tetramethyl 1H-pyrrole-2,3,4,5-tetracarboxylate | 2703-15-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: tetramethyl 1H-pyrrole-2,3,4,5-tetracarboxylate
• 英文别名: tetramethyl pyrrole-2,3,4,5-tetracarboxylate；2,3,4,5-tetra(methoxycarbonyl)pyrrole；pyrrole-2,3,4,5-tetracarboxylic acid tetramethyl ester；Pyrrol-2,3,4,5-tetracarbonsaeure-tetramethylester
• CAS: 2703-15-3
• 化学式: C₁₂H₁₃NO₈
• 分子量: 299.237
• InChiKey: IHKXNLWFHWMDMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  121
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  重氮乙酸甲酯 在 吡啶 、 dirhodium tetraacetate 作用下， 以 邻二甲苯 为溶剂， 反应 3.0h， 以38%的产率得到tetramethyl 1H-pyrrole-2,3,4,5-tetracarboxylate
  参考文献：
  名称：

  摘要：

  Thermal, photolytic, and thermocatalytic decomposition of methyl diazoacetate (MDA) in the presence of Rh-2(OAc)(4) or Cu(acac)(2) in refluxing pyridine afforded isomeric trans,cis- and cis, trans- 3,4,5,6 -tetra(methoxycarbonyl) - 1,4,5,6-tetrahydropyridazines (- 1 : 1) in a total yield of 30-70%. Decomposition of MDA in refluxing o-xylene in the presence of Rh-2(OAc)(4) and pyridine (20 mol.%) gave rise to 2,3,4,5 -tetra (methoxycarbonyl)pyrrole in a yield of up to 40%. In these transformations of MDA, neither dimethyl fumarate (or dimethyl maleate) nor the corresponding 2-pyrazolines were generated as intermediates.

  DOI：

  10.1023/a:1022421020644

文献信息

• Cu/Mn Co-oxidized Cyclization for the Synthesis of Highly Substituted Pyrrole Derivatives from Amino Acid Esters: A Strategy for the Biomimetic Syntheses of Lycogarubin C and Chromopyrrolic Acid
  作者：Nini Zhou、Tao Xie、Lin Liu、Zhixiang Xie

  DOI：10.1021/jo500740w

  日期：2014.7.3

  An effective and concise approach to synthesis of tetrasubstituted pyrroles from readily available amino acid esters by the promotion of Cu(OAc)2 in conjunction with Mn(OAc)3 has been developed. This reaction proceeds through multiple dehydrogenations, deamination, and oxidative cyclization. This oxidized system tolerates substrates bearing various electron-donating or electron-withdrawing groups.

  通过促进Cu（OAc）2与Mn（OAc）3的结合，已经开发了一种有效，简洁的方法，可以从容易获得的氨基酸酯中合成四取代的吡咯。该反应通过多次脱氢，脱氨基和氧化环化而进行。这种氧化的系统可以承受带有各种给电子或吸电子基团的底物。用这种方法，已经有效地制备了几种天然产物的关键中间体，并且高效地完成了糖木蛋白C和色吡咯酸的全部合成。
• Reactions of alkyl diazoacetates with pyridinium ylides
  作者：Yu. V. Tomilov、D. N. Platonov、D. V. Dorokhov、O. M. Nefedov

  DOI：10.1007/s11172-005-0349-6

  日期：2005.4

  Pyridinium (methoxycarbonyl)methylide generated from (methoxycarbonyl)methyl-pyridinium halides under the action of K2CO3 reacts with alkyl diazoacetates in CH2Cl2 at 20 °C, resulting in the successive addition of three CHCOOMe fragments from the ylide to form 3,6-bis(alkoxycarbonyl)-4,5-diazaoctadienoic acid diesters. Heating of the latter in the presence of pyridine leads to their isomerization to give tetraalkyl tetrahydropyridazine-tetracarboxylates in high yields. Under more drastic conditions (refluxing xylene in the presence of pyridine), the acyclic tetraesters undergo another transformation to form pyrrole-tetracarboxylic acid esters in yields of up to 60%.

