1-(4-methoxyphenyl)-1,2-dihydro[60]fullerene | 849535-66-6

• 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-(4-methoxyphenyl)-1,2-dihydro[60]fullerene
• 英文别名: 1-(4-methoxyphenyl)-1,9-dihydro[60]fullerene；1-(4-methoxyphenyl)-1,9-dihydro(C₆₀-I_h)[5,6]fullerene；1-(4-methoxyphenyl)-9-hydro[60]fullerene；9-(4-methoxyphenyl)-1H-(C60-Ih)[5,6]fullerene
• CAS: 849535-66-6
• 化学式: C₆₇H₈O
• 分子量: 828.8
• InChiKey: GVELOLGKJXIYMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.1
• 重原子数：
  68
• 可旋转键数：
  2
• 环数：
  33.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  manganese triacetate 、 1-(4-methoxyphenyl)-1,2-dihydro[60]fullerene 以 氯苯 为溶剂， 反应 2.0h， 以50%的产率得到1-acetoxy-4-(4-methoxyphenyl)-1,4-dihydro[60]fullerene
  参考文献：
  名称：

  一锅顺序合成乙氧基化[60]富勒烯衍生物

  摘要：

  [60]富勒烯与4-取代的苯肼盐酸盐在有氧条件下于回流的氯苯中反应，生成1-（4-取代的苯基）-1,2-二氢[60]富勒烯，随后可将其氧化为1-乙酰氧基-4一锅中用乙酸锰（III）二水合物制得-芳基-1,4-二氢[60]富勒烯。首次利用Mn（OAc）3 ·2H 2 O实现了ArC 60 -H到ArC 60 -OAc的转变。

  DOI：

  10.1021/jo047894g
• 作为产物：
  描述：

  足球烯 、 (4-甲氧基苯基)三氟硼酸钾 在 [Rh(1,5-cyclooctadiene)(MeCN)2]BF₄ 作用下， 以 水 、 邻二氯苯 为溶剂， 反应 12.0h， 以43%的产率得到1-(4-methoxyphenyl)-1,2-dihydro[60]fullerene
  参考文献：
  名称：

  Rh-Catalyzed Arylation and Alkenylation of C₆₀ Using Organoboron Compounds

  摘要：

  A new organoboron-based arylation and alkenylation of C-60 catalyzed by a rhodium complex was developed. A treatment of C-60 with an organoboron compound in the presence of a catalytic amount of [Rh(cod)(CH3CN)(2)]BF4 in H2O/1,2-Cl2C6H4 furnished a functionalized fullerene (R-C-60-H) with good to excellent selectivity. Aryl, heteroaryl, and alkenyl groups can be installed by the reactions using the corresponding boronic acids, pinacol esters, and potassium trifluoroborates.

  DOI：

  10.1021/ja073042x

文献信息

• Selective Introduction of Organic Groups to C60 and C70 Using Organoboron Compounds and Rhodium Catalyst: A New Synthetic Approach to Organo(hydro)fullerenes
  作者：Masakazu Nambo、Yasutomo Segawa、Atsushi Wakamiya、Kenichiro Itami

  DOI：10.1002/asia.201000583

  日期：2011.2.1

  A Rh‐catalyzed reaction of C60 and C70 with organoboron compounds is described. This new catalytic method enables introduction of various organic groups onto C60 and C70. [Rh(cod)(MeCN)2]BF4 proved to be the most effective catalyst in terms of productivity and selectivity. The reaction generally proceeds with a high regioselectivity and in a mono‐addition selective manner. It was found that water is

  描述了C 60和C 70与有机硼化合物的Rh催化反应。这种新的催化方法能够将各种有机基团引入C 60和C 70上。就产率和选择性而言，[Rh（cod）（MeCN）2 ] BF 4被证明是最有效的催化剂。反应通常以高区域选择性和单加成选择性的方式进行。发现水是促进反应的必要添加剂。通过X射线晶体结构分析，我们已经确认了C 70的有机金属基加氢芳基化反应的位点首次。可以合成各种功能性富勒烯，例如富勒烯标记的氨基酸和富勒烯封端的π系统。联苯连接的C 60的X射线晶体结构揭示了利用CH-π相互作用使巴基球组织良好的有趣机会。
• Playing with Protic Additives to Improve the Outcome of Rhodium‐Catalyzed Hydroarylation of Fullerene C₆₀ with Arylboronic Acids
  作者：Merve Ergun Dönmez、Måns Eriksson、Gustav Hulu、Michael Nordström、Helena Grennberg

