1,2,4,15-tetrakis(t-butylperoxy)-1,2,4,15-tetrahydro[60]fullerene | 686766-93-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,2,4,15-tetrakis(t-butylperoxy)-1,2,4,15-tetrahydro[60]fullerene
• 英文别名: 1,6,9,18-tetrakis(tert-butylperoxy)(C60-Ih)[5,6]fullerene
• CAS: 686766-93-8
• 化学式: C₇₆H₃₆O₈
• 分子量: 1077.12
• InChiKey: JJXBFOOBROIKHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.5
• 重原子数：
  84.0
• 可旋转键数：
  8.0
• 环数：
  32.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  73.84
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  叔丁基过氧化氢 、 1,2,4,15-tetrakis(t-butylperoxy)-1,2,4,15-tetrahydro[60]fullerene 在 碘苯二乙酸 作用下， 反应 0.08h， 生成 1,2,4,11,15,30-hexakis(tert-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
• 作为产物：
  描述：

  叔丁基过氧化氢 、 1,2-bis(t-butylperoxy)-1,2-dihydro[60]fullerene 在 碘苯二乙酸 作用下， 反应 0.33h， 生成 1,2,4,15-tetrakis(t-butylperoxy)-1,2,4,15-tetrahydro[60]fullerene 、 1,2,4,11,15,30-hexakis(tert-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