9,9-diethyl-2-diphenylaminofluorene | 148077-53-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 9,9-diethyl-2-diphenylaminofluorene
• 英文别名: 9,9-diethyl-N,N-diphenylfluoren-2-amine
• CAS: 148077-53-6
• 化学式: C₂₉H₂₇N
• 分子量: 389.54
• InChiKey: AIFJPBDCQLMTTD-UHFFFAOYSA-N

物化性质

• 沸点：
  540.7±29.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  9,9-diethyl-2-diphenylaminofluorene 在 三氯化铝 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 9.0h， 生成 7-(1,2-methano[60]fullerene-61-carbonyl)-9,9-diethyl-2-diphenylaminofluorene
  参考文献：
  名称：

  Synthesis of C60-diphenylaminofluorene dyad with large 2PA cross-sections and efficient intramolecular two-photon energy transfer

  摘要：

  首次合成了一种包含A-sp3-D共轭结构的C60衍生物，该化合物表现出在纳秒时间尺度内极佳的双光子吸收截面（σ2′ = 196 ×10−48 cm4 sec−1 molecule−1），这些数值在基于二苯胺芴的AFX染料中名列前茅。

  DOI：

  10.1039/b202681c
• 作为产物：
  描述：

  2-溴芴 在 sodium hydroxide 、 tris-(dibenzylideneacetone)dipalladium(0) 、 四丁基溴化铵 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 9,9-diethyl-2-diphenylaminofluorene
  参考文献：
  名称：

  Synthesis and characterization of photoresponsive diphenylaminofluorene chromophore adducts of [60]fullerene

  摘要：

  合成了一类接受体-酮-供体结构，包括受阻的9,9-二（3,5,5-三甲基己基）-2-二苯胺氟烯-美琅[60]富勒烯C60(>DPAF-C9)及相关的双加合物C60(>DPAF-C9)2和C60(>DPAF-C2)2。它们是多光子吸收C60(>DPAF-C2)的衍生物，在激光激发下800 nm的纳秒区域显示出增强的同时两光子吸收截面。这些C60-DPAF共轭物的分子合成涉及通过酮联结将二苯氨基氟烯部分共价连接到美琅[60]富勒烯上，以增加分子的接受体-供体极性，与富勒烯笼体结合。7-(1,2-二氢-1,2-美琅富勒烯[60]-61-羰基)-9,9-二烷基-2-二苯胺氟烯C60(>DPAF-Cn)的制备涉及用关键合成单元7-α-溴乙酰-9,9-二烷基-2-二苯胺氟烯对C60进行环丙烷化。该合成单元的合成通过三步法实现，起始于2-溴氟烯，通过对氟烯环的C9位的双烷基化，在双烷基氟烯的C2位上连接二苯胺基团，以及在二苯胺氟烯的C7位对α-溴乙酰基进行弗riedel-Craft酰化。所有C60-DPAF衍生物均经过全面表征，化学结构通过各种光谱分析确认，并通过C60(>DPAF-C2)的单晶结构分析数据进行验证。观察到C60(>DPAF-C2)、C60(>DPAF-C9)和C60(>DPAF-C9)2的强溶剂敏感荧光猝灭现象，在更极性溶剂（如DMF、PhCN和THF）中未观察到700 nm以上的荧光带，而在较少极性的溶剂（如甲苯、CHCl3和CS2）中观察到700-710 nm的富勒烯荧光带。这归因于在前一组溶剂中，通过富勒烯部分的单态激发态1C60*(>DPAF-Cn)发生电子转移。相反，在后者溶剂组中，DPAF-Cn部分向富勒烯笼体的能量转移过程更加有利。

  DOI：

  10.1039/b515055h

文献信息

• [EN] FULLERENE COMPOUNDS<br/>[FR] COMPOSES DE FULLERENES
  申请人：CHIANG LONG Y

  公开号：WO2004007426A1

  公开（公告）日：2004-01-22

  The invention relates to fullerene compounds of formula (I); in which X1, X2, X3, X4, X5, YI, Y2, V, W, F, E, R, r, n, p, and q are defined as in the specification. Also disclosed are pharmaceutical compositions containing one of the compounds described above.

