methyl 3,4-diethylpyrrole-2-carboxylate | 159427-97-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: methyl 3,4-diethylpyrrole-2-carboxylate
• 英文别名: 2-(Methoxycarbonyl)-3,4-diethylpyrrole；2-methoxycarbonyl-3,4-diethylpyrrol；methyl 3,4-diethyl-1H-pyrrole-2-carboxylate
• CAS: 159427-97-1
• 化学式: C₁₀H₁₅NO₂
• 分子量: 181.235
• InChiKey: JTPMCFYIBGSNOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  42.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 3,4-diethylpyrrole-2-carboxylate 在 盐酸 air 、 lithium chloride 作用下， 以 乙醇 、 二甲基亚砜 为溶剂， 反应 2.5h， 生成 2,3,7,8,12,13,17,18-octaethyl-21,22-dihydroporphyrin
  参考文献：
  名称：

  Nonionic Superbase-Promoted Synthesis of Oxazoles and Pyrroles: Facile Synthesis of Porphyrins and .alpha.-C-Acyl Amino Acid Esters

  摘要：

  The reaction of acyl chlorides or acid anhydrides with isocyanoacetates in the presence of the superior strong nonionic base P(MeNCH(2)CH(2))(3)N (1) gave oxazoles in 98-99% yield. Treatment of the oxazoles with HCl-MeOH gave alpha-C-acyl amino acid esters in 81-82% yield. The reaction of beta-acetoxy-alpha-nitroalkanes or nitroalkenes with isocyanoacetates in the presence of 1 gave pyrroles in 100% yield. The conjugate acid of 1 can be treated with KO-t-Bu to regenerate 1. Treatment of the pyrroles with LiAlH4, followed by PTSA-CH2(OMe)(2) and oxidation gave porphyrins in 65-69% yield. LiCl, which functions both as a strong nucleophile in the S(N)2 demethylation of the 5,5'-bis(methoxycarbonyl)-3,3',4,4'-tetramethyldipyrromethane 22a and as a Lewis acid in the electrophilic substitution cyclization of paraformaldehyde at dipyrromethane, facilitates the combination of four reactions into a one-pot synthesis of octaethylporphyrin in 67% yield from 22a.

  DOI：

  10.1021/jo00104a041
• 作为产物：
  描述：

  4-硝基-3-己烷基乙酸酯 、 异腈基乙酸甲酯 在 P(MeNCH₂CH₂)3N 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 反应 2.0h， 以100%的产率得到methyl 3,4-diethylpyrrole-2-carboxylate
  参考文献：
  名称：

  Nonionic Superbase-Promoted Synthesis of Oxazoles and Pyrroles: Facile Synthesis of Porphyrins and .alpha.-C-Acyl Amino Acid Esters

  摘要：

  The reaction of acyl chlorides or acid anhydrides with isocyanoacetates in the presence of the superior strong nonionic base P(MeNCH(2)CH(2))(3)N (1) gave oxazoles in 98-99% yield. Treatment of the oxazoles with HCl-MeOH gave alpha-C-acyl amino acid esters in 81-82% yield. The reaction of beta-acetoxy-alpha-nitroalkanes or nitroalkenes with isocyanoacetates in the presence of 1 gave pyrroles in 100% yield. The conjugate acid of 1 can be treated with KO-t-Bu to regenerate 1. Treatment of the pyrroles with LiAlH4, followed by PTSA-CH2(OMe)(2) and oxidation gave porphyrins in 65-69% yield. LiCl, which functions both as a strong nucleophile in the S(N)2 demethylation of the 5,5'-bis(methoxycarbonyl)-3,3',4,4'-tetramethyldipyrromethane 22a and as a Lewis acid in the electrophilic substitution cyclization of paraformaldehyde at dipyrromethane, facilitates the combination of four reactions into a one-pot synthesis of octaethylporphyrin in 67% yield from 22a.

  DOI：

  10.1021/jo00104a041

文献信息

• Preparation of pyrrol and oxazole compounds: formation of porphyrins and
  申请人：Iowa State University Research Foundation, Inc.

  公开号：US05367084A1

  公开（公告）日：1994-11-22

  A process for preparation of new or previously known pyrrol derivatives is provided. The process involves reacting a nitroalkane or a nitroalkene with an isocyanoacetate in the presence of a proprophosphatrane "super base" to prepare the pyrrol compounds. Through production of new pyrrol compounds, new pyrrol derivatives such as dipyrromethane and porphyrin may be synthesized. In addition, the high yields of pyrrol compounds produced according to the method of the invention provide for more efficient production of previously known dipyrromethane and porphyrin compounds. The invention further provides a mild, high yield process for de-esterification of esterified pyrrol and dipyrromethane compounds. The invention also provides a synthetic method for the production of high yields of oxazoles through reaction of an aryl halide or acid anhydride with an isocyanoacetate in the presence of a prophosphatrane "super base". The product oxazoles serve as intermediates for subsequent treatment to provide pharmaceutically interesting C-acyl-.alpha.-amino acid esters.

