1-(4-iodobenzoyl)-5-mesityldipyrromethane | 262267-40-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(4-iodobenzoyl)-5-mesityldipyrromethane
• 英文别名: (4-iodophenyl)-[5-[1H-pyrrol-2-yl-(2,4,6-trimethylphenyl)methyl]-1H-pyrrol-2-yl]methanone
• CAS: 262267-40-3
• 化学式: C₂₅H₂₃IN₂O
• 分子量: 494.375
• InChiKey: UBQLGVVJEWCYJJ-UHFFFAOYSA-N

物化性质

• 熔点：
  163 °C
• 沸点：
  619.3±55.0 °C(Predicted)
• 密度：
  1.461±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  48.6
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(4-iodobenzoyl)-5-mesityldipyrromethane 在 sodium tetrahydroborate 、 TEA 、 乙基溴化镁 、 六甲基二硅氮烷 、 ytterbium(III) triflate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 5.09h， 生成
  参考文献：
  名称：

  Meso-¹³C-Labeled Porphyrins for Studies of Ground-State Hole Transfer in Multiporphyrin Arrays

  摘要：

  Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a C-13-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of C-13 substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-C-13 label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance N-14 nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the N-14 hyperfine clock (similar to 220 ns), remains fast on the time scale of the C-13 hyperfine clock (similar to 50 ns).

  DOI：

  10.1021/jo070593x
• 作为产物：
  描述：

  S-(2-pyridyl) 4-iodothiobenzoate 在 乙基溴化镁 、 水 、 氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 1-(4-iodobenzoyl)-5-mesityldipyrromethane
  参考文献：
  名称：

  Boron complexation strategy for use in manipulating 1-acyldipyrromethanes

  摘要：

  制备金属配合物的方法包括将1-单酰基二吡咯甲烷与化合物R1R2MX（其中M为硼，R1和R2分别为有机取代基；X为离子离去基团）结合，以产生配合物DMR1R2的金属配合物，其中DH为1-单酰基二吡咯甲烷。这些方法和配合物对于二吡咯甲烷和卟啉的纯化和合成是有用的。

  公开号：

  US20050282778A1

文献信息

• Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media
  作者：Rui Liu、Mengran Liu、Don Hood、Chih-Yuan Chen、Christopher MacNevin、Dewey Holten、Jonathan Lindsey

  DOI：10.3390/molecules23010130

  日期：——

  the red region and modest fluorescence quantum yield (Φf = 0.2-0.3). A Poisson analysis implies most micelles are empty and few contain >1 chlorin. Water-soluble chlorins each bearing three PEG (oligoethyleneglycol) groups exhibit narrow emission bands (full-width-at-half maximum <25 nm). The lifetime of the lowest singlet excited state and the corresponding yields and rate constants for depopulation

  在红色光谱区域（600-700 nm）吸收和发射的荧光团在光化学和光医学中引起了极大的兴趣。已经设计并合成了八种不同极性的新目标二氢卟酚（共19种新二氢卟酚）-叶绿素类似物；7个二氢卟酚配有可生物偶联的系链。非极性有机溶剂（甲苯），极性有机溶剂（DMF）以及水性或水性胶束介质中的疏水性或两亲性二氢卟酚在红色区域显示出清晰的发射带，并且荧光量子产率适中（Φf= 0.2-0.3）。泊松分析表明，大多数胶束是空的，很少包含＞ 1的二氢卟酚。各自带有三个PEG（低聚乙二醇）基团的水溶性二氢卟酚显示出窄的发射带（半峰全宽最大<25 nm）。最低单线态激发态的寿命以及人口减少途径（荧光，系统间杂交，内部转化）的相应产率和速率常数通常不受PEG基团或在水性或有机介质中溶解的影响。一组二氢卟酚-抗生物素蛋白缀合物显示Φf增加2倍，平均二氢卟酚/抗生物素蛋白比率增加（2.3-12）。总之，本文所述的各种极性
• Rational Syntheses of Porphyrins Bearing up to Four Different Meso Substituents
  作者：Polisetti Dharma Rao、Savithri Dhanalekshmi、Benjamin J. Littler、Jonathan S. Lindsey

  DOI：10.1021/jo000882k

  日期：2000.11.1

  using EtMgBr and an acid chloride has been refined. A new procedure for the preparation of unsymmetrical diacyl dipyrromethanes has been developed that involves (1) monoacylation with EtMgBr and a pyridyl benzothioate followed by (2) introduction of the second acyl unit upon reaction with EtMgBr and an acid chloride. The scope of these acylation methods has been examined by preparing multigram quantities