  该发明涉及化学式（I）的富勒烯化合物；其中X1、X2、X3、X4、X5、Y1、Y2、V、W、F、E、R、r、n、p和q的定义如规范中所述。还公开了含有上述化合物之一的药物组合物。
• Fullerene compounds
  申请人：Chiang Y. Long

  公开号：US20050191229A1

  公开（公告）日：2005-09-01

  The invention relates to fullerene compounds of the following formula: in which X 1 , X 2 , X 3 , X 4 , X 5 , Y 1 , Y 2 , V, W, F, E, R, r, n, p, and q are defined as in the specification. Also disclosed are pharmaceutical compositions containing one of the compounds described above.

  本发明涉及以下式子的富勒烯化合物：其中X1，X2，X3，X4，X5，Y1，Y2，V，W，F，E，R，r，n，p和q如规范中所定义。还披露了含有上述化合物之一的药物组合物。
• 2,7-Diaminofluorene-Based Organic Dyes for Dye-Sensitized Solar Cells: Effect of Auxiliary Donor on Optical and Electrochemical Properties
  作者：Abhishek Baheti、Prachi Singh、Chuan-Pei Lee、K. R. Justin Thomas、Kuo-Chuan Ho

  DOI：10.1021/jo200501b

  日期：2011.6.17

  New organic dyes containing a diarylaminofluorene unit as an electron donor and cyanoacrylic acid as acceptor and anchoring group in a donor-pi-donor-pi-acceptor architecture have been synthesized and characterized as sensitizers for nanocrystalline TiO2-based dye-sensitized solar cells. They have shown three major electronic absorptions originating from the pi-pi* and charge-transfer transitions covering the broad visible range (250-550 nm) in solution. The charge-transfer transition of the dyes exhibited negative solvatochromism, suggesting a polarized ground state. They have also displayed acidochromism in solution owing to the presence of a protonation-deprotonation equilibrium. On comparison with the triphenylamine and carbazole-based parent dyes (E)-2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid and (E)-2-cyano-3-(9-ethyl-9H-carbazol-3-yl)acrylic acid they exhibited longer wavelength absorptions and facile oxidation, indicating the stronger electron-donating ability of the auxiliary chromophores. In addition, they exhibited nearly two times larger light-to-electron conversion efficiency under simulated AM 1.5 G irradiation (100 mW cm(-2)) with an aperture mask when compared to the parent dyes. Among the new dyes, the one containing the naphthylphenylamine segment showed better device characteristics attributable to the higher HOMO energy level which probably facilitates the regeneration of the dye and effective suppression of the back reaction of the injected electrons with the I-3(-) in the electrolyte. The optical properties of the dyes were modeled using TDDFT simulations employing different theoretical models (B3LYP, CAM-B3LYP, and MPW1K), and the best correlations with the observed parameters have been found for CAM-B3LYP and MPW1K calculations. The electron lifetimes extracted from the electrochemical impedance measurements of the dye-sensitized solar cells were used to interpret the solar cell efficiency alternations.
• US7132572B2
  申请人：——

  公开号：US7132572B2

  公开（公告）日：2006-11-07
• Synthesis and characterization of photoresponsive diphenylaminofluorene chromophore adducts of [60]fullerene
  作者：Prashant A. Padmawar、Taizoon Canteenwala、Sarika Verma、Loon-Seng Tan、Long Y. Chiang