  DOI：10.1002/hlca.202300206

  日期：2024.2

  A new one‐phase process for hydroarylation of C₆₀ fullerene using arylboronic acids and a rhodium catalyst in an aromatic solvent containing soluble protic additives is described. Yields of monohydroarylated product with tert‐butanol and water as the protic additive range from 14 to 50 % depending on which arylboronic acid is used after reaction times of 4 hours or less which is a significant improvement from the outcome of reactions carried out using conditions from the literature. Accurate monitoring of reaction outcomes was achieved by a combination of UV‐Vis spectroscopy and ¹H‐NMR spectroscopy: C₆₀ conversion was determined using an analytical HPLC‐UV‐vis method employing commonly available columns for the separation, while product formation was quantified by ¹H‐NMR spectroscopy with an internal standard. Moreover, two new arylboronic acids carrying 4‐alkynyl aryl substituents, synthesized using Sonogashira couplings, are reported, as well as the use of these in the hydroarylation of C₆₀.

  摘要 描述了一种在含有可溶性原生添加剂的芳香溶剂中使用芳基硼酸和铑催化剂进行 C60 富勒烯加氢反应的单相新工艺。使用叔丁醇和水作为原生添加剂，在反应时间为 4 小时或更短的情况下，根据所使用的芳基硼酸的不同，单氢芳基化产物的产率为 14% 至 50%，这比使用文献条件进行的反应结果有了显著改善。反应结果的精确监测是通过紫外可见光谱和 1H-NMR 光谱相结合来实现的：采用 HPLC-UV-vis 分析方法，使用常见的分离柱测定 C60 的转化率，同时使用内标 1H-NMR 光谱定量分析产物的形成。此外，还报道了利用 Sonogashira 偶联合成的两种携带 4- 烷基芳基取代基的新型芳基硼酸，以及在 C60 的加氢反应中使用这些芳基硼酸的情况。
• A Bench-Stable Pd Catalyst for the Hydroarylation of Fullerene with Boronic Acids
  作者：Susumu Mori、Masakazu Nambo、Liang-Chen Chi、Jean Bouffard、Kenichiro Itami

  DOI：10.1021/ol801936j

  日期：2008.10.16

  A Pd(II) catalyst for the hydroarylation of fullerene with boronic acids is presented. Treatment of C-60 with an arylboronic acid in the presence of a catalytic amount of Pd(2-PyCH=NPh)(OCOC6F5)(2) in H2O/1,2-Cl2C6H4 at room temperature furnishes the hydroarylation product (Ar-C-60-H) in good yield with high selectivity. This complex possesses high catalytic activity paired with bench stability in the solid state.
• Regioselective Synthesis of 1,4-Di(organo)[60]fullerenes through DMF-assisted Monoaddition of Silylmethyl Grignard Reagents and Subsequent Alkylation Reaction
  作者：Yutaka Matsuo、Akihiko Iwashita、Yoko Abe、Chang-Zhi Li、Keiko Matsuo、Masahiko Hashiguchi、Eiichi Nakamura

  DOI：10.1021/ja8041299

  日期：2008.11.19

  Monoaddition of Grignard reagents, in particular tri(organo)silylmethyl magnesium chlorides, to [60]fullerene took place smoothly in the presence of dimethylformamideto produce (organo)(hydro)[60]fullerenes, (C60RH)-H-1, in good yield (up to 93% isolated yield). The hydrofullerene was then deprotonated to generate the corresponding anion, C60R-, which was then alkylated to obtain 58 pi-electron di(organo)[60]fullerenes, (C60RR2)-R-1, in good to high yield (up to 93% overall yield). The two-step methodology provides a wide variety of 1,4-di(organo)[60] fullerenes bearing the same or different organic addends on the [60] fullerene core. By changing the addends, one can control the chemical and physical properties of the compounds at the molecular and bulk levels.
• AlCl3-Mediated Mono-, Di-, and Trihydroarylation of [60]Fullerene
  作者：Akihiko Iwashita、Yutaka Matsuo、Eiichi Nakamura

  DOI：10.1002/anie.200700062

  日期：2007.5.4