[2,4-Bis(2,2-dimethylpropanoylamino)-5-(2,2-dimethylpropanoyloxy)phenyl] 2,2-dimethylpropanoate | 429693-76-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: [2,4-Bis(2,2-dimethylpropanoylamino)-5-(2,2-dimethylpropanoyloxy)phenyl] 2,2-dimethylpropanoate
• CAS: 429693-76-5
• 化学式: C₂₆H₄₀N₂O₆
• 分子量: 476.613
• InChiKey: CICRHNRMZGZYOS-UHFFFAOYSA-N

物化性质

• 沸点：
  608.7±55.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  4,6-二氨基间苯二酚 、 三甲基乙酰氯 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以92%的产率得到[2,4-Bis(2,2-dimethylpropanoylamino)-5-(2,2-dimethylpropanoyloxy)phenyl] 2,2-dimethylpropanoate
  参考文献：
  名称：

  A 6π + 6π Potentially Antiaromatic Zwitterion Preferred to a Quinoidal Structure:  Its Reactivity Toward Organic and Inorganic Reagents

  摘要：

  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.

  DOI：

  10.1021/ja0354622

文献信息

• Unprecedented zwitterion in quinonoid chemistryElectronic supplementary information (ESI) available: spectroscopic data for 4 and 6 and an ORTEP view of the structure of 4. See http://www.rsc.org/suppdata/cc/b1/b107828n/.
  作者：Olivier Siri、Pierre Braunstein

  DOI：10.1039/b107828n

  日期：2002.1.30

  The first 12π-electron zwitterionic structure in quinonoid chemistry is described with the N,N,O,O -molecule 6 in which the positive charge is π-delocalized between the nitrogen atoms and the negative charge between the oxygen atoms; depending on the crystallization solvent, a 1D-tape-like H-bonded network can be generated in the solid-state.

  N,N,O,O -分子 6 描述了醌类化学中的第一个 12π 电子齐聚物结构，其中正电荷在氮原子之间π-分散，负电荷在氧原子之间π-分散；根据结晶溶剂的不同，可在固态中生成 1D 塔式 H 键网络。
• Toward a 6π+6π Zwitterion or a Bioinhibitors-Related OH-Substituted Aminoquinone: Identification of a Key Intermediate in Their pH Controlled Synthesis
  作者：Pierre Braunstein、Olivier Siri、Jean-philippe Taquet、Qing-Zheng Yang

  DOI：10.1002/chem.200400244

  日期：2004.8.6

  Their pH-controlled reactivity places the N,N'-dialkyl-2-amino-5-lithium alcoholate-1,4-benzoquinonemonoimines [C(6)H(2)(NHCH(2)R') (=NCH(2)R')(=O)(OLi)] 7 (R'=tBu) and 8 (R'=p-C(6)H(4)-tBu) at the crossroads of a new versatile strategy for the preparation of two very different classes of substituted quinones. We describe new 2-(N-alkyl)amino-5-hydroxy-1,4-benzoquinones, which are parent molecules

  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
• 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.