C60F18 | 185912-87-2

• 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: C60F18
• 英文别名: 1,2,3,7,8,9,12,15,16,17,21,22,23,36,37,38,39,40-octadecafluoro(C60-Ih)[5,6]fullerene
• CAS: 185912-87-2
• 化学式: C₆₀F₁₈
• 分子量: 1062.63
• InChiKey: MPLUIYMJTMPHRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  78
• 可旋转键数：
  0
• 环数：
  32.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  C60F18 在 air 作用下， 以 甲苯 为溶剂， 反应 65.0h， 以0.5 mg的产率得到
  参考文献：
  名称：

  Isolation and characterisation of both the first fluoroxyfluorofullerene C60F17OF and oxahomofluorofullerenol C60F17O.OH

  摘要：

  The first fluoroxyfluorofullerene C60F17OF (A) has been isolated from the fluorination of [60]fullerene with a mixture of MnF3 and K2NiF6 at 480degreesC. This compound has a shorter HPLC retention time than the isomeric fluorofullerene ethers (oxahomofullerenes) and is less stable towards El mass spectrometry. It fragments by losing OF as a single entity and shows no formation Of C60O as a fragment ion. By contrast, the ethers fragment by first losing a number of F atoms and then CO, and ultimately show also the presence Of C60O, whilst epoxides lose CO as a main fragmentation step and do not give C60O. The first oxahomofluorofullerenol C60F17O.OH (B) has been isolated from the UV-irradiation of a toluene solution of C60F18 in air during 65 It and readily eliminates HF due to adjacent F and OH groups during El mass spectrometry. The structures of both the compounds have been deduced from I D and 2D F-19 NMR spectroscopy. Just as oxygen inserts into FC-CF bonds of C60F18 to give ethers, so insertion into a C-F bond gives A. The oxahomofluorofullerenol B is produced by S(N)2' substitution of F by OH, followed by oxygen insertion into a 6:5-bond (alphabeta to the OH group) giving a motif not seen previously in fluorofullerenes. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(03)00014-9
• 作为产物：
  描述：

  足球烯 在 manganese(III) fluoride 、 potassium hexafluoronickelate(IV) 作用下， 以5.5%的产率得到C60F18
  参考文献：
  名称：

  Electrophilic substitution of C₆₀F₁₈into phenols: HF elimination between OH and a 1,3-shifted fluorine giving benzofurano[2′,3′:10,26]hexadecafluoro[60]fullerene and derivatives

  摘要：

  C60F18与苯酚、2-萘酚和喹啉在氯化铁存在下的反应导致初始亲电取代（芳基脱氟）。苯酚在邻位和对位发生反应，喹啉在邻位发生反应，2-萘酚在相对受阻但反应性最强的1位发生反应。在空间位阻有利的情况下，随后会发生HF损失，要么在OH基团和F之间（由于1,3-位移而相邻），要么在相邻双键处的OH基团攻击，损失一个β-氟，形成苯并呋喃并[2,3:10,26]十六氟并[60]富勒烯衍生物。该反应伴随着一些完全脱氟，在与苯酚和2-萘酚的反应中，分别形成苯并呋喃并[2,3:1,2][60]富勒烯和萘并[2,1:b]呋喃并[d:1,2][60]富勒烯。苯酚与C60Cl6的碱催化反应机理得到了重新评估。

  DOI：

  10.1039/b301528a

文献信息

• Design and synthesis of multi-component 18π annulenic fluorofullerene ensembles suitable for donor–acceptor applications
  作者：Glenn A. Burley、Anthony G. Avent、Ilya V. Gol’dt、Peter B. Hitchcock、Hamad Al-Matar、Demis Paolucci、Francesco Paolucci、Patrick W. Fowler、Alessandro Soncini、Joan M. Street、Roger Taylor

  DOI：10.1039/b309959h

  日期：——

  A series of trannulene (all-trans annulene) derivatives of [60]fullerene have been prepared by reacting C60F18 with methanetricarboxylate esters that incorporate a range of photoactive functions. All the compounds have the intense emerald-green colour of fullerene trannulenes, characterised by strong bands at ca. 612 and 667 nm. Single crystal X-ray studies show that the packing varies with the nature of the addend, attributable to differing steric effects. UV/vis absorption spectra display transitions of the respective fullerene and addend models, indicating absence of electronic interactions between them in the ground state. These now provide an extensive series for testing photoactive (light-harvesting) properties, with the exceptional properties of having strong visible light absorption. Their exceptional stability is attributed to the 18π aromatic circuit, inability to undergo nucleophilic substitution without disrupting this circuit, and a curved cage region that is shielded to reagents by the three bulky addends.

