(1,2-亚甲基富勒烯C60)-61-羧酸乙酯 | 150493-27-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 中文名称: (1,2-亚甲基富勒烯C60)-61-羧酸乙酯
• 中文别名: 乙基(1,2-亚甲基富勒烯C60)-61-羧酸酯
• 英文名称: ethoxycarbonylmethano-1,2-dihydro[6]fullerene
• 英文别名: ethyl 3′H-cyclopropa[1,9](C₆₀-I_h)[5,6]fullerene-3′-carboxylate；1'-ethoxycarbonyl-(C60-I(h))[5,6]fullero[2',3':1,9]cyclopropane；(1,2-Methanofullerene c60)-61-carboxylic acid ethyl ester
• CAS: 150493-27-9
• 化学式: C₆₄H₆O₂
• 分子量: 806.75
• InChiKey: CSRXALCPKNCXFL-UHFFFAOYSA-N

物化性质

• 密度：
  2.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.5
• 重原子数：
  66
• 可旋转键数：
  3
• 环数：
  33.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1,2-亚甲基富勒烯C60)-61-羧酸乙酯 426.84 ℃ 、0.01 Pa 条件下， 生成
  参考文献：
  名称：

  Electronic Interactions in a New Fullerene Dimer:  C₁₂₂H₄, with Two Methylene Bridges

  摘要：

  The isolation of a new fullerene dimer, C122H4, and its structural characterization by C-13 NMR and H-1 NMR spectroscopy and by UV/vis and IR spectroscopy are reported. The structure of this dimer consists of two fullerene cages, which are directly connected through two C-C bonds and two methylene bridges. Consequently, adjacent hexagonal faces of the two fullerene cages are arranged in a face to face manner. Molecular orbital calculations indicate that the proximity of the fullerene cages results in significant through space overlap in both the HOMO and LUMO. As a consequence of this overlap, the electrochemistry of the dimer shows electronic communication with stepwise reduction of each cage.

  DOI：

  10.1021/jo991676j
• 作为产物：
  描述：

  二溴乙酸乙酯 、 足球烯 在 sodium thiomethoxide 作用下， 以 乙腈 为溶剂， 反应 24.0h， 生成 (1,2-亚甲基富勒烯C60)-61-羧酸乙酯
  参考文献：
  名称：

  C₆₀^2- Chemistry: C₆₀ Adducts Bearing Two Ester, Carbonyl, or Alcohol Groups

  摘要：

  Reactions of activated halo compounds XCH2-A (X = Br, I; A = ester, ketone) with C-60(2-) anion give rise to C-60(CH2-A)(2) adducts (major products) along with unexpected methanofullerenes; C-60>CH-A and monosubstituted dihydrofullerenes C-60(H)(CH2-A) (minor products). Methanofullerenes are shown to come from side reactions with X2CH-A traces.

  DOI：

  10.1021/ol034545k

文献信息

• Synthesis and Reactions of 2,2-[60]Fullerenoalkanoyl Chlorides
  作者：Tomoyuki Tada、Yasuhiro Ishida、Kazuhiko Saigo

  DOI：10.1021/jo052399l

  日期：2006.2.1

  2,2-[60]Fullerenoalkanoyl chlorides (1a−d) were easily and securely prepared from the corresponding 2,2-[60]fullerenoalkanoic acids (2a−d) by the reaction with thionyl chloride in an unusual mixed solvent, CH2Cl2/dioxane. The characterization of 1a−d by 1H and 13C NMR, FT-IR, and MALDI-TOF-MASS was conducted for the first time. The 2,2-[60]fullerenoalkanoyl chlorides thus obtained were readily converted

  通过在不寻常的混合溶剂CH 2中与亚硫酰氯反应，由相应的2，2- [60]富勒烯链烷酸（2a - d）轻松安全地制备2,2- [60]富勒烯链烷酰氯（1a - d）。Cl 2 /二恶烷。用1 H和13表征1a - d首次进行13 C NMR，FT-IR和MALDI-TOF-MASS。通过分别与胺和醇缩合，由此获得的2，2- [60]富勒烯链烷酰氯易于以中等至优异的产率转化为相应的酰胺和酯。进行缩合反应后，可以轻松制备[60]富勒烯-生物分子杂化物。
• Synthesis of fullerene C60 monoadducts. Cyclopropanation of C60 with sulfonium ylides
  作者：D. N. Nikolaev、P. B. Davidovich、L. B. Piotrovskii

  DOI：10.1134/s107042801607023x

  日期：2016.7

  3′H-Cyclopropa[1,9](C60-I h )[5,6]fullerene-3′-carboxylic acid can be synthesized in a good yield by cyclopropanation of fullerene C60 with 2-(dimethyl-λ4-sulfanylidene)acetates provided that the ester residue is readily hydrolyzable in acid medium.

