tert-butyl 4-(N-phenylamino)benzoate

• 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 4-(N-phenylamino)benzoate
• 英文别名: Tert-butyl 4-(phenylamino)benzoate；tert-butyl 4-anilinobenzoate
• 化学式: C₁₇H₁₉NO₂
• 分子量: 269.343
• InChiKey: GAPUSCCDEOJMBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 4-(N-phenylamino)benzoate 在 三叔丁基膦 、 palladium diacetate 、 caesium carbonate 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 14.0h， 生成 4-((7-(5'-(2,2-dicyanovinyl)-2,2'-bithiophen-5-yl)-9,9-dihexyl-9H-fluoren-2-yl)(phenyl)amino)benzoic acid
  参考文献：
  名称：

  Arylamine-Based Dyes for p-Type Dye-Sensitized Solar Cells

  摘要：

  New arylamine-based sensitizers for p-type dye-sensitized solar cells (DSSCs) have been synthesized and used for p-type DSSCs. The best conversion efficiency reaches similar to 0.1%. Sensitizers with two anchoring carboxylic acids lead to higher open-circuit voltages, short-circuit currents, and energy conversion efficiencies.

  DOI：

  10.1021/ol202014x
• 作为产物：
  描述：

  4-溴苯甲酰氯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 tri-tert-butylphosphonium tetrafluoroborate 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.0h， 生成 tert-butyl 4-(N-phenylamino)benzoate
  参考文献：
  名称：

  Synthesis and characterization of perylene–bithiophene–triphenylamine triads: studies on the effect of alkyl-substitution in p-type NiO based photocathodes

  摘要：

  我们报道了新型供体-π-受体（D-π-A）染料的合成及其在基于氧化镍（NiO）光阴极的染料敏化太阳能电池（DSC）中的应用。这些D-π-A敏化剂包含三苯胺供体、联噻吩π桥和苝酰亚胺（PMI）受体基团。两个连在三苯胺上的羧酸基团使染料与NiO表面牢固锚定。该系列染料首先通过在联噻吩和三苯胺单元之间引入乙炔连接基团（1 vs. 2）来变化，从而增加了共轭桥的长度。尽管光电性质非常相似，但含乙炔的染料2在p-DSC中与1相比显示了约25%的功率转换效率提升，这主要归因于电流密度的增加。与最初的预期相反，纳米秒瞬态吸收光谱（TAS）测量的结果显示，染料的PMI单元与NiO表面之间的距离对光诱导的染料阴离子寿命没有主要影响。此外，改变连接桥上的联噻吩上的烷基链的位置（3和4）导致染料吸收光谱的轻微红移，这是由于PMI和π桥之间的电荷离域增加，这是由于PMI和相邻噻吩单元之间的扭转角减小。进行了量子化学DFT计算，以评估这些扭转角并研究它们对相关分子轨道中电子密度分布的影响。异构体染料3和4的分子结构的这些变化并没有转化为光伏性能的改善，这主要是由于瞬态吸收光谱探测到的较低的电荷光生率。尽管对于p型DSC，在全太阳光照下（模拟AM1.5G阳光，100 mW cm⁻²）展示了令人印象深刻的总体光-电转换效率（0.04-0.10%）和广泛的入射光子-电流效率（IPCE）响应（350-700 nm），但对于这些新型染料的研究清楚地表明，在用于光阴极DSC的p型敏化剂的设计中，需要谨慎的设计规则。

  DOI：

  10.1039/c2jm16847b

文献信息

• Synthesis and characterization of perylene–bithiophene–triphenylamine triads: studies on the effect of alkyl-substitution in p-type NiO based photocathodes
  作者：Martin Weidelener、Amaresh Mishra、Andrew Nattestad、Satvasheel Powar、Attila J. Mozer、Elena Mena-Osteritz、Yi-Bing Cheng、Udo Bach、Peter Bäuerle