  一系列由[60]富勒烯构成的全反式环烯（trannulene）衍生物已通过C60F18与含有多种光活性功能团的甲烷三羧酸酯反应制备而成。所有化合物都呈现出富勒烯环烯特有的深祖母绿色，其特征在于约612和667纳米处的强吸收带。单晶X射线研究表明，由于空间效应的差异，包合物随附加基团性质的不同而变化。UV/可见光吸收光谱显示了各自富勒烯模型和附加基团的跃迁，表明在基态时它们之间不存在电子相互作用。这些化合物如今提供了一大批用于测试光活性（光捕获）性能的系列，其独特之处在于具有强烈的可见光吸收。它们异常的稳定性归因于18π芳香环路，无法在不破坏此环路的情况下进行亲核取代反应，以及由三个庞大的附加基团保护的弯曲笼状区域。
• Synthesis and study of trannulene derivatives of fullerenes
  作者：E. A. Khakina、A. S. Peregudov、S. I. Troyanov、P. A. Troshin

  DOI：10.1007/s11172-012-0038-1

  日期：2012.2

  A series of trannulenes C60F15[CX(COOR)2]3 (X = COOMe, Br; R = Me, Et, Prn, n-Hex, But, (CH2)3NHCOOBut) was synthesized. The first water-soluble trannulenes containing six carboxyl groups (C60F15[C(COOMe)(COOH)2]3) or six protonated amino groups (C60F15[C(COOMe)(COO(CH2)3NH3 +CF3COO−)2]3) were obtained. The compositions and structures of all compounds were proved by mass spectrometry, 1H, 13C, and 19F NMR spectroscopy, and other physicochemical methods. The reactivity of trannulenes was studied for the first time. The unique isomerization of trannulenes to triumphenes accompanied by the migration of three organic addends from one hemisphere of the fullerene cage to another hemisphere was discovered. The structures of the isomerization products were proved using single-crystal X-ray diffraction analysis and 1H, 13C, and 19F NMR spectroscopy. The concerted cascade of isomerization, elimination, and addition reactions was accomplished, which made it possible to obtain photoactive dyads C60F14R2=A (R = C(X)(COOR)2, A is a fragment of fullerenes C60 or C70, anthracene, or pentacene). These dyads contain the electron-deficient fluorofullerene core and electron-donor (with respect to the fluorofullerene core of the molecule) addend A. Photoinduced charge separation can occur in these systems, which makes them analogs of natural photosynthetic antennas.

  合成了一系列trannulenes C60F15[CX(COOR)2]3 (X = COOMe, Br; R = Me, Et, Prn, n-Hex, But, (CH2)3NHCOOBut)。首先获得了含六个羧基（C60F15[C(COOMe)(COOH)2]3）或六个质子化氨基（C60F15[C(COOMe)(COO(CH2)3NH3 +CF3COO−)2]3）的水溶性trannulenes。所有化合物的组成和结构都通过质谱、1H、13C和19F核磁共振谱和其他物理化学方法得到证明。首次研究了trannulenes的反应活性，发现了trannulenes独特的异构化反应，伴随着三个有机加成物从一个富勒烯笼半球迁移到另一个半球，生成了triumphenes。通过单晶X射线衍射分析和1H、13C和19F核磁共振谱证明了异构化产物的结构。协同的级联异构化、消除和加成反应得以完成，从而有可能获得光活性的二聚体C60F14R2=A (R = C(X)(COOR)2, A是富勒烯C60或C70、蒽或并五苯的片段)。这些二聚体含有缺电子的氟富勒烯核心和相对于氟富勒烯分子核心的电子供体加成物A。在这些系统中可以发生光诱导的电荷分离，使它们成为天然光合天线的类似物。
• Synthesis and Spectroscopic Characterization of the First Symmetrically and Nonsymmetrically Substituted Fluorinated Emerald-Green Trannulenes C60F15R3 Soluble in Polar Media and Water
  作者：Pavel A. Troshin、Ekaterina A. Khakina、Alexander V. Zhilenkov、Alexander S. Peregudov、Olesya A. Troshina、Viacheslav I. Kozlovskii、Natalya V. Polyakova、Rimma N. Lyubovskaya

  DOI：10.1002/ejoc.200901169

  日期：2010.2

  trannulene derivatives of fluorofullerene C 60 F 18 possessing six carboxylic or ammonium ion groups have been synthesized and spectrally characterized. The stability of emerald-green aqueous solutions of these compounds was investigated. A novel synthetic route was developed for a step-by-step derivatization of C 60 F 18 with different organic C―H acids that yielded nonsymmetrically substituted C 60 F

  已经合成和光谱表征了具有六个羧基或铵离子基团的氟富勒烯 C 60 F 18 的第一个水溶性 C 3v 对称环烯衍生物。研究了这些化合物的翠绿色水溶液的稳定性。开发了一种新的合成路线，用于用不同的有机 C-H 酸逐步衍生 C 60 F 18，产生非对称取代的 C 60 F 15 R 2 R' 联烯。合成的 trannulenes 负载有极性羧基，大大提高了这些化合物在水性介质中的溶解度。我们表明，可以将四个增溶 COOH 基团引入到带有 R 取代基的 C 60 F 15 R 2 R' 环烯的富勒烯笼上，然后一些额外的有机官能团可以独立地与 R' 连接。R' 取代基可能包含一个配体，负责将整个 trannulene 分子选择性靶向某些特定组织或细胞内结构。具有极性羧基或铵基团的氟富勒烯核的已证明负载可能被认为是设计用于生物医学应用的复杂的水溶性双烯基组装体的重要一步。
• Synthesis of 18? annulenic fluorofullerenes from tertiary carbanions: size matters!
  作者：Glenn A. Burley、Anthony G. Avent、Olga V. Boltalina、Thomas Drewello、Ilya V. Goldt、Massimo Marcaccio、Francesco Paolucci、Demis Paolucci、Joan M. Street、Roger Taylor

