methyl 4-benzoylbutyrate p-tosylhydrazone | 571170-23-5

• 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: methyl 4-benzoylbutyrate p-tosylhydrazone
• 英文别名: Methyl 5-[(4-methylphenyl)sulfonylhydrazinylidene]-5-phenylpentanoate；methyl 5-[(4-methylphenyl)sulfonylhydrazinylidene]-5-phenylpentanoate
• CAS: 571170-23-5
• 化学式: C₁₉H₂₂N₂O₄S
• 分子量: 374.461
• InChiKey: RJLUCHQZFNDXOE-UHFFFAOYSA-N

物化性质

• 熔点：
  122 °C
• 沸点：
  524.3±60.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  93.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-benzoylbutyrate p-tosylhydrazone 在 吡啶 、 sodium methylate 作用下， 生成 1-Phenyl-1-(3-(methoxycarbonyl)propyl)diazomethane
  参考文献：
  名称：

  PCBM 甲烷富勒烯（C60 和 C70）的高效微波辅助合成

  摘要：

  PCBM是一种富勒烯衍生物（苯基-C61-丁酸甲酯），被认为是最好的n型有机半导体之一，在有机光伏太阳能电池中发挥着相关作用。许多努力致力于优化 PCBM 衍生物的合成。在本文中，PC61BM 和 PC71BM 富勒烯单加合物以及 PCBM 类衍生物在微波辐射下通过一步环丙烷化反应成功制备。在短时间内以良好的收率收集产物，在此期间，开放的 [5,6] 异构化为封闭的 [6,6] 形式在原位发生。此外，通过使用两个辐射循环，还以良好的产率获得了一系列双加合物类 PCBM 衍生物的混合物。

  DOI：

  10.1002/ejoc.201403563
• 作为产物：
  描述：

  4-苯甲酰基丁酸 在 硫酸 作用下， 以 甲醇 、 苯 为溶剂， 反应 3.0h， 生成 methyl 4-benzoylbutyrate p-tosylhydrazone
  参考文献：
  名称：

  Methanofullerenes Used as Electron Acceptors in Polymer Photovoltaic Devices

  摘要：

  A series of [6,6]-phenyl C-61-butyric acid esters, including methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) with different alkyl chain lengths (C-1-C-16) was synthesized from the reaction Of C-60 and alkyl 4-benzoylbutyrate p-tosylhydrazone in the presence of sodium methylate. The solubility Of C-60 derivatives in organic solvents increased with the increase in the length of alkyl substitutions. Photovoltaic cells with these derivatives were fabricated with the structure of ITO/PEDT/MEH-PPV + C-60 derivatives/Ba/Al. Device performances with such PCBM analogues were investigated and discussed in terms of Donor/Acceptor (D/A) phase separation and mobility of acceptor phase. The results clearly indicate that both interfacial properties of the two phases (donor and acceptor) and mobility of electrons and holes within corresponding phases play an important role in the efficiencies of PV cells. This study revealed that methanofullerenes [6,6]-phenyl C-61-butyric acid butyl ester, PCBB, possesses better photosensitivity than the PCBM, a widely investigated and well-recognized C-60 derivative for polymer PV cells The energy conversion efficiency reaches 2.84% for PCBB under AM1.5 illumination (78.2 mW/cm(2)), but 2.0% for PCBM fabricated in the same conditions.

  DOI：

  10.1021/jp048890i

文献信息

• Reaction of diazocompounds with C₇₀: unprecedented synthesis and characterization of isomeric [5,6]-fulleroids
  作者：Sara Vidal、Marta Izquierdo、Salvatore Filippone、Fulvio G. Brunetti、Nazario Martín

  DOI：10.1039/c5cc07602a

  日期：——

  Three new [5,6]-PCBM isomeric fulleroids photoisomerize, in a quantitative and highly selective way, to their respective [6,6]-PCBM methanofullerenes.

  三种新的[5,6]-PCBM同分异构富勒烯发生光异构化，以定量和高度选择性的方式转化为它们各自的[6,6]-PCBM甲基富勒烯。
• Photochemical site-selective synthesis of [70]methanofullerenes
  作者：Sara Vidal、Marta Izquierdo、Wai Kit Law、Kui Jiang、Salvatore Filippone、Josefina Perles、He Yan、Nazario Martín

  DOI：10.1039/c6cc06072b

  日期：——

  Methanofullerenes such as the well-known [70]PCBM are commonly synthesized under harsh conditions to obtain the product as a mixture of site-isomers (namely [small alpha], [small beta] and minor [gamma]) due to the...

  甲基富勒烯例如众所周知的[70] PCBM通常是在苛刻的条件下合成的，从而由于位异构体（即小α，小β和小γ）的混合物而得到产物。 。
• Supramolecular pentapeptide-based fullerene nanofibers: effect of molecular chirality
  作者：Alberto Insuasty、Carmen Atienza、Juan Luis López、Nazario Martín

  DOI：10.1039/c5cc01991e

  日期：——

  The supramolecular organization of new fullerene derivatives endowed with peptides as biomolecular templates affords ordered nanofibers of several micrometres length based on hydrogen bonds and [small pi]-[small pi] interactions.

