4-(5,5-dimethyl-1,3-dioxan-2-yl)benzylamine | 138536-82-0

• 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: 4-(5,5-dimethyl-1,3-dioxan-2-yl)benzylamine
• 英文别名: 1-[4-(5,5-Dimethyl-1,3-dioxan-2-yl)phenyl]methanamine；[4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl]methanamine
• CAS: 138536-82-0
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: BSCRAZLEPIDFGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  44.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(5,5-dimethyl-1,3-dioxan-2-yl)benzylamine 在 硫酸 、 三氟乙酸 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 生成 N-hexyl-N'<(4-formylphenyl)methyl>1,2:4,5-benzenebis(dicarboximide)
  参考文献：
  名称：

  Synthesis and Fluorescence Properties of Selectively Metallated Diporphyrins with Electron-Accepting Moieties

  摘要：

  文中描述了带有电子受体基团的金属选择性络合二卟啉的合成方法。这些化合物的稳态荧光光谱显示，自由基卟啉的荧光显著淬灭。文章讨论了一种可能的“超交换”机制，即长程电子转移机制。

  DOI：

  10.1246/bcsj.64.3005
• 作为产物：
  描述：

  4-(5,5-dimethyl-1,3-dioxan-2-yl)benzonitrile 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 5.0h， 以96%的产率得到4-(5,5-dimethyl-1,3-dioxan-2-yl)benzylamine
  参考文献：
  名称：

  Synthesis and Fluorescence Properties of Selectively Metallated Diporphyrins with Electron-Accepting Moieties

  摘要：

  文中描述了带有电子受体基团的金属选择性络合二卟啉的合成方法。这些化合物的稳态荧光光谱显示，自由基卟啉的荧光显著淬灭。文章讨论了一种可能的“超交换”机制，即长程电子转移机制。

  DOI：

  10.1246/bcsj.64.3005

文献信息

• New and Efficient Arrays for Photoinduced Charge Separation Based on Perylene Bisimide and Corroles
  作者：Lucia Flamigni、Barbara Ventura、Mariusz Tasior、Thomas Becherer、Heinz Langhals、Daniel T. Gryko

  DOI：10.1002/chem.200700866

  日期：2008.1

  Excitation of the perylene bisimide unit is followed by competing reactions of: 1) energy transfer to the corrole unit, which subsequently deactivates to the charge-separated state and; 2) electron transfer to directly form the charge-separated state. The ratio of electron-to-energy-transfer rates is 9:1 and 1:1 for C3-PI and C3-PPI, respectively. The yield of charge separation is essentially 100

  已经合成了双发色体系C2-PI，C3-PI和C3-PPI，它们由腐蚀和per双酰亚胺单元组成，代表了基于腐蚀的复杂结构的罕见情况之一。环C2和C3分别是在5和15位具有2，6-二氯苯基和五氟苯基取代基的内消旋取代的环。通过发散策略制备了三个二元组，其中形成了Corrole的反应是该序列的最后一步。C2-PI和C3-PI的性质不同，而C3-PI与C3-PPI的区别在于光敏单元之间的连接基中还存在另一个苯基单元。二面体显示的光谱性质是组分光谱的叠加，表明电子耦合非常弱。对于C2-PI，C3- PI和C3-PPI，分别以δG度> 0为特征。激发bi双酰亚胺单元后，将发生以下竞争反应：1）能量转移至Corrole单元，该单元随后失活至电荷分离状态；和 2）电子转移直接形成电荷分离状态。C3-PI和C3-PPI的电子能量传输率之比分别为9：1和1：1。对于C2-PI和C3-PI，电荷分离的产率基本上
• Photoinduced energy and electron transfer in 1,8-naphthalimide–corrole dyads
  作者：Mariusz Tasior、Daniel T. Gryko、Marek Cembor、Jan S. Jaworski、Barbara Ventura、Lucia Flamigni