  DOI：10.1039/b301820m

  日期：——

  A range of tertiary carbanions XCH(CO2Et)2 of differing sizes have been reacted with C60F18 to assess the steric effect of X on the position of nucleophilic substitution. For X = CO2Et, NO2, P(O)(OMe)2, SO2CH2Ph, the all trans annulenes (trannulenes) were obtained as a result of extended SN2′ (i.e. SN2″) substitution; in the case of the phosphorus compound, with reduced amounts of base (DBU) dephosphonylation of one or more P(O)(OMe)2 groups by hydrogen occurred. Trannulene formation did not occur for X = F, CN due to the smaller size of the nucleophile, and in the latter case substitution was shown to take place by an SN2′ mechanism, resulting in the addend being adjacent to a fluorine addend. Trannulenes (X = CO2Et, Br, Cl) exhibited reversible one-electron reductions at potentials (−0.02 to −0.09 V) significantly more positive than for [60]fullerene. Trannulene (X = NO2) exhibited an irreversible one-electron reduction (0.08 V); the irreversibility may be associated with fluorine loss. Conformational isomerism at temperatures below 298 K was observed for all trannulene derivatives as a result of eclipsing addend–addend interactions. Minimum energy conformations with a rotational energy barrier of 12–15 kcal mol−1 were observed when these interactions are calculated using molecular mechanics.

  一系列不同大小的三级碳阴离子XCH(CO2Et)2已与C60F18反应，以评估X对亲核取代位置的立体效应。对于X = CO2Et、NO2、P(O)(OMe)2、SO2CH2Ph，反应生成了全反式环烯烃（trannulenes），这得益于扩展的SN2'（即SN2''）取代；在磷化合物的情况下，在减少的碱（DBU）条件下，发生了一个或多个P(O)(OMe)2基团的去磷酸反应。对于X = F、CN，由于亲核试剂较小，未能形成反式环烯烃，而在后者的情况下，取代被证明通过SN2'机制进行，结果是加成体与氟加成体相邻。反式环烯烃（X = CO2Et、Br、Cl）在比[60]富勒烯明显更正的电位（-0.02到-0.09 V）下显示出可逆的一电子还原。反式环烯烃（X = NO2）则表现出不可逆的一电子还原（0.08 V）；该不可逆性可能与氟的损失有关。所有反式环烯烃衍生物在低于298 K的温度下都观察到了构象异构现象，这是由于加成体之间的遮掩相互作用造成的。当使用分子力学计算这些相互作用时，观察到具有12-15 kcal mol^-1旋转能量障碍的最小能量构象。
• Electrophilic Aromatic Substitution by the Fluorofullerene C60F18
  作者：Adam D. Darwish、Anthony G. Avent、Ala'a K. Abdul-Sada、Ilya V. Gol'dt、Peter B. Hitchcock、Igor V. Kuvytchko、Roger Taylor

  DOI：10.1002/chem.200400036

  日期：2004.9.20

  defines the lower reactivity limit. The low discrimination between aromatics makes it possible to isolate derivatives having different aryl groups attached to the cage. Reactions occur mainly when the reagent solutions (or solutions in 1,2-dichlorobenzene) are evaporated to dryness. In most FeCl3-catalysed reactions, unreacted C60F18 was recovered, more if the less effective SnCl4 was used as a catalyst;

  FeCl3催化的C60F18芳基化反应生成三取代的化合物C60F15Ar3，其中Ar =苯基，4-甲苯基，4-甲氧基苯基，4-苯氧基苯基，4-氯苯基，3,4-二氯苯基，2-二芴基和2-芴基与一些双取代和单取代的产品。用联苯和荧蒽进行双取代，用联苯（2-位），pyr（1-位）和萘（1-和2-位）单取代；三苯基和三联苯衍生物是荧光的。2-萘基取代基在328 K处自由旋转，而1-萘基取代基的旋转通过氢原子与氟的相互作用而被阻止。1-萘基衍生物在EI质谱分析中消除了HF分子，而2-萘基衍生物消除了HF和所有芴，从而生成了萘[60]富勒烯。反应速度不受芳基环中电子供应的影响，但是没有得到定义了反应性下限的苯并三氟化物产物。芳族化合物之间的低区分度使得可以分离具有连接到笼上的不同芳基的衍生物。反应主要是在试剂溶液（或在1,2-二氯苯中的溶液）蒸发至干时发生的。在大多数FeCl3催化的反应中，未反应的C