dimethyl 4,5-diaminophthalate | 52412-57-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 4,5-diaminophthalate
• 英文别名: dimethyl 4,5-diaminobenzene-1,2-dicarboxylate
• CAS: 52412-57-4
• 化学式: C₁₀H₁₂N₂O₄
• 分子量: 224.216
• InChiKey: MKTXFIRTNWIOOY-UHFFFAOYSA-N

物化性质

• 沸点：
  442.3±40.0 °C(Predicted)
• 密度：
  1.320±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  105
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 4,5-diaminophthalate 在 氢氧化钾 、 sodium methylate 、 乙酸酐 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.0h， 生成 1-methyl-5-[[(1-adamantylmethyl)amino]carbonyl]benzimidazole-6-carboxylic acid
  参考文献：
  名称：

  Nonpeptide Cholecystokinin-2 Receptor Agonists

  摘要：

  In the course of structural explorations around a series of potent CCK2 receptor antagonists, it was noted that simple N-methylation of the indolic N-H in the parent molecule gave rise to behavior in vivo that was consistent with the compound acting as an agonist. Exploration in vitro confirmed this property, and it was shown that the agonist action could be blocked by the reference CCK2 receptor antagonist, L-365,260. Further examples of this type of modification were explored, and a common theme with regard to agonist behavior was uncovered. Some molecular modeling is also presented in an attempt to throw light on the nature of the ligand receptor interactions that may be giving rise to the differing properties of these, apparently, structurally similar molecules.

  DOI：

  10.1021/jm0010668
• 作为产物：
  描述：

  4-乙酰基氨基邻苯二甲酸二甲酯 在 硫酸 、 palladium on activated charcoal 、 氢气 、 硝酸 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 dimethyl 4,5-diaminophthalate
  参考文献：
  名称：

  鲁米诺相关的邻羟基苯并咪唑类似物的化学发光性质：基于实验和基于DFT的光物理性质方法

  摘要：

  由芳族醛和二氨基邻苯二甲酸酯合成了含有邻羟基苯基苯并咪唑单元的新型鲁米诺-异鲁米诺衍生物，然后与水合肼加热回流。在过氧化氢，六氰合铁酸钾（III）和氢氧化钠溶液中研究了化学发光性质。将化学发光性质与标准鲁米诺和异鲁米诺体系进行了比较，观察到新型衍生物的化学发光性质优于鲁米诺和异鲁米诺。为了更好地了解结构，分子，电子和光物理性质，已使用密度泛函理论计算。实验的吸收和发射波长值与计算的垂直激发和发射值非常吻合。

  DOI：

  10.1016/j.dyepig.2014.08.009

文献信息

• Cyclosporin derivatives
  申请人：Fischer Gunter

  公开号：US09453051B2

  公开（公告）日：2016-09-27

  The present invention relates to novel cyclosporin derivatives that do not cross the cellular membrane. The compounds according to the invention are used in medicine, more particularly in the treatment/diagnosis of acute and chronic inflammatory diseases, viral infections, cancer, degenerative muscle diseases, neurodegenerative diseases and damage that is associated with calcium homeostasis impairment. The novel cyclosporin derivatives additionally have no immunosuppressive effect.

  本发明涉及不穿过细胞膜的新型环孢素衍生物。根据本发明的化合物用于医药，特别是在治疗/诊断急性及慢性炎症疾病、病毒感染、癌症、退行性肌肉疾病、神经退行性疾病以及与钙稳态受损相关的损害。这些新型环孢素衍生物另外不具有免疫抑制作用。
• An Effective Synthetic Entry to Fused Benzimidazoles via Iodocyclization
  作者：Xu Zhang、Yu Zhou、Hengshuai Wang、Diliang Guo、Deju Ye、Yungen Xu、Hualiang Jiang、Hong Liu

  DOI：10.1002/adsc.201100038

  日期：2011.6

  A protocol for the synthesis of the fused heterocyclic polycyclic compounds pyrrole[1,2‐a]benzimidazoles, piperidine[1,2‐a]benzimidazoles and oxa‐fused benzimidazoles using iodine and silver nitrate by an exo‐dig or endo‐dig cyclization pathway at room temperature has been developed. Silver nitrate is a key additive for improving the yield, and the improvement is a result of this additive eliminating

  一种用于合成协议稠合杂环多环化合物的吡咯并[1,2一]苯并咪唑，哌啶并[1,2一]苯并咪唑和使用碘和硝酸银通过氧杂稠合的苯并咪唑外切挖或内切挖环化室温下的通路已经被开发出来。硝酸银是用于提高产量的关键添加剂和改进是这种添加剂消除碘离子的影响的结果（I -），否则会导致形成双碘副产物。进行涉及末端炔基和取代炔基的环化。进一步的官能化表明，所获得的碘衍生物是可能增加分子复杂性的潜在合成中间体。
• [EN] MACROCYCLIC COMPOUNDS<br/>[FR] COMPOSÉS MACROCYCLIQUES
  申请人：ZIYLO LTD

  公开号：WO2018167503A1

  公开（公告）日：2018-09-20

  The present invention relates to macrocyclic compounds which are capable of selective binding to a target saccharide (e.g. glucose), making them particularly well suited for use in saccharide sensing applications. The present invention also relates to processes for the preparation of said compounds, to compositions and devices comprising them, and to their use in the detection of a target saccharide.

