1,3-bis(1,2-dicarba-closo-dodecaboran-1-yl)benzene | 857665-52-2

• 英文名称: 1,3-bis(1,2-dicarba-closo-dodecaboran-1-yl)benzene
• 英文别名: 3-(4-C6H4-(3'-o-CB10H10CH))-1.2-C2B10H11；1,3-bis(1'-ortho-carboranyl)benzene；1,3-bis(o-carboran-1-yl)benzene；1,1'-(1,3-C6H4)-(1,2-C2B10H11)2
• CAS: 857665-52-2
• 化学式: C₁₀H₂₆B₂₀
• 分子量: 362.536
• InChiKey: AUABKJQNGCJBJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,3-bis(1,2-dicarba-closo-dodecaboran-1-yl)benzene 、 溴甲苯 在 NaH 作用下， 以 乙二醇二甲醚 为溶剂， 以44%的产率得到1,3-bis(2-benzyl-1,2-dicarba-closo-dodecaboran-1-yl)benzene
  参考文献：
  名称：

  Conformational Control of Benzyl-o-carboranylbenzene Derivatives and Molecular Encapsulation of Acetone in the Dynamically Formed Space of 1,3,5-Tris(2-benzyl-o-carboran-1-yl)benzene

  摘要：

  A 1,3,5-substituted benzene platform has been widely used in the fields of supramolecular chemistry and molecular recognition. Here, we show that 1,3,5-tris(2-benzyl-o-carboran-1-yl)benzene 6 exhibits solvent-dependent conformation in the crystalline state. Recrystallization from dichloromethane-n-pentane gave the anti conformation 6-anti, while recrystallization from methanol-acetone gave the syn conformation 6-syn, in which the three benzyl-o-carboranyl moieties are located to one side of the central benzene ring. Interestingly, one acetone molecule is captured in the pi-rich space of 6-syn and two complexes facing each other encapsulate two acetone molecules in a pi-rich container formed by the eight benzene rings. The inclusion involves several weak interactions, that is, T-shaped C-H center dot center dot center dot pi interactions, and C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions. Two C-H center dot center dot center dot O interactions involving benzylic C-H hydrogens activated by the electron-withdrawing character of the o-carborane cage and the oxygen atom of the acetone seem to be the most important. DFT calculations indicate that the binding energy for entrapment of acetone is 6.6 kcal/mol. Inclusion of acetone is achieved through not only multiple C-H center dot center dot center dot O interactions but also a number of C-H center dot center dot center dot pi interactions. The third benzyl-o-carborane moiety is fixed in the syn conformation by intramolecular and intermolecular C-H center dot center dot center dot pi interactions.

  DOI：

  10.1021/ic101862n
• 作为产物：
  描述：

  癸硼烷 、 1,3-二乙炔苯 在 1-butyl-3-methylimidazolium chloride 作用下， 以 further solvent(s) 为溶剂， 以35%的产率得到1,3-bis(1,2-dicarba-closo-dodecaboran-1-yl)benzene
  参考文献：
  名称：

  离子液体促进的十硼烷脱氢炔烃插入反应：通往邻氨基甲酸酯的新途径。

  摘要：

  与需要路易斯碱催化剂的常规有机溶剂不同，十硼烷脱氢炔烃插入反应会在带有多种末端和内部炔烃的双相离子-液体/甲苯混合物中快速进行，从而提供了有效的，一步一步的途径来官能化-碳氢化合物1-R-1,2-C2B10H11和1-R-2-R'-1,2-C2B10H10衍生物，包括R = C6H5-（1），C6H13-（2），HC [三键] C- （CH2）5-（3），（1-C2B10H11）-（CH2）5-（4），CH3CH2C（O）OCH2-（5），（C2H5）2NCH2-（6），NC-（CH2）3- （7），3-HC [三键] C-C6H4-（8），（1-C2B10H11）-1,3-C6H4-（9），HC [三键] C-CH2-O-CH2-（10 ）; R，R'＝ C2H5-（11）；R = HOCH 2-，R'= CH 3-（12）；R = BrCH 2-；R′＝ CH 3-（13）； R 3 ＝

