αH-Undecachlorodiphenylmethane | 33119-38-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: αH-Undecachlorodiphenylmethane
• 英文别名: Chlorobis(pentachlorophenyl)methane；1,2,3,4,5-pentachloro-6-[chloro-(2,3,4,5,6-pentachlorophenyl)methyl]benzene
• CAS: 33119-38-9
• 化学式: C₁₃HCl₁₁
• 分子量: 547.134
• InChiKey: KRRCADOEYZFNSN-UHFFFAOYSA-N

物化性质

• 熔点：
  232-233.5 °C
• 沸点：
  528.1±45.0 °C(Predicted)
• 密度：
  1.820±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  αH-Undecachlorodiphenylmethane 以 二乙二醇二甲醚 为溶剂， 生成 双(五氯苯基)甲烷
  参考文献：
  名称：

  Inert carbon free radicals. I. Perchlorodiphenylmethyl and perchlorotriphenylmethyl radical series

  摘要：

  DOI：

  10.1021/ja00738a021
• 作为产物：
  描述：

  二苯氯甲烷 在 二氯化二硫 、 三氯化铝 、 磺酰氯 作用下， 生成 αH-Undecachlorodiphenylmethane
  参考文献：
  名称：

  Inert carbon free radicals. I. Perchlorodiphenylmethyl and perchlorotriphenylmethyl radical series

  摘要：

  DOI：

  10.1021/ja00738a021

文献信息

• An Easy, High-yield Synthesis of Highly Chlorinated Mono-, Di- and Triarylmethanes
  作者：Manuel Ballester、Juan Riera、Juan Castañer、Concepción Rovira、Olag Armet

  DOI：10.1055/s-1986-31479

  日期：——

  A simple, direct, high-yield Friedel-Crafts synthesis of highly chlorinated, overcrowded αH-aryl, αH-diaryl, and αH-triarylmethanes is described. The latter compounds are most valuable chemical precursors of inert free radicals, which are frequently obtained through otherwise cumbersome, medium-to-low-yield aromatic chlorination of triphenylmethane derivatives. The condensation is performed with aluminium chloride at temperatures ranging from 70 to 160°C. The substrate is a benzene with all its hydrogens flanked by two ortho chlorines. The alkylating component is chloroform, αH-heptachlorotoluene (2a) or αH-undecachlorodiphenylmethane (3a). For comparison, the condensation with a few non-sterically-hindered substrates has also been performed.

  描述了一种简单、直接、高产率的Friedel-Crafts合成反应，用于合成高度氯化的拥挤型αH-芳基、αH-二芳基和αH-三芳基甲烷。这些化合物是惰性自由基的最有价值的化学前体，通常通过繁琐的中到低产率的芳香氯化三苯甲烷衍生物获得。该缩合反应在70至160°C的温度下使用氯化铝进行。底物是一个苯环，其所有氢原子旁边都有两个邻位氯原子。烷基化组分为氯仿、αH-七氯甲苯（2a）或αH-十氯二苯甲烷（3a）。为了进行比较，也对一些非立体障碍底物进行了缩合反应。
• Chemistry, kinetics, and spectroscopy of highly hindered diarylcarbenes. The case of decachlorodiphenylcarbene
  作者：Hideo Tomioka、Katsuyuki Hirai、Takehito Nakayama

  DOI：10.1021/ja00057a010

  日期：1993.2

  Bis(pentachlorophenyl)diazomethane (1a) was prepared, and reactivities of perchlorodiphenylcarbene (2a) generated by photolysis of 1a were investigated not only in terms of product analysis but also by using flash photolysis techniques. Although the major reaction found for 2a was dimerization forming perchlorotetraphenylethylene and was essentially similar to that observed for 2,2',4,4',6,6'-hexachlorodiphenylcarbene (2b), product distribution clearly indicated that the carbenic center in 2a is more rigidly protected than that in 2b by the four ortho chloro substituents which are buttressed by the four meta chloro groups. Irradiation of 1a in a 2-methyltetrahydrofuran glass at 77 K resulted in the appearance of the absorption due to triplet 2a at 356, 493, and 525 nm. Flash photolysis of 1a in benzene solution produced a transient absorption due to 2a at 357 nm, which decayed in second order in accordance with the product analysis data. The rate constant for dimerization of 2a was determined to be 2.5 +/- 0.1 x 10(6) M-1 s-1, 3 orders of magnitude smaller than that of unsubstituted diphenylcarbene. The triplet carbene (2a) was trapped by oxygen to generate the perchlorobenzophenone oxide showing its maximum at 390 nm (t1/2 = 510 +/- 9 ms) and also by 1,4-cyclohexadiene to produce bis(perchlorophenyl)methyl radical (lambda(max) 376 nm with the rate constant of 6.2 x 10(3) M-1 s-1.
• Synthesis of the sterically hindered bis(pentachlorophenyl)acetic acid and derived stable free radicals
  作者：Pat O'Neill、Anthony F. Hegarty

  DOI：10.1021/jo00042a021

  日期：1992.7

  Bis(pentachlorophenyl)acetic acid esters were synthesized from the alpha-hydroxydiaryl acetate esters 13 via the free radicals 15 formed on homolytic cleavage of the alpha-chloro compounds 14. The acid 8 underwent rapid decarboxylation in basic solution (e.g., Et3N in THF) but could be dehydrated to the corresponding ketene 17. Nucleophilic addition to the ketene provided a route to the corresponding amides (21 and 19) and nitrile 20, the enolates of which underwent ready oxidation to the corresponding stable free radicals 15, 22, and 23. Evidence for the structure and unusual stability of these free radicals is presented. Attempts to observe enols of acids or esters on the addition of water or alcohols to the sterically hindered ketene 17 were unsuccessful.
• BALLESTER, M.;RIERA, J.;CASTANER, J.;ROVIRA, C.;ARMET, O., SYNTHESIS, BRD, 1986, N 1, 64-66
  作者：BALLESTER, M.、RIERA, J.、CASTANER, J.、ROVIRA, C.、ARMET, O.

  DOI：——

  日期：——
• Inert carbon free radicals. I. Perchlorodiphenylmethyl and perchlorotriphenylmethyl radical series
  作者：Manuel Ballester、Juan Riera-Figueras、Juan Castaner、Carlos Badfa、Jose M. Monso

  DOI：10.1021/ja00738a021

  日期：1971.5