[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]di(1H-pyrrol-2-yl)methane | 614752-70-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]di(1H-pyrrol-2-yl)methane
• 英文别名: 2-[[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]-(1H-pyrrol-2-yl)methyl]-1H-pyrrole
• CAS: 614752-70-4
• 化学式: C₂₁H₂₄N₂O₂
• 分子量: 336.434
• InChiKey: NHSPKSANMPUTBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]di(1H-pyrrol-2-yl)methane 在 乙基溴化镁 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.17h， 生成 1,9-bis(3,5-di-tert-butylbenzoyl)-5-[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]dipyrromethane
  参考文献：
  名称：

  Porphyrin Dyads Bearing Carbon Tethers for Studies of High-Density Molecular Charge Storage on Silicon Surfaces

  摘要：

  [graphics]Redox-active molecules that afford high charge density upon attachment to an electroactive surface are of interest for use in molecular-based information- storage applications. One strategy for increasing charge density is to covalently link a second redox center to the first in an architecture that uses the vertical dimension in essentially the same molecular footprint. Toward this end, a set of four new porphyrin dyads have been prepared and characterized. Each dyad consists of two zinc porphyrins, an intervening linker (p-phenylene or 4,4'-diphenylethyne), and a surface attachment group (ethynyl or triallyl group). The porphyrin dyads were attached to an electroactive Si(100) surface and interrogated via electrochemical and FTIR techniques. The charge density obtainable for the ethynyl -functional ized porphyrin dyads is approximately double that observed for an analogously functionalized monomer, whereas that for the triallyl-functionalized dyads is at most 40% larger. These results indicate that the molecular footprint of the former dyads is similar to that of a monomer while that of the latter dyads is larger. For both the ethynyl- and triallyl-functionalized porphyrin dyads, higher charge densities (smaller molecular footprints) are obtained for the molecules containing the 4,4'-diphenylethyne versus the p-phenylene linker. This feature is attributed to the enhanced torsional flexibility of the former linker compared with that of the latter, which affords better packed monolayers. The FTIR studies indicate that the adsorption geometry of all the dyads is qualitatively similar and similar to that of monomers. However, the dyads containing the 4,4'-diphenylethyne linker sit somewhat more upright on the surface than those containing the p-phenylene linker, generally consistent with the smaller molecular footprint for the former dyads. Collectively, the high surface charge density (34-58 mu C center dot cm(-2)) of the porphyrin dyads makes these constructs viable candidates for molecular-information-storage applications.

  DOI：

  10.1021/jo0522761
• 作为产物：
  描述：

  吡咯 、 4-(5,5-dimethyl-1,3-dioxan-2-yl)benzaldehyde 在 三氟乙酸 作用下， 反应 0.08h， 以48%的产率得到[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]di(1H-pyrrol-2-yl)methane
  参考文献：
  名称：

  Porphyrin Dyads Bearing Carbon Tethers for Studies of High-Density Molecular Charge Storage on Silicon Surfaces

  摘要：

  [graphics]Redox-active molecules that afford high charge density upon attachment to an electroactive surface are of interest for use in molecular-based information- storage applications. One strategy for increasing charge density is to covalently link a second redox center to the first in an architecture that uses the vertical dimension in essentially the same molecular footprint. Toward this end, a set of four new porphyrin dyads have been prepared and characterized. Each dyad consists of two zinc porphyrins, an intervening linker (p-phenylene or 4,4'-diphenylethyne), and a surface attachment group (ethynyl or triallyl group). The porphyrin dyads were attached to an electroactive Si(100) surface and interrogated via electrochemical and FTIR techniques. The charge density obtainable for the ethynyl -functional ized porphyrin dyads is approximately double that observed for an analogously functionalized monomer, whereas that for the triallyl-functionalized dyads is at most 40% larger. These results indicate that the molecular footprint of the former dyads is similar to that of a monomer while that of the latter dyads is larger. For both the ethynyl- and triallyl-functionalized porphyrin dyads, higher charge densities (smaller molecular footprints) are obtained for the molecules containing the 4,4'-diphenylethyne versus the p-phenylene linker. This feature is attributed to the enhanced torsional flexibility of the former linker compared with that of the latter, which affords better packed monolayers. The FTIR studies indicate that the adsorption geometry of all the dyads is qualitatively similar and similar to that of monomers. However, the dyads containing the 4,4'-diphenylethyne linker sit somewhat more upright on the surface than those containing the p-phenylene linker, generally consistent with the smaller molecular footprint for the former dyads. Collectively, the high surface charge density (34-58 mu C center dot cm(-2)) of the porphyrin dyads makes these constructs viable candidates for molecular-information-storage applications.