  DOI：10.1039/b515055h

  日期：——

  A class of acceptor–keto–donor structures as hindered 9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluoreno-methano[60]fullerene C60(>DPAF-C9) and the related bisadducts C60(>DPAF-C9)2 and C60(>DPAF-C2)2 were synthesized. They are derivatives of multiphoton absorptive C60(>DPAF-C2) showing enhanced cross-sections of simultaneous two-photon absorption under laser excitation at 800 nm in nanosecond region. Molecular synthesis of these C60–DPAF conjugates involved the covalent attachment of a diphenylaminofluorene moiety to methano[60]fullerene via a keto linkage for increasing molecular acceptor–donor polarization of the chromophore in conjunction with the fullerene cage. Preparation of 7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-dialkyl-2-diphenylaminofluorene C60(>DPAF-Cn) involved cyclopropanation of C60 with a key synthon 7-α-bromoacetyl-9,9-dialkyl-2-diphenylaminofluorene. Synthesis of this synthon was achieved by a three-steps procedure starting from 2-bromofluorene via dialkylation at C9 of the fluorene ring, attachment of a diphenylamino group at C2 of dialkylfluorene, and Friedel–Craft acylation of the α-bromoacetyl group at C7 of diphenylaminofluorene. All C60–DPAF derivatives were fully characterized with the chemical structures confirmed by various spectroscopic analyses and validated by the single-crystal structural analysis data of C60(>DPAF-C2). Strong solvent-sensitive fluorescence quenching phenomena of C60(>DPAF-C2), C60(>DPAF-C9), and C60(>DPAF-C9)2 were noticed, showing no fluorescence band above 700 nm in more polar solvents, such as DMF, PhCN, and THF, while in less polar solvents (toluene, CHCl3, and CS2) a fullerenyl fluorescence band at 700–710 nm was observed. It was attributed to the occurrence of electron transfer via the singlet excited state of the fullerene moiety 1C60*(>DPAF-Cn) in the former group of the solvents. On the contrary, energy transfer processes from DPAF-Cn moiety to the fullerene cage are favored in the latter group of the solvents.

  合成了一类接受体-酮-供体结构，包括受阻的9,9-二（3,5,5-三甲基己基）-2-二苯胺氟烯-美琅[60]富勒烯C60(>DPAF-C9)及相关的双加合物C60(>DPAF-C9)2和C60(>DPAF-C2)2。它们是多光子吸收C60(>DPAF-C2)的衍生物，在激光激发下800 nm的纳秒区域显示出增强的同时两光子吸收截面。这些C60-DPAF共轭物的分子合成涉及通过酮联结将二苯氨基氟烯部分共价连接到美琅[60]富勒烯上，以增加分子的接受体-供体极性，与富勒烯笼体结合。7-(1,2-二氢-1,2-美琅富勒烯[60]-61-羰基)-9,9-二烷基-2-二苯胺氟烯C60(>DPAF-Cn)的制备涉及用关键合成单元7-α-溴乙酰-9,9-二烷基-2-二苯胺氟烯对C60进行环丙烷化。该合成单元的合成通过三步法实现，起始于2-溴氟烯，通过对氟烯环的C9位的双烷基化，在双烷基氟烯的C2位上连接二苯胺基团，以及在二苯胺氟烯的C7位对α-溴乙酰基进行弗riedel-Craft酰化。所有C60-DPAF衍生物均经过全面表征，化学结构通过各种光谱分析确认，并通过C60(>DPAF-C2)的单晶结构分析数据进行验证。观察到C60(>DPAF-C2)、C60(>DPAF-C9)和C60(>DPAF-C9)2的强溶剂敏感荧光猝灭现象，在更极性溶剂（如DMF、PhCN和THF）中未观察到700 nm以上的荧光带，而在较少极性的溶剂（如甲苯、CHCl3和CS2）中观察到700-710 nm的富勒烯荧光带。这归因于在前一组溶剂中，通过富勒烯部分的单态激发态1C60*(>DPAF-Cn)发生电子转移。相反，在后者溶剂组中，DPAF-Cn部分向富勒烯笼体的能量转移过程更加有利。