  本发明涉及能够选择性结合目标糖类（例如葡萄糖）的大环化合物，使其特别适用于糖类传感应用。本发明还涉及制备所述化合物的方法，包括含有它们的组合物和装置，以及它们在检测目标糖类中的使用。
• Assembly of Amphiphilic Baskets into Stimuli-Responsive Vesicles. Developing a Strategy for the Detection of Organophosphorus Chemical Nerve Agents
  作者：Shigui Chen、Yian Ruan、Jason D. Brown、Judith Gallucci、Veselin Maslak、Christopher M. Hadad、Jovica D. Badjić

  DOI：10.1021/ja408585j

  日期：2013.10.9

  We designed basket 1 to comprise a C3-symmetric hydrophobic cage (477 Å(3)) at its southern edge and three polar ammonium caps at the northern edge. This amphiphilic molecule was observed to assemble into large unilamellar vesicles (350 nm, TEM) in water and thereby entrap dimethyl phenylphosphonate (184 Å(3)) in its cavity (K(app) = (1.97 ± 0.02) × 10(3) M(-1)). The entrapment of the organophosphonate

  我们设计的篮子 1 在其南边缘包括一个 C3 对称疏水笼 (477 Å(3))，在北边缘包括三个极性铵帽。观察到这种两亲分子在水中组装成大的单层囊泡（350 nm，TEM），从而将苯基膦酸二甲酯（184 Å（3））捕获在其腔中（K（app）=（1.97±0.02）×10（3） M(-1))。有机膦酸盐的截留，类似于梭曼大小 (186 Å(3))，触发囊泡材料转化为纳米颗粒（100 nm，TEM）。刺激响应囊泡在其双层膜中包含 1 型篮子，是独特的组件，对于获得新型传感装置很重要。
• On the role of guests in enforcing the mechanism of action of gated baskets
  作者：Yian Ruan、Bao-Yu Wang、Jeremy M. Erb、Shigui Chen、Christopher M. Hadad、Jovica D. Badjić

  DOI：10.1039/c3ob41511b

  日期：——

  We designed and prepared a spacious and gated basket of type 2 (V = 318 Å3) in ten synthetic steps. With the assistance of 1H NMR spectroscopy, we found that the pyridine gates at the rim of 2 form a seam of N–H⋯N hydrogen bonds, thereby adopting right- (P) and left-handed (M) helical arrangements. The recognition characteristics of the smaller basket 1 (V = 226 Å3) and the larger 2 for various solvents as guests were quantified by 1H NMR spectroscopy in CD2Cl2 (61 Å3), CDCl3 (75 Å3), CFCl3 (81 Å3) and CCl4 (89 Å3); the apparent guest binding equilibria Ka were found to be inversely proportional to the affinity of bulk solvents KS for populating each host. The rate of the P/M racemization (krac, s−1) was, for both 1 and 2, studied in all four solvents using dynamic NMR spectroscopy. From these experiments, two isokinetic relationships (ΔS‡P/Mvs. ΔH‡P/M) were identified with each one corresponding to a different mechanism of P/M racemization. A computational study (B3LYP/6-31+G**//PM6) of 1 and 2 in the gas phase indicates two competing racemization pathways: (a) RM1–2 describes a pivoting of a single gate followed by the rotation of the remaining two gates, while (b) RM3 depicts simultaneous (geared) rotation of all three gates. The racemization of the larger basket 2, in all four solvents (packing coefficient, PC = 0.19–0.28), conformed to one isokinetic relationship, which also coincided with the operation of the smaller basket 1 in CD2Cl2 (PC = 0.27). However, in CDCl3, CFCl3 and CCl4 (PC = 0.33–0.39), the mode of action of 1 appears to correlate with a different isokinetic relationship. Thus, we propose that the population of the basket's inner space (PC) determines the mechanism of P/M racemization. When PC < 0.3, the mechanism of operation is RM1–2, whereas, a greater packing, represented when PC > 0.3, enforces the geared RM3 mechanistic alternative.

  我们通过十个合成步骤设计并制备了一个宽敞且有门控的 2 型篮子（V = 318 Å3）。在 1H NMR 光谱的帮助下，我们发现 2 边缘的吡啶门形成了 N-H⋯N 氢键的接缝，从而采用了右手（P）和左手（M）螺旋排列。在 CD2Cl2（61 Å3）、CDCl3（75 Å3）、CFCl3（81 Å3）和 CCl4（89 Å3）中，通过 1H NMR 光谱定量分析了较小的筐体 1（V = 226 Å3）和较大的筐体 2 对各种溶剂作为客体的识别特征；发现表观客体结合平衡 Ka 与大块溶剂 KS 填充每个宿主的亲和力成反比。使用动态核磁共振光谱法研究了 1 和 2 在所有四种溶剂中的 P/M 消旋化速率（krac，s-1）。通过这些实验，确定了两种等动力学关系（ΔS‡P/Mvs.对 1 和 2 在气相中的计算研究（B3LYP/6-31+G**//PM6）表明了两种相互竞争的消旋化途径：(a) RM1-2 描述了单个栅极的旋转，然后是其余两个栅极的旋转，而 (b) RM3 描述了所有三个栅极的同时（定向）旋转。较大的筐体 2 在所有四种溶剂中的消旋化（堆积系数，PC = 0.19-0.28）符合一种等动力学关系，这也与较小的筐体 1 在 CD2Cl2 中的操作（PC = 0.27）相吻合。然而，在 CDCl3、CFCl3 和 CCl4（PC = 0.33-0.39）中，1 的作用模式似乎与不同的等动力学关系相关。因此，我们认为篮内空间（PC）的人口数量决定了 P/M 消旋化的机制。当 PC < 0.3 时，运行机制为 RM1-2，而当 PC > 0.3 时，更大的包装则强制执行等速 RM3 机制。