Cubane-1,5,7-tricarbonyl trichloride | 161980-56-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: Cubane-1,5,7-tricarbonyl trichloride
• 英文别名: Cubane-1,3,5-tricarbonyl chloride
• CAS: 161980-56-9
• 化学式: C₁₁H₅Cl₃O₃
• 分子量: 291.518
• InChiKey: KZKMOCAIMDHESU-UHFFFAOYSA-N

物化性质

• 沸点：
  349.0±42.0 °C(Predicted)
• 密度：
  2.265±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Cubane-1,5,7-tricarbonyl trichloride 在 叠氮基三甲基硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 Cubane-1,5,7-tricarbonyl triazide
  参考文献：
  名称：

  Systematic substitution on the cubane nucleus. Synthesis and properties of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane

  摘要：

  A systematic methodology is developed for the synthesis of highly symmetric, polysubstituted cubanes. The synthesis of cubanes with C3v and T(d) symmetry is achieved. Details are given for the preparation of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane, compounds of interest as superior high-energy, shock-insensitive explosives. The structures of these new materials, determined by single-crystal X-ray analysis, are discussed in detail. DSC analysis of their thermal decomposition is presented. The effect of nitro groups on the C-13-NMR spectra of cubanes is noted.

  DOI：

  10.1021/ja00075a039
• 作为产物：
  描述：

  1-立方烷羧酸 在 草酰氯 作用下， 反应 0.83h， 生成 Cubane-1,5,7-tricarbonyl trichloride
  参考文献：
  名称：

  1,3,5,7-四硝基立方烷的合成和化学，包括酸度测量、邻硝基阴离子的形成以及五硝基立方烷和六硝基立方烷的初步制备1

  摘要：

  立方烷交替角上的硝基增强了立方氢的酸度（pKa~21），并为准备好的阴离子形成提供足够的活化。1,3,5,7-四硝基立方烷的钠盐很容易与亲电子试剂反应，从而产生更高取代度的立方烷，如甲氧基-和（三甲基甲硅烷基）四硝基立方烷。这些物种的阴离子也很容易形成，可用于进一步取代立方核。四氧化二氮与四硝基立方烷的阴离子反应生成 1,2,3,5,7-五硝基立方烷，这是第一个含有邻位硝基的立方烷。该反应可能涉及将阴离子氧化为相应的自由基。同样，五硝基立方烷的阴离子用于制备 1,2,3,4,5,7-六硝基立方烷，这是迄今为止制造的硝化程度最高的立方烷。

  DOI：

  10.1021/ja970552q

文献信息

• Photochemical Functionalization of Cubanes
  作者：A. Bashir-Hashemi、J. Li、Nathan Gelber、Herman Ammon

  DOI：10.1021/jo00108a037

  日期：1995.2

  A wide range of cubanecarboxylic acids has been prepared by a simple and efficient photochemical process. Chlorocarbonylation of cubanecarboxylic acid with oxalyl chloride under UV irradiation produced polysubstituted cubanes with chlorocarbonyl groups predominantly on the remote sites (beta or gamma). The T-d-tetraacid chloride 6b, in which chlorocarbonyl groups are in alternate positions, was the major product. Irradiation of 1,2,3,7-tetrasubstituted cubane 9 with oxalyl chloride gave pentasubstituted cubane 10. Other isomers, 1,3,5,7-tetrasubstituted cubane 6 and 1,2,4,7-tetrasubstituted cubane 8, in which chlorocarbonylation would occur at positions ortho to three or two carbonyl groups, gave only chlorinated products. Photochemical reaction of oxalyl chloride with nitrocubanes gave chlorocarbonylated and chlorinated nitrocubanes. Ab initio calculations show carbon-hydrogen bond strength at different positions of the cubane is not the major factor in determining the regioselectivity of the chlorocarbonylation. A polar effect might be the key factor in site selectivity.