  3' ħ -Cyclopropa [1,9]（C 60 -我 ħ）[5,6]富勒烯-3'-羧酸可以以良好的产率来合成由富勒烯C的环丙烷化60用2-（二甲基- λ 4 -亚磺酰基乙酸酯），条件是该酯残基在酸性介质中易于水解。
• Structures and Chemistry of Methanofullerenes: A Versatile Route intoN-[(Methanofullerene)carbonyl]-Substituted Amino Acids
  作者：Lyle Isaacs、Fran�ois Diederich

  DOI：10.1002/hlca.19930760705

  日期：1993.11.3

  higher single-bond character at 6-5 bonds. Reaction of C60 with diazo diester 15 gave the fullerene diester 14 which was hydrolyzed with BBr3 in benzene to the methanofullerenecarboxylic acid 10, a versatile synthon for the preparation of amphiphilic fullerene derivatives. Treatment of 10 with alcohols and amino acid esters under DCC coupling conditions afforded the esters 5 and 17 and the amino-acid

  C 60与恶二唑13的反应以32％的产率提供了二甲氧基甲基富勒烯7，为具有闭合的跨环键的6-6环桥联的异构体。文献调查显示，所有6-6环桥联的亚甲基富勒烯均为带有封闭的跨环键（6-6-封闭）的σ-芳香族芳香族化合物，所有6-5环桥联的都是具有开放式跨环键的π-芳香族芳香族（6 -5-打开）。对6-6封闭和6-5-开放结构的偏爱不是由于取代基效应引起的，而是用这些异构体中在C 60中看到的有利键的保守性进行了最好的解释，C 60在6-6键上具有较高的双键特性和更高的单键性状（6-5个键）。C 60与重氮二酯15的反应将得到的富勒烯二酯14与苯中的BBr 3水解为亚甲基富勒烯羧酸10，后者是一种用于制备两亲性富勒烯衍生物的通用合成子。在DCC偶联条件下用醇和氨基酸酯处理10，分别得到酯5和17以及氨基酸衍生物11和12。
• Electroreductive retro-cyclopropanation reactions of nitrophenyl-methanofullerene derivativesDedicated to Professor Waldemar Adam on the occasion of his 65th birthday.
  作者：M. Ángeles Herranz、Marcel W. J. Beulen、José A. Rivera、Luis Echegoyen、Marta C. Díaz、Beatriz M. Illescas、Nazario Martín

  DOI：10.1039/b202040h

  日期：2002.6.21

  Spiromethanofullerenes 5, 8 and 10 containing a nitrophenyl substituent attached to the methano adduct, were synthesized via the diazomethane route or via the Bingel reaction. The electrochemistry and electrolysis of these compounds were investigated in THF. Reductive electrolysis leads to the removal of the addend, formation of [60]fullerene, and to the formation of bis-adducts from the mono-adducts. The extent of the retro-cyclopropanation reaction varied as a function of the structural and electronic differences between the compounds. Electron spin resonance studies (ESR) allowed the observation of spin localization on the fullerene core or on the nitrobenzene moiety upon successive reductions.

  通过重氮甲烷路线或宾格尔反应合成了含有硝基苯基取代基的甲烷加合物螺旋甲富勒烯 5、8 和 10。研究了这些化合物在四氢呋喃中的电化学和电解。还原电解导致了添加物的去除、[60]富勒烯的形成以及单加合物双加合物的形成。逆环丙烷化反应的程度随化合物之间的结构和电子差异而变化。通过电子自旋共振研究（ESR），可以观察到连续还原时富勒烯核心或硝基苯分子上的自旋定位。
• 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。