  DOI：10.1039/b613640k

  日期：——

  A series of corrole-1,8-naphthalimide dyads has been synthesized. The dyads were assembled in a convergent fashion from two fragments via a corrole forming reaction. Central to the success of the synthetic strategy was the preparation of suitably functionalized derivatives of naphthalene-1,8-carboxymide. Six different dyads possessing either a different linker (a meta-phenylene or a para-phenylmethylene) or a corrole with different substituents at the 5 and 15 positions were prepared. A photophysical and spectroscopic characterization of the dyads and the reference models show that whereas upon selective excitation of the corrole component no photo-induced process occurs, excitation of the naphthalimide unit results in very efficient energy or electron transfer processes. The electron transfer contributes to the quenching process with a ratio between 0% and 85% depending on the nature of the corrole accepting unit. The processes are discussed in the frame of current theories. This is the first report of stable corrole-based dyads with interesting photo-activity at ambient temperature.

  我们合成了一系列 1,8-萘二甲酰亚胺吡咯。这些二元化合物是由两个片段通过珊瑚醛形成反应以聚合方式组装而成的。合成策略成功的关键在于制备了萘-1,8-羧酰亚胺的适当官能化衍生物。我们制备了六种不同的二元化合物，它们要么具有不同的连接物（元亚苯基或对位苯基亚甲基），要么具有在 5 和 15 位上具有不同取代基的珊瑚虫。对二元化合物和参考模型的光物理和光谱特性分析表明，在选择性激发珊瑚虫成分时不会发生光诱导过程，而激发萘二甲酰亚胺单元时则会产生非常有效的能量或电子转移过程。电子转移对淬火过程的贡献率在 0% 到 85% 之间，具体取决于珊瑚虫接受单元的性质。本文在现有理论框架内对这一过程进行了讨论。这是首次报道稳定的基于珊瑚虫的二元化合物在常温下具有有趣的光活性。
• Synthesis and Intramolecular Charge Separation of Fixed-Distance Triads Consisting of Zinc Porphyrin, Metal-Free Porphyrin, and Electron-Accepting Diimide Moiety
  作者：Atsuhiro Osuka、Run-Ping Zhang、Kazuhiro Maruyama、Takeshi Ohno、Koichi Nozaki

  DOI：10.1246/bcsj.66.3773

  日期：1993.12

  the occurrence of intramolecular singlet-singlet energy transfer form the ZnP to the H2P. Formation of long-lived charge-separated states (ZnP)+–H2P–(PIm)− and (ZnP)+–H2P–(NIm)− with lifetimes of 0.14—80 μs in THF was observed by nanosecond to microsecond transient absorption spectroscopy. The lifetimes of the (ZnP)+–H2P–(Im)− states depend on the distances between the charged sites as well as the

  描述了由锌卟啉 (ZnP)、无金属卟啉 (H2P) 和均苯四甲酰亚胺 (PIm) 或 1,4: 5,8-萘四甲酰亚胺 (NIm) 组成的固定距离三元组的合成。ZnP 和 部分由芳族间隔基桥接，例如 1,4-亚苯基、4,4'-亚联亚苯基、亚甲基双 (1,4-亚苯基) 和双环 [2.2.2] 辛烷-1,4-二基双 (1 ,4-亚苯基）基团。稳态荧光光谱表明发生了分子内单线态-单线态能量从 ZnP 到 的转移。通过纳秒至微秒瞬态吸收光谱法观察到在 THF 中形成寿命为 0.14-80 μs 的长寿命电荷分离态 (ZnP)+– –(PIm)- 和 (ZnP)+– –(NIm)- .
• Solvent polarity effect on intramolecular electron transfer in a corrole–naphthalene bisimide dyad
  作者：Lucia Flamigni、Dagmara Wyrostek、Roman Voloshchuk、Daniel T. Gryko

  DOI：10.1039/b916525h

  日期：——

  A dyad (C3–NI) based on corrole and naphthalene bisimide has been synthesized and its photoreactivity compared to that of the model component corrole (C3) and naphthalene bisimide (NI) in solvents of different polarity: toluene (TL) and dichloromethane (DCM). The major emitting species in NI solutions, in TL, is identified as a dimeric species (λ = 470 nm, τ = 2.3 ns) but traces of monomer can also

