tert-Butyl 5-acetoxymethyl-4-butyl-3-methyl-1H-pyrrole-2-carboxylate | 172805-97-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: tert-Butyl 5-acetoxymethyl-4-butyl-3-methyl-1H-pyrrole-2-carboxylate
• 英文别名: tert-butyl 5-(acetoxymethyl)-4-n-butyl-3-methylpyrrole-2-carboxylate；tert-butyl 5-acetoxymethyl-4-butyl-3-methylpyrrole-2-carboxylate；tert-butyl 5-(acetyloxymethyl)-4-butyl-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 172805-97-9
• 化学式: C₁₇H₂₇NO₄
• 分子量: 309.406
• InChiKey: MUBJAEMTNOLHGZ-UHFFFAOYSA-N

物化性质

• 熔点：
  85-87 °C(Solv: chloroform (67-66-3); ligroine (8032-32-4))
• 沸点：
  408.3±45.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-Butyl 5-acetoxymethyl-4-butyl-3-methyl-1H-pyrrole-2-carboxylate 在 palladium on activated charcoal Montmorillonite K₁₀ clay 、 硫酸 、 氢气 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  The polymer-supported MacDonald-type porphyrin synthesis: coupling of two dissimilar dipyrromethanes

  摘要：

  Syntheses of two completely unsymmetrical porphyrins have been achieved by MacDonald-type condensations of polymer-bound 9-formyldipyrromethanes with dissimilar solution-phase dipyrromethanes. The chemoselectivity of the process depends on the nature of the substituents at the a positions of the substrates. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01269-7
• 作为产物：
  描述：

  t-Butyl oximinoacetoacetate 在 sodium acetate 、 乙酸酐 、 溶剂黄146 、 锌 作用下， 反应 4.0h， 生成 tert-Butyl 5-acetoxymethyl-4-butyl-3-methyl-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins

  摘要：

  5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities Of p-tolenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding alpha-unsubstituted pyrroles with KOH in ethylene glycol at 180-190 degrees C and these condensed with 2 equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52-83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV-vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the '3 + 11 strategy. Instead, alpha-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolitioporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.089

文献信息

• A new synthesis of [2,3]naphthoporphyrins
  作者：Satoshi Ito、Naoyuki Ochi、Takashi Murashima、Noboru Ono、Hidemitsu Uno

  DOI：10.1039/b002213f

  日期：——

  A new synthesis of [2,3]naphthoporphyrins using 4,9-ethano-2H-benz[f]isoindole as a synthon of 2H-benz[f]- isoindole is described; soluble precursors of [2,3]naphthoporphyrins are converted into insoluble [2,3]naphthoporphyrins by simply heating at 290 °C.

  描述了使用 4,9-ethano-2H-benz[f]isoindole 作为 2H-benz[f]-isoindole 的合成子合成 [2,3] 萘卟啉的新方法；[2,3] 萘卟啉的可溶性前体通过简单地在 290 °C 加热即可转化为不溶性 [2,3] 萘卟啉。
• Porphyrin synthesis by the “3 + 1” methodology: A superior approach for the preparation of porphyrins with fused 9,10-phenanthroline subunits
  作者：Vanning Lin、Timothy D. Lash

  DOI：10.1016/0040-4039(95)02100-0

  日期：1995.12

  Porphyrins with fused 1,10-phenanthroline subunits have been prepared in exceptionally high yields by the acid catalyzed condensation of phenanthroline substituted tripyrranes with a 2,5-pyrroledicarboxaldehyde.

  带有1,10-菲咯啉亚基稠合的卟啉已通过酸催化菲咯啉取代的三吡喃与2,5-吡咯烷二醛的缩合反应以极高的产率制备。
• Synthesis of [2,3]naphthoporphyrins using 4,9-dihydro-4,9-ethano-2H-benz[f]isoindole as a benz[f]isoindole equivalent
  作者：Yutaro Ishii、Satoshi Ito、Yuki Saito、Daiki Uno、Toru Oba

  DOI：10.1016/j.tet.2015.09.072

  日期：2015.11

  We report a new synthesis of 1,4-dihydro-1,4-ethanonaphthalene using 4,9-dihydro-4,9-ethano-2H-benz[f]isoindole as the equivalent of benz[f]isoindole, from p-benzoquinone as a starting material via the Diels–Alder reaction, Luche reduction, and dehydroxylation. We also report the synthesis of various new [2,3]naphthoporphyrin derivatives and their metal complexes.

