2,5-二氢-2,5-二氧代-1H-吡咯-1-乙酸甲酯 | 164025-07-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2,5-二氢-2,5-二氧代-1H-吡咯-1-乙酸甲酯
• 英文名称: (2,5-dioxo-2,5-dihydro-pyrrol-1-yl)acetic acid methyl ester
• 英文别名: 1H-Pyrrole-1-acetic acid, 2,5-dihydro-2,5-dioxo-, methyl ester；methyl 2-(2,5-dioxopyrrol-1-yl)acetate
• CAS: 164025-07-4
• 化学式: C₇H₇NO₄
• 分子量: 169.137
• InChiKey: FJGBWUWWURPIJN-UHFFFAOYSA-N

物化性质

• 熔点：
  45-48℃ (ethyl acetate ligroine )
• 沸点：
  286.6±23.0 °C(Predicted)
• 密度：
  1.368±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,5-二氢-2,5-二氧代-1H-吡咯-1-乙酸甲酯 以 乙腈 为溶剂， 反应 2.0h， 以94%的产率得到(5-Methoxycarbonylmethyl-1,3,4,6-tetraoxo-octahydro-cyclobuta[1,2-c;3,4-c']dipyrrol-2-yl)-acetic acid methyl ester
  参考文献：
  名称：

  Investigations of Novel Azomethine Ylide-Forming Photoreactions of N-Silylmethylimides

  摘要：

  The scope of a recently discovered (Yoon, E. C. et al. J. Am. Chem. Sec. 1995, 117, 2698), azomethine ylide-forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. Photolysis of N-[(trimethylsilyl)methyl]maleimide (4) in acetonitrile leads to efficient production of the tricyclic product 16, formed by trapping of the photogenerated azomethine ylide intermediate 15 through cydoaddition with 4. Irradiation 4 in solutions containing high concentrations of the dipolarophiles, acrylonitrile or fumaronitrile, results in production of the products (19-21 and 23-24, respectively) arising by cycloaddition of the ylide 15 with the added dipolarophiles. In contrast, photolysis of the nonconjugated cyclic imide, N-[(trimethylsilyl)methyl]succinimide (5), brings about N-acyl migration resulting in the exclusive production of the unstable, iminolactone 30. On the other hand, acyclic, N-trimethylsilylmethyl aroyl imides 6-8 undergo the excited state C to O silyl migration reaction to produce azomethine ylide intermediates 35. Both in the presence or absence of added dipolarophiles, these ylides undergo electrocyclization to form transient aziridine intermediates 36 which react further by ring opening to generate N-phenacylamide products 32-34. In contrast, the nonconjugated imide, N-[(trimethylsilyl)methyl]-N-acetylacetamide (9), is unreactive upon irradiation. Similarly, simple N-[(trimethylsilyl)methyl] amides 10-13, while being photochemically labile, do not react to form ''trappable'' ylide intermediates upon irradiation. The results outlined above are presented and discussed in terms of the scope and limitations of the new, azomethine ylide-forming photoreaction of silylmethyl imides.

  DOI：

  10.1021/jo00113a012
• 作为产物：
  描述：

  (Z)-4-((carboxymethyl)amino)-4-oxobut-2-enoic acid 在 caesium carbonate 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 2,5-二氢-2,5-二氧代-1H-吡咯-1-乙酸甲酯
  参考文献：
  名称：

  自我复制与反应性二元复合物——通过简单的结构修饰来操纵识别介导的环加成。

  摘要：

  通过在反应物种类上引入互补识别位点，可以提高呋喃和马来酰亚胺之间的 Diels-Alder 环加成反应速率和选择性。其他结构元素的微妙操作允许通过自我复制或形成预反应二元复合物来产生观察到的速率增强和选择性。

  DOI：

  10.1039/b406862a

文献信息

• [EN] GLUCOCORTICOID RECEPTOR AGONIST AND IMMUNOCONJUGATES THEREOF<br/>[FR] AGONISTE DU RÉCEPTEUR DES GLUCOCORTICOÏDES ET IMMUNOCONJUGUÉS DE CELUI-CI
  申请人：ABBVIE INC

  公开号：WO2017210471A1

  公开（公告）日：2017-12-07

  Provided herein are glucocorticoid receptor agonist immunoconjugates, glucocorticoid receptor agonists, and methods of using the same, e.g., to treat autoimmune or inflammatory diseases.

