1,2-diethyl-3-methyldiaziridine | 39169-68-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,2-diethyl-3-methyldiaziridine
• CAS: 39169-68-1
• 化学式: C₆H₁₄N₂
• 分子量: 114.191
• InChiKey: MWEHSJCMXKPFNI-UHFFFAOYSA-N

物化性质

• 沸点：
  43-45 °C(Press: 20 Torr)
• 密度：
  0.875±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丁炔二酸二乙酯 、 1,2-diethyl-3-methyldiaziridine 在 1-ethyl-3-methylimidazolium hydrogensulfate 作用下， 反应 0.52h， 以35%的产率得到diethyl 1-[3-ethoxy-1-(ethoxycarbonyl)-3-oxoprop-1-enyl]-3-ethyl-2,6-dimethyl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate
  参考文献：
  名称：

  1,2-二烷基和1,2,3-三烷基二氮丙啶的新反应：在离子液体中乙炔二羧酸二乙酯作用下的扩环

  摘要：

  在乙二烯二羧酸二乙酯作用于离子中的1,2-二-和1,2,3-三烷基二氮丙啶的作用下，发现了二氮丙啶环扩环的新反应，从而生成1,2,3,6-四氢嘧啶-4,5-二羧酸二乙酯衍生物液体。J.杂环化​​学，（2009）。

  DOI：

  10.1002/jhet.204
• 作为产物：
  描述：

  N,N-二氯乙胺 、 乙胺 在 水 、 potassium carbonate 作用下， 以 氯仿 为溶剂， 反应 72.0h， 以42%的产率得到1,2-diethyl-3-methyldiaziridine
  参考文献：
  名称：

  Syntheses of 1,2-di- and 1,2,3-trialkyldiaziridines

  摘要：

  The reactions of 1,3,5-trialkylhexahydro-1,3,5-triazines with N-chloroalkylamines resulted in 1,2-dialkyldiaziridines, whereas the reactions of N-chloroalkylamines or N,N-dichloroalkylamines with an excess of primary aliphatic amines gave 1,2,3-trialkyldiaziridines.

  DOI：

  10.1070/mc2005v015n03abeh002107

文献信息

• New method for the synthesis and the mechanism of formation of 1,2-di-and 1,2,3-trialkyldiaziridines
  作者：V. V. Kuznetsov、V. B. Ovchinnikova、V. P. Ananikov、N. N. Makhova

  DOI：10.1007/s11172-006-0548-9

  日期：2006.11

  A new simple approach to the synthesis of 1,2-di-and 1,2,3-trialkyldiaziridines has been developed based on direct chlorination of a mixture of the corresponding aldehyde and an excess of primary aliphatic amine in water. The mechanism of this reaction is proposed and confirmed by quantum chemical calculations at the density functional theory level.

  基于在水中直接氯化相应的醛和过量初级脂肪胺的混合物，开发出了一种合成 1,2- 二和 1,2,3- 三烷基二氮丙啶的新的简单方法。密度泛函理论量子化学计算提出并证实了这一反应的机理。
• The study of the formation mechanism of 1,2,3-trialkyldiaziridines by kinetic and quantum chemistry methods
  作者：V. V. Kuznetsov、V. V. Seregin、D. V. Khakimov、T. S. Pivina、M. D. Vedenyapina、A. A. Vedenyapin、N. N. Makhova

  DOI：10.1007/s11172-014-0691-7

  日期：2014.9

  Using UV spectrometry, we studied for the first time the regularities of AlkNHBr consumption in two variations of the formation of 1,2,3-trialkyldiaziridines in aqueous media: by mixing acetaldehyde and AlkNHBr in excess of AlkNH2 (method 1) and by the reaction of MeCH=NEt with EtNHBr in excess of EtNH2 (method 2). We determined the rate constants of the individual stages of the reaction. Using quantum chemistry methods (DFT/B3LYP/3-21G), we performed calculations of spatial and electronic structures of the reacting compounds, indices of local reactivity, and global electrophilicity of atoms of the individual reaction intermediates, based on which we explained the decrease in the reaction rate when using EtNHBr instead of MeNHBr in method 1. In method 2, the formation of 1,2-diethyl-3-methyldiaziridine occurs exclusively through the intermediate iminium cation.

  利用紫外光谱法，我们首次研究了在水介质中形成 1,2,3-三烷基二氮杂环丁烷的两种变化过程中 AlkNHBr 消耗的规律性：乙醛和 AlkNHBr 在 AlkNH2 过量的情况下混合（方法 1），以及 MeCH=NEt 与 EtNHBr 在 EtNH2 过量的情况下反应（方法 2）。我们测定了反应各个阶段的速率常数。我们使用量子化学方法（DFT/B3LYP/3-21G）计算了反应化合物的空间结构和电子结构、局部反应性指数以及各个反应中间体原子的全局亲电性，并据此解释了在方法 1 中使用 EtNHBr 而不是 MeNHBr 时反应速率降低的原因。在方法 2 中，1,2-二乙基-3-甲基二氮丙啶的生成完全通过中间体亚氨基阳离子进行。
• The role of pH in the synthesis of diaziridines
  作者：V. V. Kuznetsov、N. N. Makhova、Yu. A. Strelenko、L. I. Khmel'nitskii

  DOI：10.1007/bf00959732

  日期：1991.12

  The greatest yield in the synthesis of diaziridines from carbonyl compounds, amines, and aminating reagents in water is achieved at a specific pH, which shifts to less alkaline values with increasing -I effect of the substituents in the carbonyl compound and with decreasing pK(BH+) value of the amine. The role of pH is related to the conditions for the generation of an immonium from the intermediate alpha-aminocarbinol. The nuclear Overhauser effect was used to determine the orientation of the substituents in several diastereomers of the didikyldiaziridines obtained.
• N-bromoalkylamines and NaOBr in the synthesis of diaziridines
  作者：V. V. Kuznetsov、N. N. Makhova、L. I. Khmel'nitskii

  DOI：10.1007/bf00957792

  日期：1989.9
• High pressure‐assisted synthesis of 1,2,3‐trialkyldiaziridines from N‐chloroalkylamines
  作者：Vladimir V. Kuznetsov、Julia S. Syroeshkina、Dmitrii I. Moskvin、Marina I. Struchkova、Nina N. Makhova、Alexey A. Zharov

  DOI：10.1002/jhet.5570450230

  日期：2008.3

  Abstractmagnified imageNew method for the preparation of 1,2,3‐trialkyldiaziridines 1 in high yields, based on the transformation of N‐chloroalkylamines 3 without using carbonyl compounds in the presence of primary aliphatic amines with the same alkyl fragment, potassium carbonate and a small amount of water in CHCl3 under high pressure (500 MPa), was developed. Diaziridines 1 can be synthesized in the same conditions using a larger amount of potassium carbonate instead of primary aliphatic amines however in lower yields. The kinetic investigations on the synthesis of 1,2‐diethyl‐3‐methyldiaziridine 1a from N‐chloroethylamine 3a have shown that the reaction leading to diaziridine 1a proceeds according to the law of the second order.