  合成了一种基于腐蚀物和萘双酰亚胺的二元体（C3- NI），与模型成分腐蚀剂（C3）和萘二酰亚胺（NI）相比，在不同极性的溶剂中其光反应性：甲苯 （TL） 和 二氯甲烷 （DCM）。NI解决方案中的主要发射物质TL被鉴定为二聚体（λ = 470 nm，τ = 2.3 ns），但也可以检测到痕量单体（λ约390 nm，τ = 40 ps）。在DCM中，主要的发射成分是单体（λ = 383 nm，τ = 20 ps），但存在痕量的不同聚集体（λ = 540和570 nm，τ = 4.5和11 ns）。C3的荧光几乎不受溶剂极性的影响，最大值约为655，在DCM和DCM中的寿命为3.5或3.8 ns。TL， 分别。二元体C3- NI似乎不受任何溶剂中聚集问题的影响。在酰亚胺成分的激励C3- NI（C 3 -C 1 NI中的能量转移到corrole（）结果1 C3- NI与率）ķ = 2.0×10
• Linkage Dependent Charge Separation and Charge Recombination in Porphyrin-Pyromellitimide-Fullerene Triads
  作者：Hiroshi Imahori、Koichi Tamaki、Yasuyuki Araki、Taku Hasobe、Osamu Ito、Akihisa Shimomura、Santi Kundu、Tadashi Okada、Yoshiteru Sakata、Shunichi Fukuzumi

  DOI：10.1021/jp014433f

  日期：2002.3.1

  A homolocous series of zincporphyrin (ZnP)-pyromellitimide (Im)-C-60 linked triads where the pyromellitimide (Im) moiety is incorporated as an intermediate acceptor between the above two chromophores with a linkage of different spacers, ZnP-Im-CH2-C-60, ZnP-IM-C-60, and ZnP-CH2-Im-C-60 as well as the reference dyads (ZnP-Im-CH2-ref, ZnP-Im-ref, and ZnP-CH2-Im-ref) have been prepared to investigate linkage dependence of photoinduced electron transfer (ET) and back ET to the ground state in the triads. Time-resolved transient absorption spectra of the triads measured by picosecond laser photolysis as well as the fluorescence lifetimes in THF reveal the occurrence of photoinduced ET from the singlet excited state of the ZnP to the Im moiety to give the initial charge-separated state, i.e., the zincporphyrin radical cation (ZnP.+)-imide radical anion (Im(.-)) pair, followed by a charge shift (CSH) to produce the final charge-separated state, the ZnP.+-C-60(.-) pair. The rate constants of photoinduced ETs in ZnP-Im-C-60 (1.8 x 10(10) s(-1)) and ZnP-Im-CH2-C-60 (1.3 x 10(10) s(-1)) in THF are much larger than those in ZnP-CH2-IM-C-60 (2.9 x 10(9) s(-1)) and ZnP-CH2-Im-ref (1.9 x 10(9)) s-1). The larger charge separation (CS) rates in the former case are ascribed to the relatively strong electronic coupling because of the absence of a methylene linkage between the ZnP and the Im moieties in ZnP-Im-C-60 and ZnP-Im-CH2-C60 as compared to the triad and dyad with the methylene linkage. The transient absorption spectra of the final charge-separated state, the ZnP.+-C-60(.-) pair, have been also measured by nanosecond laser photolysis. It has been found that the rate constants of charge recombination (CR) of ZnP.+-Im-C-60(.-) are temperature independent, but that the CR rate constants of ZnP.+-Im-CH2-C-60(.-) exhibit an Arrhenius-like temperature dependence with an activation energy of 0.13 eV which corresponds to the energy difference between ZnP.+-Im(.-)CH(2)-C-60 and ZnP.+-Im-CH2-C-60(.-). This indicates that the relatively strong electronic coupling without methylene linkage in ZnP-IM-C60 results in the preference of the tunneling superexchange ET over the sequential ET in the CR process which requires the thermal activation to reach the higher energy state (i.e., ZnP.+-Im(.-)-C-60), whereas the sequential ET predominates in the triads with the methylene linkage.