N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium | 429693-77-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium
• CAS: 429693-77-6
• 化学式: C₁₆H₂₆N₂O₂
• 分子量: 278.395
• InChiKey: JBHKIRFOWVPNAD-UHFFFAOYSA-N

物化性质

• 沸点：
  381.9±42.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  61.69
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium 在 lithium hydroxide 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 3.0h， 生成 2-(4-Dicyanomethyl-phenyl)-2-[5-(2,2-dimethyl-propylamino)-2-hydroxy-3,6-dioxo-cyclohexa-1,4-dienyl]-malononitrile
  参考文献：
  名称：

  TCNE或TCNQ与醌型环之间的区域选择性碳-碳键形成反应。

  摘要：

  DOI：

  10.1002/anie.200502574
• 作为产物：
  描述：

  [2,4-Bis(2,2-dimethylpropanoylamino)-5-(2,2-dimethylpropanoyloxy)phenyl] 2,2-dimethylpropanoate 在 lithium aluminium tetrahydride 、 水 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium
  参考文献：
  名称：

  迈向6pi + 6pi两性离子或与生物抑制剂相关的OH取代的氨基醌：鉴定其pH受控合成中的关键中间体。

  摘要：

  他们的pH值控制的反应性放置N，N'-二烷基-2-氨基-5-锂醇盐-1,4-苯醌单亚胺[C（6）H（2）（NHCH（2）R'）（= NCH（2 ）R'）（= O）（OLi）] 7（R'= tBu）和8（R'= pC（6）H（4）-tBu）的交叉路口，用于制备两个不同种类的取代醌。我们描述了新的2-（N-烷基）氨基-5-羟基-1,4-苯醌，这是生物活性取代的氨基苯醌的母体分子，对于它，N-取代基的变化将变得可能。还报道了此类化合物的首次X射线结构测定结果[[C（6）H（2）（NHCH（2）tBu）（OH）（= O）（2）] 13），我们比较了C（6）环的N-取代基数量对由13个两性离子N，N'自组装产生的超分子网络的影响

  DOI：

  10.1002/chem.200400244

文献信息

• A 6π + 6π Potentially Antiaromatic Zwitterion Preferred to a Quinoidal Structure:  Its Reactivity Toward Organic and Inorganic Reagents
  作者：Pierre Braunstein、Olivier Siri、Jean-philippe Taquet、Marie-Madeleine Rohmer、Marc Bénard、Richard Welter

  DOI：10.1021/ja0354622

  日期：2003.10.1

  A straightforward synthesis of the zwitterionic benzoquinonemonoimine 8 is reported. This molecule is a rare example of a zwitterion being more stable than its canonical forms. It is shown that 8 is best described as constituted of two chemically connected but electronically not conjugated 6 pi electron subunits. Its reactivity with electrophiles such as H+, CH3+, and metal salts leads to the synthesis of new 12,7 electron molecules 12 (H+), 14 (CH3+), and 20 (Pd2+), respectively, in which one or both 6 pi electron subsystems localize into an alternation of single and double bonds, as established by X-ray diffraction. The acidity of the N-H protons of 8 can be modulated by an external reagent. Dependent on the electrophile used, the control of the pi system delocalization becomes possible. When the electrophile simply adds to the zwitterion as in 12, 14, or 15, there is no more negative charge to be delocalized and only the positive charge remains delocalized between the nitrogen atoms. Furthermore, when a reaction with the electrophilic reagent results in deprotonation, as in 17-21, there remains no charge in the system to be delocalized. DFT calculations were performed on models of 8, 12, 14, 20, and on other related zwitterions 9 and 10 in order to examine the influence of the fused cycles on the charge separation and on the singlet-triplet energy gap. An effect of the nitrogen substituents in 8 is to significantly stabilize the singlet state. The dipole moment of 8 was measured to be 9.7 D in dichloromethane, in agreement with calculated values. The new ligands and complexes described in this article constitute new classes of compounds relevant to many areas of chemistry.
• Model Reactions for the Quinone-Containing Copper Amine Oxidases. Anaerobic Reaction Pathways and Catalytic Aerobic Deamination of Activated Amines in Buffered Aqueous Acetonitrile
  作者：Younghee Lee、Lawrence M. Sayre

  DOI：10.1021/ja00116a014

  日期：1995.3

  The quinone form 2 of the N-pivaloyl derivative of 6-hydroxydopamine, developed as a model for the quinone form of the peptidyl 2,4,5-trihydroxyphenylalanine (TOPA) cofactor of the copper amine oxidases, is an effective catalyst for aerobic oxidative deamination of activated amines (e.g., benzylamine and cinnamylamine) in buffered aqueous acetonitrile. The reaction efficiency increases at higher pH and exceeds six turnovers for benzylamine at pH 10, where an apparent alpha-C deuterium kinetic isotope effect of 10 is observed. The yield is limited by the eventual conversion of 2 to the corresponding benzoxazoles (confirming nucleophilic attack of amine at the most electrophilic C-5 carbonyl) and other forms which are incapable of oxidative recycling. Copper(II) inhibits the reaction, in contrast to the free TOPA amino acid, which deaminates benzylamine only when Cu(II) is present. Under anaerobic ''single turnover'' conditions, the products of catalyst reduction are (alkylamino)resorcinols formed via redox cycling reactions of the initial reduced cofactor (either benzenehiol or aminoresorcinol) in the presence of excess amine. Unactivated amines exhibit low deaminative turnover and at high concentrations effect side-chain cleavage of the quinone catalyst induced by C-l Michael addition of amine to the intermediate N-alkyl quinone imines.