(1,2-methano[60]fullerene-61-carbonyl)benzene

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (1,2-methano[60]fullerene-61-carbonyl)benzene
• 化学式: C₆₈H₆O
• 分子量: 838.795
• InChiKey: QZDSZMBZTVDPJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.6
• 重原子数：
  69
• 可旋转键数：
  2
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1,2-methano[60]fullerene-61-carbonyl)benzene 、 丙二腈 在 吡啶 、 四氯化钛 作用下， 以 甲苯 为溶剂， 反应 0.08h， 以66%的产率得到(1,2-methano[60]fullerene-61-{1,1-dicyanoethylene})benzene
  参考文献：
  名称：

  Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential

  摘要：

  我们报告了一类新型光致伸缩性 C60âDCEâ 二苯胺芴纳米结构的合成及其分子内光诱导的能量和电子转移现象。通过化学方法将 C60(>DPAF-Cn) 中的酮基转化为电子吸附性更强的 1,1-二氰基乙烯（DCE）单元，对其进行了结构改造，从而得到了电子极化程度更高的 C60(>CPAF-Cn)。这种改性还导致可见光谱中的主要波段发生了很大的浴色偏移，使吸收波长达到 600 纳米，并将 C60âDCEâDPAF 纳米结构的光致发光能力扩展到比 C60(>DPAF-Cn) 更长的红色波长。因此，C60(>DPAF-Cn) 可以使用 1000â1200 nm 的光波长进行 2γ-PDT 以增强组织穿透深度。研究发现，密切相关的 C60(>DPAF-C2M) 产生单线态氧的效率与四苯基卟啉光敏剂相当。值得注意的是，C60(>CPAF-C2M) 的单线态氧量子产率比 C60(>DPAF-C2M) 高出近 6 倍，这表明 CPAF-C2M 分子的光收集能力大大增强，并导致 C60> 笼分子产生更高效的三重态。这导致 C60(>CPAF-C2M) 通过光动力疗法（200 J cmâ2 白光）高效杀死 HeLa 细胞。我们认为，与酮基相比，1,1-二氰基乙烯基具有扩展的Ï-共轭作用和更强的电子吸收能力。

  DOI：

  10.1039/c0jm00037j
• 作为产物：
  描述：

  苯甲酰甲基-二甲基-溴化硫 、 足球烯 在 四丁基溴化铵 potassium carbonate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 (1,2-methano[60]fullerene-61-carbonyl)benzene
  参考文献：
  名称：

  Quantitative Spectroscopic Studies of the Photoexcited State Properties of Methano- and Pyrrolidino-[60]fullerene Derivatives

  摘要：

  UV/vis absorption and fluorescence spectra and fluorescence quantum yields and lifetimes of a series of methano- and pyrrolidino-[60]fullerene derivatives in different solvents are studied systematically. The absorption and fluorescence properties of the derivatives with different substituents are somewhat different from those of [60]fullerene, but very similar among themselves, indicating that the low-lying transitions and the photoexcited state processes are dictated by the electronic structures of functionalized [60]fullerene cages. The results also allow an examination of the issue concerning discrepancies between experimentally determined transition probabilities and those calculated in terms of the Strickler-Berg equation for fullerene molecules. In addition, quenchings of the excited singlet states of the [60]fullerene derivatives by electron donor N,N-diethylaniline (DEA) and the formation of emissive fullerene-DEA exciplexes in solvents of different polarities are investigated.

  DOI：

  10.1021/jp971067k

文献信息

• Cycloaddition of diazoketones to [60]fullerene in the presence of the catalytic system Pd(acac)2—PPh3—Et3Al
  作者：A. R. Tuktarov、A. R. Akhmetov、L. M. Khalilov、U. M. Dzhemilev

  DOI：10.1007/s11172-010-0124-1

  日期：2010.3

  A method for the selective and efficient synthesis of methanofullerenes by cycloaddition of diazoketones to [60]fullerene in the presence of a three-component catalytic system Pd(acac)2—PPh3—Et3Al has been developed.

  一种选择性和高效合成甲烷富勒烯的方法被开发，该方法通过在三组分催化体系Pd(acac)2—PPh3—Et3Al的存在下，将二唑酮与[60]富勒烯进行环加成反应。
• Synthesis of C60-fused tetrahydrothiophene derivatives via nucleophilic cycloaddition of thiocyanates
  作者：Guan-Wu Wang、Jia-Xing Li、Yu Xu

  DOI：10.1039/b807394e

  日期：——

  Nucleophilic cycloaddition of thiocyanates 1a–e with C60 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene afforded C60-fused 2-iminotetrahydrothiophene derivatives 2a–e and methanofullerenes 3a–d. The product distributions were highly sensitive to the substrates employed. The 2-iminotetrahydrothiophene derivatives 2a–e could be further manipulated by hydrolysis and acetylation to give 2-oxotetrahydrothiophene derivatives 4a–e and 2-acetamidotetrahydrothiophene derivatives 5a–e. A possible reaction mechanism for the formation of products 2a–e and 3a–d was proposed.