  DOI：10.1039/c2jm16847b

  日期：——

  We report the synthesis of new donor–π–acceptor (D–π–A) dyes and their application in dye-sensitized solar cells (DSCs) with nickel(II) oxide (NiO)-based photocathodes. These D–π–A sensitizers incorporate a triphenylamine donor, a bithiophene π-bridge, and a perylenemonoimide (PMI) acceptor group. Two carboxylate groups attached to the triphenylamine afford strong anchoring to the NiO surface. The dyes in this series were varied firstly by the inclusion of an ethynyl linker between bithiophene and the triphenylamine moieties (1vs. 2), thereby increasing the length of the conjugated bridge. Despite very similar optoelectronic properties, the ethynyl-containing dye 2 showed a ∼25% improvement in power conversion efficiency in p-DSCs compared to 1, mostly attributed to the increased current density. Contrary to initial expectations, there was no major influence of the distance between the PMI unit of the dye and the NiO surface on the photoinduced dye anion lifetime, as measured by nanosecond transient absorption spectroscopy (TAS). Furthermore, altering the position of the alkyl chains on the bridging bithiophene in 3 and 4 resulted in a modest red shift in the dye absorption on account of increased charge delocalisation between the PMI and the π-bridge, owing to a reduced torsion angle between the PMI and the adjacent thiophene unit. Quantum-chemical DFT calculations were performed in order to evaluate these torsion angles and to study their influence on the electron density distribution in the relevant molecular orbitals. These changes of the molecular structure of the isomeric dyes 3 and 4 did not translate into improved photovoltaic performance, which is primarily attributed to lower charge photogeneration rates probed by transient absorption spectroscopy. While for p-type DSCs impressive overall solar-to-electric conversion efficiency of 0.04–0.10% under full sun illumination (simulated AM1.5G sunlight, 100 mW cm−2) and a broad incident photon to current efficiency (IPCE) response (350–700 nm) is demonstrated for these new dyes, the study clearly shows the need for judicious design rules for p-type sensitizers for application in photocathodic DSCs.

  我们报道了新型供体-π-受体（D-π-A）染料的合成及其在基于氧化镍（NiO）光阴极的染料敏化太阳能电池（DSC）中的应用。这些D-π-A敏化剂包含三苯胺供体、联噻吩π桥和苝酰亚胺（PMI）受体基团。两个连在三苯胺上的羧酸基团使染料与NiO表面牢固锚定。该系列染料首先通过在联噻吩和三苯胺单元之间引入乙炔连接基团（1 vs. 2）来变化，从而增加了共轭桥的长度。尽管光电性质非常相似，但含乙炔的染料2在p-DSC中与1相比显示了约25%的功率转换效率提升，这主要归因于电流密度的增加。与最初的预期相反，纳米秒瞬态吸收光谱（TAS）测量的结果显示，染料的PMI单元与NiO表面之间的距离对光诱导的染料阴离子寿命没有主要影响。此外，改变连接桥上的联噻吩上的烷基链的位置（3和4）导致染料吸收光谱的轻微红移，这是由于PMI和π桥之间的电荷离域增加，这是由于PMI和相邻噻吩单元之间的扭转角减小。进行了量子化学DFT计算，以评估这些扭转角并研究它们对相关分子轨道中电子密度分布的影响。异构体染料3和4的分子结构的这些变化并没有转化为光伏性能的改善，这主要是由于瞬态吸收光谱探测到的较低的电荷光生率。尽管对于p型DSC，在全太阳光照下（模拟AM1.5G阳光，100 mW cm⁻²）展示了令人印象深刻的总体光-电转换效率（0.04-0.10%）和广泛的入射光子-电流效率（IPCE）响应（350-700 nm），但对于这些新型染料的研究清楚地表明，在用于光阴极DSC的p型敏化剂的设计中，需要谨慎的设计规则。
• Aqueous Hydroxide as a Base for Palladium-Catalyzed Amination of Aryl Chlorides and Bromides
  作者：Ryoichi Kuwano、Masaru Utsunomiya、John F. Hartwig

