1,2-epoxy-4,11,15,30-tetrakis(t-butylperoxy)-1,2,4,11,15,30-hexahydro[60]fullerene | 476413-16-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2-epoxy-4,11,15,30-tetrakis(t-butylperoxy)-1,2,4,11,15,30-hexahydro[60]fullerene
• 英文别名: 1,2-epoxy-4,11,15,30-tetra-tert-butylperoxy-1,2,4,11,15,30-hexahydro[60]fullerene；1,2-epoxy-4,11,15,30-tetra-t-butylperoxy-1,2,4,11,15,30-hexahydro[60]fullerene
• CAS: 476413-16-8
• 化学式: C₇₆H₃₆O₉
• 分子量: 1093.12
• InChiKey: ZBSIIEDNXSCRKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.83
• 重原子数：
  85.0
• 可旋转键数：
  8.0
• 环数：
  33.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  86.37
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  1,2-epoxy-4,11,15,30-tetrakis(t-butylperoxy)-1,2,4,11,15,30-hexahydro[60]fullerene 在 ferric(III) bromide 作用下， 以 苯 为溶剂， 反应 0.08h， 以78%的产率得到1-bromo-2-hydroxy-4,11,15,30-tetra(tert-butylperoxy)-1,2,4,11,15,30-hexahydro[60]fullerene
  参考文献：
  名称：

  Preparation of Covalent-Bound Iodofullerene through Selective Opening of Fullerene Epoxide To Form Halohydrin Fullerene Derivatives

  摘要：

  富勒烯混合过氧化物中的环氧分子可以通过各种路易斯酸进行选择性开环，形成卤代富勒烯衍生物。通过用三苯基膦和碘处理富勒烯环氧化物，获得了第一种碘富勒烯。氯醇衍生物的单晶结构证实了这一结果。

  DOI：

  10.1055/s-2006-932462
• 作为产物：
  描述：

  叔丁基过氧化氢 、 4,15-bis(t-butylperoxy)-1,2-epoxy-1,2,4,15-tetrahydro[60]fullerene 在 碘苯二乙酸 作用下， 生成 1,2-epoxy-4,11,15,30-tetrakis(t-butylperoxy)-1,2,4,11,15,30-hexahydro[60]fullerene
  参考文献：
  名称：

  Selective Preparation of Oxygen-Rich [60]Fullerene Derivatives by Stepwise Addition of tert-Butylperoxy Radical and Further Functionalization of the Fullerene Mixed Peroxides

  摘要：

  tert-Butylperoxy radicals add to C-60 selectively to form multi-adducts C-60(O)(m)((OOBu)-Bu-t), (m = 0, n = 2, 4, 6; m = 1, n = 0, 2, 4, 6) in moderate yields under various conditions. Visible light irradiation favors epoxide formation. High concentration of tert-butylperoxy radicals mainly produces the hexa-homoadduct C-60((OOBu)-Bu-t)(6) 6; low concentration and long reaction time favor the epoxy-containing C-60(O)((OOBu)-Bu-t)(4) 7. The reaction can be stopped at the bis-adducts with limited TBHP. A stepwise addition mechanism is discussed involving mono-, allyl-, and cyclopentadienyl C-60 radical intermediates. m-CPBA reacts with the 1,4-bis-adduct to form C-60(O)((OOBu)-Bu-t)(2) and C-60(O)(3)((OOBu)-Bu-t)(2). The C-O bond of the epoxy ring in 7 can be cleaved with HNO3 and CF3COOH. Nucleophilic addition of NaOMe to 7 follows the S(N)1 and extended S(N)2' mechanism, from which four products are isolated with the general formula C-60(O)(a)(OH)(b)(OMe)(c)((OOBu)-Bu-t)(d). Visible light irradiation of the hexa-adduct 6 results in partial cleavage of both the C-O and O-O bonds of peroxide moieties and formation of the cage-opened compound C-60(O)(O)(2)((OOBu)-Bu-t)(4). All the fullerene derivatives are characterized by spectroscopic data. A single-crystal structure has been obtained for an isomer Of C-60(O)(OH)(2)(OMe)(4)((OOBu)-Bu-t)(2).

  DOI：

  10.1021/jo049974q

文献信息

• Reactivity of Fullerene Epoxide:  Preparation of Fullerene-Fused Thiirane, Tetrahydrothiazolidin-2-one, and 1,3-Dioxolane
  作者：Xiaobing Yang、Shaohua Huang、Zhenshan Jia、Zuo Xiao、Zhongping Jiang、Qianyan Zhang、Liangbing Gan、Bo Zheng、Gu Yuan、Shiwei Zhang

  DOI：10.1021/jo7023587

  日期：2008.4.1

  BF3·Et2O yields the fullerene-fused [1,3,2]-dioxoborolane derivative C60(O2BOH)(OOtBu)4. In the presence of aldehyde or acetone, BF3·Et2O catalyzes the conversion of epoxide to fullerene-fused 1,3-dioxolane derivatives. The products are characterized by spectroscopic data. Two of the compounds are also characterized by single-crystal X-ray analysis.

