFT计算显示了高激活能量 (26.4 kcal mol-1) 的异构化.
- 这些化合物被锁定在非反应性 (Z) 形状中,防止循环.
结论:
- 基于1,2,4-triazine的亚齐多克西姆不适用于需要循环转化为1-hydroxytetrazoles的应用.
- 异构化的高激活能障碍是它们缺乏反应性的主要原因.
- 这些发现凸显了结构分析在设计新能源材料中的重要性.
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