  DOI：10.1021/jo0258913

  日期：2002.9.1

  amination of aryl halides in the presence of inexpensive and air-stable alkali metal hydroxide bases and Pd[P(t-Bu)3]2 as catalyst gave arylamines in high yields. The reactions were conducted with a catalytic amount of cetyltrimethylammonium bromide as phase-transfer agent and either aqueous hydroxide or solid hydroxide in the presence of water. This combination of alkali metal hydroxide base, H2O, and

  在廉价且空气稳定的碱金属氢氧化物碱和Pd [P（t-Bu）3] 2作为催化剂的存在下，芳基卤化物的胺化反应可高收率得到芳基胺。反应是在水的存在下，用催化量的十六烷基三甲基溴化十六烷基铵作为相转移剂，并用氢氧化物水溶液或固体氢氧化物进行的。在对氯甲苯与二丁胺的胺化反应中，碱金属氢氧化物碱，H2O和铵盐的这种组合与NaO-t-Bu的作用相同。氢氧化物碱适用于各种芳基氯化物和溴化物与脂肪族和芳香族胺的反应。氢氧化碱，H2O，H2O，
• Nickel-Catalyzed Synthesis of Diarylamines via Oxidatively Induced C–N Bond Formation at Room Temperature
  作者：Laurean Ilies、Tatsuaki Matsubara、Eiichi Nakamura

  DOI：10.1021/ol302688u

  日期：2012.11.2

  A nickel-catalyzed oxidative coupling of zinc amides with organomagnesium compounds selectively produces diarylamines under mild reaction conditions, with tolerance for chloride, bromide, hydroxyl, ester, and ketone groups. A diamine is bis-monoarylated. A bromoaniline undergoes N-arylation followed by Kumada-Tamao-Corriu coupling in one pot. The reaction may proceed via oxidatively induced reductive elimination of a nickel species.
• π-Expanded dibenzo-BODIPY with near-infrared light absorption: Investigation of photosensitizing properties of NiO-based p-type dye-sensitized solar cells
  作者：Yuta Higashino、Sule Erten-Ela、Yuji Kubo

  DOI：10.1016/j.dyepig.2019.107613

  日期：2019.11

  Much attention has been devoted to the synthesis of dyes that absorb near-infrared (NIR) radiation because of numerous demands for them as functional materials. Given that NIR sensitizers applicable to p-type dye-sensitized solar cell (DSSC) devices are extremely rare, p-extended dibenzo-BODIPY sensitizer 1 containing triphenylamine and nitrothiophene units was synthesized; the absorption spectrum of 1 showed an intense absorption band at 730 nm with a molar extinction coefficient of 7.14 x 10 (4) M-1 cm(-1). A p-type DSSC device with a 1-loaded NiO electrode was fabricated and its cell performance was investigated. It showed an open circuit voltage (V-OC), a short circuit current density (J(SC)), and a fill factor (FF) of 79 mV, 0.61 mA cm(-2), and 0.25, respectively. Consequently, the power conversion efficiency was 0.012%. Its performance was low, mainly owing to very fast recombination between the NiO and reduced dye at the surface of the electrode. However, EQE measurement showed that the 1-loaded p-type DSSC devices convert photons into current at wavelengths up to 850 nm, so further investigation to improve the cell performance is deserved.
• Arylamine-Based Dyes for p-Type Dye-Sensitized Solar Cells
  作者：Yung-Sheng Yen、Wei-Ting Chen、Chih-Yu Hsu、Hsien-Hsin Chou、Jiann T. Lin、Ming-Chang P. Yeh

  DOI：10.1021/ol202014x

  日期：2011.9.16

  New arylamine-based sensitizers for p-type dye-sensitized solar cells (DSSCs) have been synthesized and used for p-type DSSCs. The best conversion efficiency reaches similar to 0.1%. Sensitizers with two anchoring carboxylic acids lead to higher open-circuit voltages, short-circuit currents, and energy conversion efficiencies.