  富勒烯混合的过氧化物C 60（O）（OO t Bu）4 1中的环氧化物部分容易与异氰酸芳基酯ArNCS（Ar = Ph，Naph）反应形成硫杂环丁烷衍生物C 60（S）（OO t Bu）4和富勒烯稠合的四氢噻唑烷-2--2-。的反应1与三甲基甲硅烷基异硫氰酸酯TMSNCS产生异硫氰酸酯衍生物Ç 60（NCS）（OH）（OO吨丁基）4，异硫氰酸酯和其中羟基部分可以转换到富勒烯稠合tetrahydrothiazolidin -2-酮用氧化铝环数量上。用BF 3 ·Et处理12 O产生富勒烯稠合的[1,3,2]-二氧杂硼烷衍生物C 60（O 2 BOH）（OO t Bu）4。在醛或丙酮的存在下，BF 3 ·Et 2 O催化环氧化物转化为富勒烯稠合的1,3-二氧戊环衍生物。产品通过光谱数据表征。两种化合物的特征还在于单晶X射线分析。
• Preparation of [5,6]- and [6,6]-Oxahomofullerene Derivatives and Their Interconversion by Lewis Acid Assisted Reactions of Fullerene Mixed Peroxides
  作者：Shaohua Huang、Zuo Xiao、Fudong Wang、Jiang Zhou、Gu Yuan、Shiwei Zhang、Zhongfang Chen、Walter Thiel、Paul von Ragué Schleyer、Xiang Zhang、Xiangqing Hu、Bichu Chen、Liangbing Gan

  DOI：10.1002/chem.200500393

  日期：2005.9.5

  [60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes)

  [60]富勒烯混合过氧化物C60（O）（OOtBu）4在温和条件下表现出化学和区域选择性反应。环氧部分被氯化铁打开，形成邻位羟基氯化物C60Cl（OH）（OOtBu）4。BF 3对打开环氧部分也有效。富勒烯混合过氧化物的OO键被氯化铝裂解，形成[5,6]-和[6,6]-富勒烯半缩酮（氧代[60]富勒烯）。提出了霍克型重排用于形成半缩酮，其中富勒烯CC键被裂解。路易斯酸和/或可见光可以引发半酮异构体的异构化。单晶X射线分析和理论计算证实了结果。
• Pentafluorophenyl Transfer Reaction: Preparation of Pentafluorophenyl [60]Fullerene Adducts through Opening of Fullerene Epoxide Moiety with Trispentafluorophenylborane
  作者：Sisi Liang、Liang Xu、Zhenshan Jia、Liangbing Gan

  DOI：10.1021/jo5009228

  日期：2014.6.20

  extensively studied perfluoroalkyl fullerene adducts, perfluorophenyl fullerene adducts are quite difficult to prepare by known methods. Trispentafluorophenylborane was found to react with fullerene epoxide to form the 1,2-perfluorophenylfullerenol. The method can be applied to both the simple epoxide C60(O) and fullerene multiadducts containing an epoxide moiety. Single crystal X-ray structure analysis

  与广泛研究的全氟烷基富勒烯加合物不同，全氟苯基富勒烯加合物很难通过已知方法制备。发现三五氟苯基硼烷与富勒烯环氧化物反应形成1，2-全氟苯基富勒烯醇。该方法可以应用于简单的环氧化物C 60（O）和含有环氧化物部分的富勒烯多加合物。单晶X射线结构分析证实添加了五氟苯基。
• Synthesis of Open‐Cage Fullerenes with Pyrrole, Pyrrolone, Pyridinone, Iminofuran, and Pyranone Fragments Embedded on the Rim of the Orifice
  作者：Zhen Liu、Rui Gao、Zeyu Liu、Zongpu Xia、Xueli Liu、Jialin Ming、Xiaoge Wang、Jie Su、Liangbing Gan

  DOI：10.1002/ejoc.202100908

  日期：2021.11.8

  The open-cage fullerene with a keto-lactone moiety reacted with aniline to form open-cage fullerenes with various functional groups on the rim of the expanded orifice. Decarbonylation and decarboxylation process took place under milder conditions compared to those for classical organic compounds. One water molecule could be trapped in the cavity of the new open-cage compounds as revealed by NMR and

  带有酮内酯部分的开笼富勒烯与苯胺反应形成开笼富勒烯，在膨胀孔的边缘具有各种官能团。与经典有机化合物相比，脱羰和脱羧过程在更温和的条件下进行。核磁共振和单晶 X 射线衍射数据表明，一个水分子可能被困在新的开放笼式化合物的空腔中。
• Open‐Cage Fullerene as Molecular Container for F ⁻ , Cl ⁻ , Br ⁻ and I ⁻
  作者：Shijun Sun、Zhen Liu、Francesca Colombo、Rui Gao、Yuming Yu、Yi Qiu、Jie Su、Liangbing Gan

  DOI：10.1002/anie.202212090

  日期：2022.12.23

  Halide anions have been successfully inserted into the cavity of a 19-membered open-cage fullerene derivative at 60 °C for Cl− and 90 °C for F−, Br− and I− under atmospheric pressure. The encapsulation ratio is quantitative as shown by single crystal X-ray diffraction analysis data and spectroscopic data. The presence of halide ions improves the stability of the cage structure, which could be stored

  卤化物阴离子已成功插入到 19 元开笼富勒烯衍生物的空腔中，在大气压下，Cl -为 60 °C ，F -、Br -和 I -为 90 °C。如单晶X射线衍射分析数据和光谱数据所示，包封率是定量的。卤化物离子的存在提高了笼结构的稳定性，可以在室温下储存数周而没有明显变化。