2,3-diisopropyl-2,3-diazabicyclo[2.2.2]octane | 152050-08-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: 2,3-diisopropyl-2,3-diazabicyclo[2.2.2]octane
• 英文别名: 2,3-di(propan-2-yl)-2,3-diazabicyclo[2.2.2]octane
• CAS: 152050-08-3
• 化学式: C₁₂H₂₄N₂
• 分子量: 196.336
• InChiKey: ZZGYYKPESRIKDZ-UHFFFAOYSA-N

物化性质

• 沸点：
  255.1±23.0 °C(predicted)
• 密度：
  0.938±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-diisopropyl-2,3-diazabicyclo[2.2.2]octane 在 nitrosyl hexafluorophosphate 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以78.5%的产率得到2,3-isopropyl-2,3-diazabicyclo<2.2.2>octane radical cation hexafluorophosphate
  参考文献：
  名称：

  构象保护的肼自由基阳离子和对肼电子转移反应的传动效应

  摘要：

  来自 7 (22/tBu,iPr) 和 9 (22/iPr 2 ) 的 N-异丙基化肼自由基阳离子是可分离的，并且是缺乏所有 Ca-H 键的可分离肼自由基阳离子的第一个例子，它们被保护为双环中的桥头碳戒指。9 的循环伏安图显示铂的电化学不可逆氧化和还原波。有人认为，这是由于异丙基的传动效应，导致中性 9 的自由基阳离子以不稳定的构象生成。对比导致肼循环伏安曲线电化学不可逆的动力学和热力学构象效应

  DOI：

  10.1021/ja00076a020
• 作为产物：
  描述：

  以 乙腈 为溶剂， 生成 2,3-diisopropyl-2,3-diazabicyclo[2.2.2]octane
  参考文献：
  名称：

  Intermolecular Electron-Transfer Reactions Involving Hydrazines

  摘要：

  The self-exchange electron-transfer (ET) rate constant k(22) for 1,2,3,4,5-pentamethylferrocene was determined by NMR line broadening to be 8.5(+/-0.8) x 10(6) M(-1) s(-1) (25 degrees C, CD3CN/0.09 M Et(4)NBF(4)) and k(11) for the bis-N,N-bicyclic hydrazine, 9,9'-bi-9-azabicyclo[3.3.1]nonane, to be 8.7(0.5) x 10(3) M(-1) s(-1) (25 degrees C, CH2Cl2). These self-exchange rate constants are used to analyze cross reactions of these molecules with hydrazines, ferrocenes, and tetramethyl-p-phenylenediamine (TMPD) using Marcus theory. Cross-reaction rate constants for eight reactions are reported. Included are six cross-reactions between methylferrocenes and four cyclic hydrazines, one hydrazine, hydrazine-reaction, and the reduction of TMPD(+) by a cyclic hydrazine. These are the first cross-reaction rate constants reported for hydrazine-hydrazine and hydrazine-TMPD(+) ET reactions. The crossreaction rate constants are used to test the application of Marcus theory to hydrazine ET reactions and to extract estimates of hydrazine self-exchange ET rate constants in systems for which direct measurement is presently impossible.

  DOI：

  10.1021/jo9510090

文献信息

• Conformationally protected hydrazine radical cations and the gearing effect on a hydrazine electron-transfer reaction
  作者：Stephen F. Nelsen、Ling Jen Chen、Peter A. Petillo、Dennis H. Evans、Franz A. Neugebauer

  DOI：10.1021/ja00076a020

  日期：1993.11

  The N-isopropylated hydrazine radical cations from 7 (22/tBu,iPr) and 9 (22/iPr 2 ) are isolable and are the first examples of isolable hydrazine radical cations which lack all Ca-H bonds being protected as bridgehead carbons in bicyclic rings. The cyclic voltammogram of 9 shows electrochemically irrevesible oxidation and reduction waves at platinum. It is argued that this results from a gearing effect

  来自 7 (22/tBu,iPr) 和 9 (22/iPr 2 ) 的 N-异丙基化肼自由基阳离子是可分离的，并且是缺乏所有 Ca-H 键的可分离肼自由基阳离子的第一个例子，它们被保护为双环中的桥头碳戒指。9 的循环伏安图显示铂的电化学不可逆氧化和还原波。有人认为，这是由于异丙基的传动效应，导致中性 9 的自由基阳离子以不稳定的构象生成。对比导致肼循环伏安曲线电化学不可逆的动力学和热力学构象效应
• Intermolecular Electron-Transfer Reactions Involving Hydrazines
  作者：Stephen F. Nelsen、Ling-Jen Chen、Michael T. Ramm、Gilbert T. Voy、Douglas R. Powell、Molly A. Accola、Troy R. Seehafer、Jobiah J. Sabelko、Jack R. Pladziewicz

  DOI：10.1021/jo9510090

  日期：1996.1.1

  The self-exchange electron-transfer (ET) rate constant k(22) for 1,2,3,4,5-pentamethylferrocene was determined by NMR line broadening to be 8.5(+/-0.8) x 10(6) M(-1) s(-1) (25 degrees C, CD3CN/0.09 M Et(4)NBF(4)) and k(11) for the bis-N,N-bicyclic hydrazine, 9,9'-bi-9-azabicyclo[3.3.1]nonane, to be 8.7(0.5) x 10(3) M(-1) s(-1) (25 degrees C, CH2Cl2). These self-exchange rate constants are used to analyze cross reactions of these molecules with hydrazines, ferrocenes, and tetramethyl-p-phenylenediamine (TMPD) using Marcus theory. Cross-reaction rate constants for eight reactions are reported. Included are six cross-reactions between methylferrocenes and four cyclic hydrazines, one hydrazine, hydrazine-reaction, and the reduction of TMPD(+) by a cyclic hydrazine. These are the first cross-reaction rate constants reported for hydrazine-hydrazine and hydrazine-TMPD(+) ET reactions. The crossreaction rate constants are used to test the application of Marcus theory to hydrazine ET reactions and to extract estimates of hydrazine self-exchange ET rate constants in systems for which direct measurement is presently impossible.