  DOI：

  10.1021/jo0522761

文献信息

• Porphyrin building blocks bearing two or four divergent ethynes
  作者：Phuong-Lien Doan Cao、Zhiyuan Wu、Jie Rong、Jonathan S. Lindsey

  DOI：10.1142/s1088424623500219

  日期：2023.10

  Tetrapyrrole building blocks are invaluable constituents in the construction of molecular architectures for use in biomimicry, functional materials, and biomedicine. The reaction of dipyrromethane and the triisopropylsilyl-protected 3,5-diethynylbenzaldehyde afforded the corresponding trans-[Formula: see text]-porphyrin (free base) bearing four ethynes. Subsequent meso-bromination, Suzuki coupling, and protecting group removal afforded a porphyrin building block bearing four ethynes and one benzylamine. The reaction of dipyrromethane and 3,5-bis(propargyloxy)benzaldehyde afforded the corresponding trans-[Formula: see text]-porphyrin (free base) bearing four ethynes. The reaction of 5-(3,5-bis(propargyloxy)phenyl)dipyrromethane and the Eschenmoser (1,9-dimethylaminomethyl) derivative of a 5-([Formula: see text]-substituted aryl)dipyrromethane was used to create two trans-AB-porphyrins (zinc chelates). The [Formula: see text]-substituent of the aryl group was cyano or an acetal moiety. Hydrolysis of the acetal and a click reaction with m-PEG24-azide gave the bis(PEGylated)porphyrin-carboxaldehyde. The porphyrins present readily derivatizable functional groups in a compact architecture.

  四吡咯结构单元是构建分子结构的宝贵成分，可用于生物模拟、功能材料和生物医学。二吡咯甲烷与受三异丙基硅烷保护的 3,5-二乙炔基苯甲醛反应生成了相应的反式-[式：见正文]-卟啉（游离基），其中含有四个乙炔。随后进行中溴化、铃木偶联和去除保护基，得到了含有四个乙炔和一个苄胺的卟啉结构单元。二吡咯甲烷和 3,5-双（丙炔氧基）苯甲醛反应生成相应的反式-[式：见正文]-卟啉（游离基），其中含有四个乙炔。通过 5-(3,5-双(丙炔氧基)苯基)二吡咯甲烷和 5-([式：见正文]取代芳基)二吡咯甲烷的埃申莫瑟（1,9-二甲基氨基甲基）衍生物的反应，生成了两种反式-AB-卟啉（锌螯合物）。芳基的[式：见正文]取代基为氰基或缩醛基。乙缩醛水解后与 m-PEG24-azide 发生点击反应，得到双（PEG 化）卟啉甲醛。卟啉以紧凑的结构呈现出易于衍生的官能团。
• Porphyrin Dyads Bearing Carbon Tethers for Studies of High-Density Molecular Charge Storage on Silicon Surfaces
  作者：Patchanita Thamyongkit、Lianhe Yu、Kisari Padmaja、Jieying Jiao、David F. Bocian、Jonathan S. Lindsey

  DOI：10.1021/jo0522761

  日期：2006.2.1

  [graphics]Redox-active molecules that afford high charge density upon attachment to an electroactive surface are of interest for use in molecular-based information- storage applications. One strategy for increasing charge density is to covalently link a second redox center to the first in an architecture that uses the vertical dimension in essentially the same molecular footprint. Toward this end, a set of four new porphyrin dyads have been prepared and characterized. Each dyad consists of two zinc porphyrins, an intervening linker (p-phenylene or 4,4'-diphenylethyne), and a surface attachment group (ethynyl or triallyl group). The porphyrin dyads were attached to an electroactive Si(100) surface and interrogated via electrochemical and FTIR techniques. The charge density obtainable for the ethynyl -functional ized porphyrin dyads is approximately double that observed for an analogously functionalized monomer, whereas that for the triallyl-functionalized dyads is at most 40% larger. These results indicate that the molecular footprint of the former dyads is similar to that of a monomer while that of the latter dyads is larger. For both the ethynyl- and triallyl-functionalized porphyrin dyads, higher charge densities (smaller molecular footprints) are obtained for the molecules containing the 4,4'-diphenylethyne versus the p-phenylene linker. This feature is attributed to the enhanced torsional flexibility of the former linker compared with that of the latter, which affords better packed monolayers. The FTIR studies indicate that the adsorption geometry of all the dyads is qualitatively similar and similar to that of monomers. However, the dyads containing the 4,4'-diphenylethyne linker sit somewhat more upright on the surface than those containing the p-phenylene linker, generally consistent with the smaller molecular footprint for the former dyads. Collectively, the high surface charge density (34-58 mu C center dot cm(-2)) of the porphyrin dyads makes these constructs viable candidates for molecular-information-storage applications.