  具有肽作为生物分子模板的新富勒烯衍生物的超分子组织提供了基于氢键和小π-小π相互作用的几微米长的有序纳米纤维。
• Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units
  作者：David Kreher、Michel Cariou、Sheng-Gao Liu、Eric Levillain、Jaume Veciana、Concepció Rovira、Alain Gorgues、Piétrick Hudhomme

  DOI：10.1039/b201695h

  日期：2002.6.21

  Our recent works on fused TTF–C60 dyads, (TTF)n–C60 polyads and C60–TTF–C60 dumbbell triads in which the acceptor C60 is doubly tethered to the donor tetrathiafulvalene through a rigidified cyclohexene ring are presented. This approach was developed in order to control the relative orientation as well as the distance between both donor and acceptor entities. Thereby, through-space interactions which are of great importance for photoinduced electron- and/or energy-transfer processes are expected to dominate because of the special topology of the molecules. The two linked C60 and TTF chromophores in such adducts are not only in close proximity but also have optimal orbital orientations, thus facilitating these through-space electronic interactions. These new C60-based assemblies were synthesized by [4 + 2] Diels–Alder cycloaddition reactions. The different methodologies considered for their synthesis are discussed, their analytical, spectroscopic characterizations and electrochemical properties are also described. The selective electro-oxidation or reduction afforded the corresponding radical cation and radical anion which were characterized by EPR. These C60-based assemblies were studied for their nonlinear optical and optical limiting applications. Moreover, intramolecular photoinduced charge-separation and charge-recombination processes in a fused C60–TTF–C60 dumbbell triad which was designed to be soluble in organic solvents were investigated by time-resolved absorption and fluorescence techniques. Appreciable interaction between the C60 moiety and TTF moiety in the ground state was suggested by steady-state absorption spectra and the fluorescence spectra showed considerable interaction in the singlet excited state. The nanosecond transient absorption spectra displayed the formation of the charge-separated radical pair C60–TTF˙+–C60˙−, characterized by a lifetime of ca. 20 ns in benzonitrile.

  我们最近的研究工作集中在融合的TTF–C60二聚体、(TTF)n–C60多聚体和C60–TTF–C60哑铃三聚体，这些体系中受体C60通过刚性的环己烯环与供体四硫富瓦烯双重连接。此方法的开发旨在控制供体和受体之间的相对方向和距离。因此，由于分子的特殊拓扑结构，空间内的相互作用在光诱导电子及/或能量转移过程中预计将占主导地位。这种加合物中连接的C60和TTF色团不仅相互接近，而且具有最佳的轨道取向，从而促进这些跨空间的电子相互作用。这些新的基于C60的组装体是通过[4 + 2]迪尔斯－阿尔德环加成反应合成的。文中讨论了其合成过程中考虑的不同方法，并描述了它们的分析、光谱特性及电化学性质。选择性电氧化或还原生成了相应的自由基阳离子和自由基阴离子，这些都通过电子顺磁共振（EPR）进行了表征。这些基于C60的组装体也被研究用于其非线性光学和光限制应用。此外，设计为可溶于有机溶剂的融合C60–TTF–C60哑铃三聚体中的分子内光诱导电荷分离和电荷重组过程通过时间分辨吸收和荧光技术进行了研究。在基态中，稳态吸收光谱表明C60基团与TTF基团之间存在显著的相互作用，而荧光光谱则显示在单重激发态中也存在较强的相互作用。纳秒瞬态吸收光谱显示了电荷分离的自由基对C60–TTF˙+–C60˙–，其在苯腈中表征的寿命约为20纳秒。
• Efficient microwave-mediated synthesis of fullerene acceptors for organic photovoltaics
  作者：Vincenzo Campisciano、Serena Riela、Renato Noto、Michelangelo Gruttadauria、Francesco Giacalone

  DOI：10.1039/c4ra10495a

  日期：——

  Two different processes, namely the Bamford–Stevens and [4 + 2] Diels Alder reactions, have been optimized under microwave irradiation for the functionalization of fullerenes. In this manner, all the main C60- and C70-based acceptor derivatives for organic solar cells such as PCBM, DPM, BHN and ICBA, have been prepared in higher yields and shorter reaction times with respect to the reported data. These findings represent a step forward toward the wide production of cheaper organic solar cells as a consequence of the cost abatement of the acceptors given by higher yields, lower waste production, and reduced reaction time which means a strong energy saving.

  在微波辐照下优化了富勒烯功能化的两种不同过程，即 BAmford-Stevens 反应和 [4 + 2] Diels Alder 反应。通过这种方式，制备出了用于有机太阳能电池的所有基于 C60 和 C70 的主要受体衍生物，如 PCBM、DPM、BHN 和 ICBA，与报告数据相比，产率更高、反应时间更短。这些发现标志着向广泛生产更廉价的有机太阳能电池迈进了一步，因为更高的产量、更低的废物产生量和更短的反应时间降低了受体的成本，这意味着极大地节约了能源。