  DOI：

  10.1021/ic800999y

文献信息

• Nickel-Catalyzed Cross-Coupling Reactions of<i>o</i>-Carboranyl with Aryl Iodides: Facile Synthesis of 1-Aryl-<i>o</i>-Carboranes and 1,2-Diaryl-<i>o</i>-Carboranes
  作者：Cen Tang、Zuowei Xie

  DOI：10.1002/anie.201502502

  日期：2015.6.22

  A nickel‐catalyzed arylation at the carbon center of o‐carborane cages has been developed, thus leading to the preparation of a series of 1‐aryl‐o‐carboranes and 1,2‐diaryl‐o‐carboranes in high yields upon isolation. This method represents the first example of transition metal catalyzed C,C′‐diarylation by cross‐coupling reactions of o‐carboranyl with aryl iodides.

  已经开发了在邻-甲硼烷笼碳中心的镍催化的芳基化反应，从而导致在分离后以高收率制备了一系列的1-芳基-邻-碳戊烷和1,2-二芳基-邻碳烷。该方法是过渡金属催化邻氨基甲酰基与芳基碘化物交叉偶联反应的C，C'-二芳基化的第一个实例。
• Studies on bis(1′-ortho-carboranyl)benzenes and bis(1′-ortho-carboranyl)biphenyls
  作者：Rachel A. Harder、J.A. Hugh MacBride、Graham P. Rivers、Dmitry S. Yufit、Andrés E. Goeta、Judith A.K. Howard、Ken Wade、Mark A. Fox

  DOI：10.1016/j.tet.2014.05.102

  日期：2014.8

  the carborane cages via the para-phenylene bridge in 4. B3LYP/6-31G∗ computations have been carried out on compounds 2 and 4, on 4,4′-bis(ortho-carboranyl)biphenyl 6 and on 1,2-bis(1′-ortho-carboranyl)benzene 7. Those on 2, 4 and 6 show the computed geometries to be in very good agreement with the experimental geometries: those on 7 allowed the reported molecular geometry of this compound to be revised

  之间的反应Ç，C' -dicopper（I）衍生物的邻位-carborane和邻- ，间位-和对位-diiodobenzene报告。与1,2-C 6 H 4 I 2的反应出乎意料地提供了2,2'-双（1'-邻-甲碳烷基）联苯[HCB 10 H 10 CC 6 H 4 ] 2 2，而与1,3的反应-或1,4-C 6 H 4 I 2提供了通往1,3-bis（1'-邻位的替代路线-碳硼烷基）苯3和1,4-双（1'-邻-碳硼烷基）苯4。联苯衍生物2的晶体结构显示出联苯骨架中的明显变形，这是由于两个大体积的碳硼烷笼的接近所致。紫外吸收光谱和电化学数据2和3显示两种碳硼烷笼之间无论是在两者之间可忽略的π共轭的小电子通信，和邻位在亚苯基环2。然而，大量证据表明，碳硼烷笼中的电子通过对苯撑桥在4中发生了相互作用。。B3LYP / 6-31G *的计算已经对化合物进行2和4，在4,4'-双（邻-carboranyl）联苯6和1
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.12, 5.2.1, page 220 - 250
  作者：

  DOI：——

  日期：——
• Synthesis of distorted molecules based on spatial control with icosahedral carboranes
  作者：Yasuyuki Endo、Chalermkiat Songkram、Kiminori Ohta、Kentaro Yamaguchi

  DOI：10.1016/j.jorganchem.2005.01.014

  日期：2005.6

  In the crystal structure of 1,2-bis(o-carboranyl) benzene (2), the benzene ring is remarkably twisted out of planarity, owing to the steric bulkiness of two adjacent carboranyl groups. In the carboracycle (3), the two benzene rings are slantingly stacked owing to spatial control by the carborane cages. (c) 2005 Elsevier B.V. All rights reserved.
• Zakharkin, L. I.; Kozlova, V. S., Zhurnal Obshchei Khimii, 1972, vol. 42, p. 472 - 472
  作者：Zakharkin, L. I.、Kozlova, V. S.

  DOI：——

  日期：——