  在 K2CO3 的作用下，由（甲氧基羰基）甲基吡啶鎓卤化物生成的吡啶鎓（甲氧基羰基）甲化物与重氮乙酸烷基酯在 CH2Cl2 中于 20 °C 下发生反应，结果从醯胺中连续加入三个 CHCOOMe 片段，形成 3,6-双（烷氧基羰基）-4,5-二氮杂辛二烯酸二酯。在吡啶存在下加热后者，会导致它们发生异构化，从而以高产率生成四烷基四氢哒嗪四羧酸盐。在更苛刻的条件下（在吡啶存在下回流二甲苯），无环四酯会发生另一种转化，生成吡咯-四羧酸酯，产率高达 60%。
• Reactions of 2-Hydrazino- and 8-Hydrazinocyclohepta[<i>b</i>]pyrroles with Dimethyl Acetylenedicarboxylate
  作者：Noritaka Abe、Kumiko Yatabe

  DOI：10.1246/bcsj.64.1704

  日期：1991.5

  2-Hydrazinocyclohepta[b]pyrrole reacted with dimethyl acetylenedicarboxylate (DMAD) to give the hydrazones (2a), the pyrimidinone-fused cyclohepta[b]pyrrole (3), 1,2,4-triazinone-fused cyclohepta[b]pyrroles, and the 1,2-dihydro-3H-pyrazol-3-one derivative. Thermolysis of 2a gave 3 and tetramethyl pyrrole-2,3,4,5-tetracarboxylate. The reaction of ethyl cyclohepta[b]pyrrole-3-carboxylate with DMAD at

  2-肼基环庚烷[b]吡咯与乙炔二羧酸二甲酯（DMAD）反应得到腙（2a），嘧啶酮稠合的环庚酮[b]吡咯（3），1,2,4-三嗪酮稠合的环庚酮[b]吡咯，和 1,2-二氢-3H-吡唑-3-酮衍生物。2a 的热解得到 3 和四甲基吡咯-2,3,4,5-四羧酸酯。环庚[b]吡咯-3-羧酸乙酯与DMAD在室温下反应得到腙和螺吡唑啉衍生物。
• Effective synthesis of symmetrical oxygen- and nitrogen-heterocycles from electron-deficient alkynes via the catalysis of electrogenerated base and Fe3+ ions
  作者：Chuan-Hua Li、Gao-Qing Yuan、Jun-Hua Zheng、Zai-Jun He、Chao-Rong Qi、Huan-Feng Jiang

  DOI：10.1016/j.tet.2011.04.058

  日期：2011.6

  An efficient method has been developed for the synthesis of oxygen- and nitrogen-heterocycles from electron-deficient alkynes and alcohol or amines via electrochemically induced two-step process. The first step involves that the electrogenerated base (EGB) catalyzes hydroalcoholization or hydroamination process. In the second step, Fe3+ ions and strong bases electrogenerated can synergically catalyze

  已开发出一种有效的方法，可通过电化学诱导的两步法从缺电子的炔烃和醇或胺合成氧和氮杂环。第一步涉及电生成碱（EGB）催化加氢醇化或加氢胺化过程。第二步，电生成的Fe 3+离子和强碱可以协同催化环化过程，得到对称的杂环。研究了一些关键因素并讨论了反应机理。
• New route to 1H-aziridines: O-mesitylenesulphonylhydroxylamine addition to electrophilic alkenes
  作者：Pierre Métra、Jack Hamelin

  DOI：10.1039/c39800001038

  日期：——

  O-Mesitylenesulphonylhydroxylamine (MSH) reacts with electrophilic alkenes and, after treatement with triethylamine, 1H-aziridines are formed.

  O-亚甲基亚磺酰基羟胺（MSH）与亲电烯烃反应，并用三乙胺处理后，形成1 H-氮丙啶。

表征谱图