tert-butyl 2-[5-[bis(1H-pyrrol-2-yl)methyl]-2,3-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]phenoxy]acetate | 1277116-16-1

• 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: tert-butyl 2-[5-[bis(1H-pyrrol-2-yl)methyl]-2,3-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]phenoxy]acetate
• CAS: 1277116-16-1
• 化学式: C₃₃H₄₄N₂O₉
• 分子量: 612.72
• InChiKey: NSWCDAWCGJTBOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  44
• 可旋转键数：
  18
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  138
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  thiophen-2-yl-propynal 、 tert-butyl 2-[5-[bis(1H-pyrrol-2-yl)methyl]-2,3-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]phenoxy]acetate 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  高效合成具有不同内消旋取代基的卟啉，可避免在水性介质中发生争夺

  摘要：

  我们已经开发出了新的条件，可以提供区域异构纯的带有芳基和芳基乙炔基取代基的反式A 2 B 2，A 3 B和反式AB 2 C卟啉。卟啉的制备方法是：将二吡咯甲烷与醛进行酸催化缩合，然后用对氯苯醌或2,3-二氯-5,6-二氰基-1,4-苯并醌（DDQ）进行氧化。通过检查各种反应参数（例如溶剂组成，酸浓度和反应时间），可以确定最佳的缩合条件。确定的条件（对于芳族醛：EtOH / H 2 O 4：1，[DPM] = 4 m M，[醛] = 4 mM，[HCl] ＝ 38m M，16小时；m，[m / z] 。对于芳基乙炔醛：THF / H 2 O 2：1，[DPM] = 13 m M，[醛] = 13 m M，[HCl] = 150 m M，3小时）导致卟啉的形成，产率为9 –38％，无可检测的加扰。该合成与各种官能团如酯或腈相容。总共有20个新的trans- A 2 B 2-，A 3 B-和trans-

  DOI：

  10.1002/chem.201403677
• 作为产物：
  描述：

  氯乙酸叔丁酯 、 3,4,5-三羟基苯甲醛 在 potassium carbonate 、 potassium iodide 作用下， 以 乙腈 为溶剂， 反应 10.17h， 生成 tert-butyl 2-[5-[bis(1H-pyrrol-2-yl)methyl]-2,3-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]phenoxy]acetate
  参考文献：
  名称：

  Synthesis of trans-A₂B₂-Porphyrins Bearing Phenylethynyl Substituents

  摘要：

  Efficient and convenient conditions for the preparation of trans-A(2)B(2)-porphyrins bearing two phenylethynyl moieties directly from phenylpropargyl aldehydes and dipyrromethanes of diversified lipophilicity and reactivity have been developed. This new procedure allows the preparation of a library of porphyrins of this architecture with a wide range of substituents. Thanks to the identification of the reagent solubility as one of the key factors influencing the yield of the porphyrinogens, we were able to improve yields to ca. 30%. The scope and limitations of two sets of conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in the last step without the need for deprotection of the triple bond or bromination and consecutive coupling reaction, which often demands copper salts to proceed smoothly, especially with electron-deficient alkyne partners. Therefore, it prevents undesired copper porphyrin formation, as well as the need for utilizing expensive alkynes. A two-step method for the preparation of phenylpropargyl aldehydes has also been refined.

  DOI：

  10.1021/jo1025578

文献信息

• Synthesis of <i>trans</i>-A₂B₂-Porphyrins Bearing Phenylethynyl Substituents
  作者：Agnieszka Nowak-Król、Beata Koszarna、Su Yeon Yoo、Jan Chromiński、Marek K. Wȩcławski、Chang-Hee Lee、Daniel T. Gryko

  DOI：10.1021/jo1025578

  日期：2011.4.15

  Efficient and convenient conditions for the preparation of trans-A(2)B(2)-porphyrins bearing two phenylethynyl moieties directly from phenylpropargyl aldehydes and dipyrromethanes of diversified lipophilicity and reactivity have been developed. This new procedure allows the preparation of a library of porphyrins of this architecture with a wide range of substituents. Thanks to the identification of the reagent solubility as one of the key factors influencing the yield of the porphyrinogens, we were able to improve yields to ca. 30%. The scope and limitations of two sets of conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in the last step without the need for deprotection of the triple bond or bromination and consecutive coupling reaction, which often demands copper salts to proceed smoothly, especially with electron-deficient alkyne partners. Therefore, it prevents undesired copper porphyrin formation, as well as the need for utilizing expensive alkynes. A two-step method for the preparation of phenylpropargyl aldehydes has also been refined.
• An Efficient Synthesis of Porphyrins with Different<i>meso</i>Substituents that Avoids Scrambling in Aqueous Media
  作者：Agnieszka Nowak-Król、Rémi Plamont、Gabriel Canard、Judicaelle Andeme Edzang、Daniel T. Gryko、Teodor Silviu Balaban

  DOI：10.1002/chem.201403677

  日期：2015.1.19

  aldehydes: THF/H2O 2:1, [DPM]=13 mM, [aldehyde]=13 mM, [HCl]=150 mM, 3 h) resulted in the formation of porphyrins in yields of 9–38 % without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans‐A2B2‐, A3B‐, and trans‐AB2C‐porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored

  我们已经开发出了新的条件，可以提供区域异构纯的带有芳基和芳基乙炔基取代基的反式A 2 B 2，A 3 B和反式AB 2 C卟啉。卟啉的制备方法是：将二吡咯甲烷与醛进行酸催化缩合，然后用对氯苯醌或2,3-二氯-5,6-二氰基-1,4-苯并醌（DDQ）进行氧化。通过检查各种反应参数（例如溶剂组成，酸浓度和反应时间），可以确定最佳的缩合条件。确定的条件（对于芳族醛：EtOH / H 2 O 4：1，[DPM] = 4 m M，[醛] = 4 mM，[HCl] ＝ 38m M，16小时；m，[m / z] 。对于芳基乙炔醛：THF / H 2 O 2：1，[DPM] = 13 m M，[醛] = 13 m M，[HCl] = 150 m M，3小时）导致卟啉的形成，产率为9 –38％，无可检测的加扰。该合成与各种官能团如酯或腈相容。总共有20个新的trans- A 2 B 2-，A 3 B-和trans-