  噻吩氰酸盐1a–e与C60在1,8-二氮-双环[5.4.0]十一烯存在下进行亲核环加成反应，生成C60融合的2-亚氨基四氢噻吩衍生物2a–e和甲烷全氟烯3a–d。产物分布对所采用的底物非常敏感。2-亚氨基四氢噻吩衍生物2a–e可通过水解和乙酰化进一步转化为2-氧四氢噻吩衍生物4a–e和2-乙酰基四氢噻吩衍生物5a–e。提出了生成产物2a–e和3a–d的可能反应机理。
• Formation of fulleroids as major products and application of solid state reaction in the functionalization of [60]fullerene by aromatic diazoketones
  作者：Yosuke Nakamura、Ken'ichi Inamura、Ryosuke Oomuro、Richard Laurenco、Thomas T. Tidwell、Jun Nishimura

  DOI：10.1039/b505558j

  日期：——

  examined, the fulleroid with the methine proton located over a six-membered ring was obtained as a major product along with a slight amount of the other fulleroid diastereoisomer and methanofullerene. Solid-state reactions considerably enhanced the reaction efficiency with minor effects on the selectivity. The thermal isomerization and photoisomerization from fulleroids into methanofullerene were relatively

  在溶液（邻二氯苯）或固态下研究了各种芳族​​重氮酮与[60]富勒烯的反应。在所有检查的条件下，均获得了以次甲基质子位于六元环上的富勒烯作为主要产物，以及少量的其他富勒烯非对映异构体和甲基富勒烯。固态反应大大提高了反应效率，而对选择性的影响却很小。从富勒烯到甲基富勒烯的热异构化和光异构化相对较慢，在所考察的条件下几乎与取代基无关。
• Solvent-free reactions of C60 with active methylene compounds, either with or without carbon tetrabromide, in the presence of bases under high-speed vibration milling conditions
  作者：Ting-Hu Zhang、Guan-Wu Wang、Ping Lu、Yu-Jin Li、Ru-Fang Peng、You-Cheng Liu、Yasujiro Murata、Koichi Komatsu

  DOI：10.1039/b403027c

  日期：——

  Solvent-free reactions of C(60) with active methylene compounds, either with or without carbon tetrabromide (CBr(4)), in the presence of a base under high-speed vibration milling (HSVM) conditions were investigated. The reaction of C(60) with diethyl bromomalonate was conducted under HSVM conditions in the presence of piperidine, triethylamine or Na(2)CO(3) to afford cyclopropane derivative. In the

  在高速振动研磨（HSVM）条件下，在碱的存在下，研究了C（60）与活性亚甲基化合物（有或没有四溴化碳（CBr（4）））的无溶剂反应。C（60）与溴代丙二酸二乙酯的反应在HSVM条件下在哌啶，三乙胺或Na（2）CO（3）的存在下进行，得到环丙烷衍生物。在存在CBr（4）的情况下，可以通过将C（60）与丙二酸二乙酯，丙二酸二甲酯，乙酰乙酸乙酯和氰基乙酸乙酯分别直接反应，并借助1,8-二氮杂双环[5]来获得甲富勒烯。 ，4,0]十一碳-7-烯，哌啶，三乙胺或Na（2）CO（3）。更有趣的是，在哌啶的存在下，C（60）与丙二酸二乙酯和丙二酸二甲酯反应生成1,4-双加合物，三乙胺或Na（2）CO（3）在HSVM条件下。另一方面，二氢呋喃稠合的C（60）衍生物，是由C（60）与乙酰乙酸乙酯，2,4-戊二酮和5,5-二甲基-1,3-环己二酮反应制得的。一个基地。在相同条件下，活化较少的芳基甲基酮，例如2
• CuBr/PMDETA-Mediated Reactions of [60]Fullerene with Active Halides: Preparation of Methano[60]Fullerene Derivatives
  作者：Hai-Tao Yang、Zong-Yong Tian、Xiao-Jiao Ruan、Min Zhang、Chun-Bao Miao、Xiao-Qiang Sun

  DOI：10.1002/ejoc.201200759

  日期：2012.9

  methano[60]fullerene derivatives linked with a single electron-withdrawing group has been developed through one-step reaction of [60]fullerene with active halides mediated by CuBr/pentamethyldiethylenetriamine. Many functional groups including esters, ketones, amides, and sulfonyl groups could be easily introduced onto the fullerene skeleton by using this methodology. A plausible reaction mechanism

  通过 [60] 富勒烯与由 CuBr/五甲基二亚乙基三胺介导的活性卤化物的一步反应，开发了一种用于合成与单个吸电子基团相连的甲烷 [60] 富勒烯衍生物的有效方案。使用这种方法可以很容易地将包括酯、酮、酰胺和磺酰基在内的许多官能团引入富勒烯骨架。提出了一种看似合理的反应机制，但不是原子转移自由基过程，用于形成甲 [60] 富勒烯衍生物。