  提供的是糖皮质激素受体激动剂免疫偶联物、糖皮质激素受体激动剂以及使用它们的方法，例如，用于治疗自身免疫性或炎症性疾病。
• Synthesis and antimicrobial activities of N-substituted imides
  作者：Frederic Zentz、Alain Valla、Regis Le Guillou、Roger Labia、Anne-Gabrielle Mathot、Danielle Sirot

  DOI：10.1016/s0014-827x(02)01217-x

  日期：2002.4

  toluene. Most of N-substituted maleimides showed an interesting antimicrobial activity towards bacteria from the ATCC collection (Staphylococcus aureus ATCC 25923, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853) but the MIC values for P. aeruginosa were always high (128 microg/ml). The imides with alkyl substituents showed higher activities than aromatic

  在我们关于新型抗菌剂的研究计划领域中，合成了一系列N-取代的酰亚胺。这些化合物是通过将酰胺基酸在乙酸酐/乙酸钠或六甲基二硅氮烷/溴化锌中的羟基芳族衍生物环化而获得的。羟基烷基马来酰亚胺是通过将相应的氨基醇与马来酸酐在沸腾的甲苯中缩合而直接制备的。大多数N-取代的马来酰亚胺对来自ATCC集合的细菌（金黄色葡萄球菌ATCC 25923，粪肠球菌ATCC 29212，大肠杆菌ATCC 25922和铜绿假单胞菌ATCC 27853）显示出有趣的抗菌活性，但铜绿假单胞菌的MIC值始终很高（ 128微克/毫升）。具有烷基取代基的酰亚胺显示出比​​MIC值在8-32 microg / ml范围内的芳族类似物更高的活性。相比之下，琥珀酰亚胺几乎没有活性。
• Structure–reactivity relationships in a recognition mediated [3+2] dipolar cycloaddition reaction
  作者：Andrew J. Sinclair、Vicente del Amo、Douglas Philp

  DOI：10.1039/b908072d

  日期：——

  The [3+2] dipolar cycloaddition between an azide and maleimide can be accelerated by a factor of more than 100 simply by attaching complementary recognition sites to the reactive partners. This rate acceleration derives from the formation of a reactive binary complex between the azide and the maleimide. The variation of the observed rate acceleration with simple structural changes, such as adding additional rotors, should be relatively predictable. However, the application of a simple, rotor-based increment in the systems reported here is insufficient to predict reactivity correctly. Computational studies suggest that the nature of the available reaction pathways within the binary complex formed by the reactants is important in determining the reactivity of a given complex.

  通过在活性伙伴上附加互补识别位点，[3+2]偶极环加成反应中叠氮与马来酰亚胺之间的反应速度可以加快超过100倍。这种加速源于叠氮与马来酰亚胺之间反应性二元复合体的形成。观察到的反应加速对于简单的结构变化，如增加额外的旋转体，应该是相对可预测的。然而，对于此处报道的系统，仅依靠基于旋转体的简单增量不足以准确预测反应活性。计算研究表明，反应物形成的二元复合体内可用的反应路径的性质对于决定特定复合体的反应活性至关重要。
• Photochemical Reaction of <i>N</i> , <i>N</i> ‐Dimethylanilines with N‐Substituted Maleimides Utilizing Benzaldehyde as the Photoinitiator
  作者：Nikolaos F. Nikitas、Maria A. Theodoropoulou、Christoforos G. Kokotos

  DOI：10.1002/ejoc.202001593

  日期：2021.2.19

  Benzaldehyde can be employed as the photoinitiator for the introduction of a low‐cost, simple, photochemical protocol for the reaction between N‐substituted maleimides with N,N‐dialkylanilines.

  苯甲醛可用作光引发剂，用于引入低成本，简单的光化学方案，用于N取代的马来酰亚胺与N，N－二烷基苯胺之间的反应。
• Azasteroids. Reaction of Chiral N,N-Maleoyl Amino Acids with 1-(1-Trimethylsiloxyvinyl)-3,4-dihydronaphthalene
  作者：Anja Bodtke、Milton T. Stubbs、Hans-Hartwig Otto

  DOI：10.1007/s00706-005-0406-8

  日期：2006.1

  cycloaddition between N , N -maleoyl amino acid esters and 1-(1-trimethylsiloxyvinyl)-3,4-dihydronaphthalene gave 11-(trimethylsiloxy) derivatives of 16-azaestra-1,3,5(10)-trienes. These were transformed by desilylation into the parent 11-oxo-derivatives, which reacted with hydroxylamines to 11-hydroxyimino derivatives. The stereochemistry of the products was elucidated using different NMR methods, HPLC, CD

  N ， N 之间的环加成 -马来酰基氨基酸酯和1-（1-三甲基甲硅烷氧基乙烯基）-3,4-二氢萘得到了16-氮杂-1,3,5（10）-三烯的11-（三甲基甲硅烷氧基）衍生物。通过去甲硅烷基化将它们转化成母体11-氧代衍生物，其与羟胺反应生成11-羟基亚氨基衍生物。使用不同的NMR方法，HPLC，CD，X射线结构分析和计算来阐明产物的立体化学。发现从这些环加成物中获得非对映异构体的混合物。使用手性马来酰基氨基酸衍生物的反应没有改变该结果。手性中心没有引起立体选择性，这可能是由于手性侧链的柔韧性引起的。仅在与苯丙氨酸衍生物的反应中发现侧链的直接影响。这可以解释为芳族体系与酰亚胺部分的羰基之间的相互作用。这种相互作用使芳香环保持在最终产物中的位置，并在X射线晶体学分析中发现，并与计算结果相符。