  带有特定取代基图案的卟啉是仿生和材料化学中至关重要的组成部分。我们已开发出避免统计反应的方法，采用最少的色谱法，并提供最多克量的区域异构纯卟啉，带有多达四个不同内消旋取代基的预先指定图案。该方法基于几克数量的二吡咯甲烷的可用性。使用EtMgBr和酰氯对二吡咯甲烷进行二酰化的方法已经完善。已经开发出一种新的制备不对称二酰基二吡咯甲烷的方法，该方法涉及（1）用EtMgBr和吡啶硫基吡啶酯单酰化，然后（2）在与EtMgBr和酰氯反应时引入第二个酰基单元。通过制备多克量的带有各种取代基的二酰基二吡咯甲烷，已经检验了这些酰化方法的范围。用NaBH（4）在甲醇THF中将二酰基二吡咯甲烷还原为相应的二吡咯甲烷-二甲醇。卟啉的形成涉及二吡咯甲烷-二甲醇和二吡咯甲烷的酸催化缩合，然后用DDQ氧化。通过检查各种反应参数（溶剂，温度，酸，浓度，时间），可以确定最佳的缩合条件。确定的条件（2.5 mM反应物在室温下含有30
• Efficient Synthesis of Monoacyl Dipyrromethanes and Their Use in the Preparation of Sterically Unhindered <i>trans</i>-Porphyrins
  作者：Polisetti Dharma Rao、Benjamin J. Littler、G. Richard Geier、Jonathan S. Lindsey

  DOI：10.1021/jo9915473

  日期：2000.2.1

  the corresponding carbinol, and self-condensation of the carbinol to form the porphyrin. The monoacylation procedure has wide scope as demonstrated by the preparation of a set of 15 diverse monoacyl dipyrromethanes in good yield at the multigram scale. The dipyrromethanecarbinol self-condensation reaction is extremely rapid (<3 min) under mild room-temperature conditions and affords the trans-porphyrin

  醛与在5位带有空间不受阻碍的芳基取代基的二吡咯甲烷的缩合反应通常会导致收率低以及由酸解加扰得到的卟啉产物的混合物。我们已经开发出了一种简洁易读的反式卟啉合成方法，该方法利用了数克量的二吡咯甲烷的可用性。该途径涉及用吡啶基硫酯选择性地将二吡咯甲烷单酰化，将单酰基二吡咯甲烷还原成相应的甲醇，以及使甲醇自缩合以形成卟啉。单酰化方法的范围很广，如制备一组15种多样的单酰基二吡咯甲烷，以克数计的高收率证明了这一点。二吡咯甲烷甲醇的自缩合反应非常快（< 3分钟）在温和的室温条件下，以16-28％的收率得到反式卟啉。通过激光解吸质谱法（LD-MS）对来自粗制反应混合物的样品进行分析，结果表明在检测限内（100份中有1份）没有加扰。该自缩合与一系列吸电​​子或释放电子的取代基以及用于构件应用的取代基（TMS-乙炔，乙炔，碘，酯）相容。自冷凝中不存在任何可检测的加扰，因此可以进行简单纯化。该合成在涉及最少色
• Boron-Complexation Strategy for Use with 1-Acyldipyrromethanes
  作者：Kannan Muthukumaran、Marcin Ptaszek、Bruce Noll、W. Robert Scheidt、Jonathan S. Lindsey

  DOI：10.1021/jo0492620

  日期：2004.8.1

  1-Acyldipyrromethanes are important precursors in rational syntheses of diverse porphyrinic compounds. 1-Acyldipyrromethanes are difficult to purify, typically streaking upon chromatography and giving amorphous powders upon attempted crystallization. A solution to this problem has been achieved by reacting the 1-acyldipyrromethane with a dialkylboron triflate (e.g., Bu2B-OTf or 9-BBN-OTf) to give the corresponding B,B-dialkyl-B-(1-acyldipyrromethane)boron(III) complex. The reaction is selective for a 1-acyldipyrromethane in the presence of a dipyrromethane. The 1-acyldipyrromethane-boron complexes are stable to routine handling, are soluble in common organic solvents, are hydrophobic, crystallize readily, and chromatograph without streaking. The 1-acyldipyrromethane can be liberated in high yield from the boron complex upon treatment with 1-pentanol. Alternatively, the 1-acyldipyrromethane-boron complex can be used in the formation of a trans-A(2)B(2)-porphyrin. In summary, the boron-complexation strategy has broad scope and greatly facilitates the isolation of 1-acyldipyrromethanes.