  提供了一种制备新的或已知的吡咯衍生物的方法。该方法涉及在丙基膦酸三乙酯“超强碱”存在下，将硝基烷或硝基烯与异氰酸乙酯反应以制备吡咯化合物。通过生产新的吡咯化合物，可以合成新的吡咯衍生物，如二吡咯甲烷和卟啉。此外，根据本发明方法生产的高产量吡咯化合物可更有效地生产以前已知的二吡咯甲烷和卟啉化合物。本发明还提供了一种温和的高产率的去酯化吡咯和二吡咯甲烷化合物的方法。本发明还提供了一种合成高产率噁唑的方法，该方法涉及在丙基膦酸三乙酯“超强碱”的存在下，将芳基卤化物或酸酐与异氰酸乙酯反应以制备噁唑化合物。产物噁唑可作为中间体进行后续处理，以提供具有药物学兴趣的C-酰基-α-氨基酸酯。
• Preparation of pyrrol and oxazole compounds; formation of porphyrins and
  申请人：Iowa State University Research Foundation, Inc.

  公开号：US05672717A1

  公开（公告）日：1997-09-30

  A process for preparation of new or previously known pyrrol derivatives is provided. The process involves reacting a nitroalkane or a nitroalkene with an isocyanoacetate in the presence of a prophosphatrane "super base" to prepare the pyrrol compounds. Through production of new pyrrol compounds, new pyrrol derivatives such as dipyrromethanes and porphyrins may be synthesized. In addition, the high yields of pyrrol compounds produced according to the method of the invention provide for more efficient production of previously known dipyrromethane and porphyrin compounds. The invention further provides a mild, high yield process for de-esterification of esterified pyrrol and dipyrromethane compounds. The invention also provides a synthetic method for the production of high yields of oxazoles through reaction of an aryl halide or acid anhydride with an isocyanoacetate in the presence of a prophosphatrane "super base". The product oxazoles serve as intermediates for subsequent treatment to provide pharmaceutically interesting C-acyl-.alpha.-amino acid esters.

  本发明提供了一种制备新的或已知的吡咯衍生物的方法。该方法涉及在超碱丙磷胺的存在下，将硝基烷或硝基烯与异氰乙酸酯反应以制备吡咯化合物。通过生产新的吡咯化合物，可以合成新的吡咯衍生物，如二吡咯甲烷和卟啉。此外，根据本发明的方法生产的高产量吡咯化合物可更高效地生产以前已知的二吡咯甲烷和卟啉化合物。本发明还提供了一种温和、高产率的去酯化吡咯和二吡咯甲烷化合物的方法。本发明还提供了一种合成高产量噁唑的方法，该方法涉及在超碱丙磷胺的存在下，将芳基卤化物或酸酐与异氰乙酸酯反应。产物噁唑可作为中间体，进行后续处理以提供具有药学兴趣的C-酰基-α-氨基酸酯。
• Synthesis, Structure, and Aromaticity of the Nickel(II) Complex of Pyricorrole, a Molecular Hybrid of Porphyrin and Corrole
  作者：Saburo Neya、Masaaki Suzuki、Takashi Matsugae、Tyuji Hoshino

  DOI：10.1021/ic3001043

  日期：2012.3.19

  Formal migration of one meso-carbon atom in the porphyrin ring into the pyrrole moiety results in an isomer “pyricorrole”, a pyridine-containing corrole macrocycle. We prepared the nickel(II) complex of pyricorrole by the nickel(II)-induced cyclization of a linear precursor. Electronic absorption and proton NMR spectra of this compound revealed the presence of an 18π-electron circuit over the macrocycle

  卟啉环中的一个内消碳原子正式迁移到吡咯部分中，导致异构体“吡咯”，一个含吡啶的大环化合物。我们通过镍（II）诱导的线性前体环化反应制备了吡咯啉的镍（II）配合物。该化合物的电子吸收和质子NMR光谱表明，在大环上存在18π电子电路，这表明在卟啉核的强烈重排后保留了芳香性。镍（II）配合物的X射线晶体学证实了其平面结构，并表明它具有卟啉和腐蚀物的杂化特性。
• US5367084A
  申请人：——

  公开号：US5367084A

  公开（公告）日：1994-11-22
• US5446166A
  申请人：——

  公开号：US5446166A

  公开（公告）日：1995-08-29