  我们使用4,9-二氢-4,9-亚乙基2报告1,4-二氢-1,4- ethanonaphthalene的新合成ħ苯并〔˚F ]异吲哚如苯并〔相当于˚F ]异吲哚，从p苯醌经由Diels-Alder反应的起始材料，luche还原反应，和脱羟基。我们还报告各种新[2,3] naphthoporphyrin衍生物及其金属络合物的合成。
• Porphyrins with exocyclic rings. Part 24. Synthesis and spectroscopic properties of pyrenoporphyrins, potential building blocks for porphyrin molecular wires
  作者：Virajkumar Gandhi、Michelle L. Thompson、Timothy D. Lash

  DOI：10.1016/j.tet.2010.01.046

  日期：2010.3

  Porphyrins with fused pyrene units have been prepared by ‘2+2’ and ‘3+1’ methodologies. Nitration of 1,2,3,6,7,8-tetrahydropyrene, followed by oxidation with DDQ, gave 4-nitropyrene and this condensed with ethyl isocyanoacetate in the presence of DBU or a phosphazene base to generate a pyrenopyrrole ethyl ester. Ester saponification and decarboxylation with KOH in ethylene glycol at 190 °C gave the

  具有稠合pyr单元的卟啉已通过“ 2 + 2”和“ 3 + 1”方法制备。硝化1,2,3,6,7,8-四氢py，然后用DDQ氧化，得到4-硝基py，在DBU或磷腈碱存在下，将其与异氰基乙酸乙酯缩合，生成吡咯并吡咯乙酯。在190°C下用乙二醇在KOH中进行酯化和脱羧，得到母体吡啶并[4,5- c ]吡咯，并进一步与2当量的乙酰氧基甲基吡咯缩合，得到相应的三吡喃并在叔端被保护。丁酯。在一锅法中，用TFA裂解酯保护基，然后用二氯甲烷稀释，用吡咯二醛'3 + 1'缩合，再用DDQ脱氢，生成的目标卟啉卟啉具有良好的总收率。还从pyrenopyrrole中间体制备的二醛和此反应得到的OPP -dipyrenoporphyrin。吡咯并吡咯乙酯在酸催化剂的存在下与二甲氧基甲烷反应生成二戊基吡咯烷基甲烷，并用于制备adj-使用麦当劳“ 2 + 2”方法提取双肾上腺素。吡咯并吡咯二醛还用于制备具有稠合的an
• Synthesis of Porphyrin Dimers Fused with a Benzene Unit
  作者：Hidemitsu Uno、Ken-ichi Nakamoto、Kenji Kuroki、Akiko Fujimoto、Noboru Ono

  DOI：10.1002/chem.200601644

  日期：2007.7.6

  Bicyclo[2.2.2]octadiene-connected pyrrolo-porphyrins have been prepared by an inverse-type [3+1] porphyrin synthesis of a bicyclo[2.2.2]octadiene-fused dipyrrole with a tripyrrane dicarbaldehyde. Another [3+1] porphyrin synthesis of pyrrole-connected porphyrins with the same or other tripyrrane dicarbaldehydes gave bicyclo[2.2.2]octadiene-bridged diporphyrins, the central metals and/or peripheral substituents

  双环[2.2.2]辛二烯连接的吡咯并卟啉已通过反式[3 + 1]卟啉与三吡喃二卡甲醛的双环[2.2.2]辛二烯稠合的双吡咯合成而制备。吡咯连接的卟啉与相同或其他三吡喃二甲醛的另一种[3 + 1]卟啉合成产生双环[2.2.2]辛二烯桥联的二卟啉，其中心金属和/或外围取代基不同。将双环[2.2.2]辛二烯骨架热分解为苯部分，得到高纯度形式的π系统稠合的卟啉二聚体。