dichloromethyl radical | 32180-91-9

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属盐
• 英文名称: dichloromethyl radical
• 英文别名: dichloromethyl(1-)；dichloromethanide；dichloromethane
• CAS: 32180-91-9
• 化学式: CHCl₂
• 分子量: 83.9249
• InChiKey: HVARDXWNRGKZKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  {(η6-C6H5NO2)Fe(η5-cyclopentadienyl)}hexafluorophosphate 、 二氯甲烷 、 dichloromethyl radical 以 四氢呋喃 、 正己烷 为溶剂， 生成
  参考文献：
  名称：

  环戊二烯铁介导的加成-脱金属序列将官能化的烷基或炔基引入芳烃

  摘要：

  硝基甲基，氰基甲基和苯基乙炔基阴离子选择性地将邻位添加到含有吸电子基团并与环戊二烯基铁络合的芳烃上。在相似的反应条件下，阴离子如烷基，二氯甲基和三氯甲基以非选择性方式添加。的三氯甲基阴离子的加成在延长反应时间是热力学控制的，并且由于阴离子的大小，元加成产物是有利的。加合物的脱金属导致邻位-硝基甲基化，氰基甲基化或苯基乙炔化的芳烃。对于对称的芳烃配合物，加成-脱金属顺序导致将三氯甲基基团引入芳烃环，从而产生单一产物。从合适的环戊二烯基铁络合物开始的一锅法二烷基芳烃的三氯甲基化可以良好的产率得到β-三氯甲基化的二烷基芳烃。

  DOI：

  10.1016/0022-328x(91)80248-i
• 作为产物：
  描述：

  氯仿 以 solid matrix 为溶剂， 生成 dichloromethyl radical
  参考文献：
  名称：

  Matrix‐Isolation Study of the Vacuum‐Ultraviolet Photolysis of Chloroform. Infrared Spectra of the CCl₃⁺, HCCl₂⁺, and HCCl₂⁻ Molecular Ions

  摘要：

  Photolysis of samples of HCCl3 isolated in an argon matrix at 14°K using 1216-Å radiation leads not only to the isolation of a high yield of CCl3, but also to the photoionization of CCl3, resulting in the stabilization of a sufficient concentration of CCl3+ for direct infrared spectroscopic identification. The assignment of still other infrared absorptions which appear in this system to negatively charged species has been confirmed by experiments in which a small concentration of an alkali metal atom is also present in the matrix, providing a photoelectron source. When matrix-isolated HCCl3 is subjected to photolysis by 1067-Å argon resonance radiation, very little CCl3 is produced, but HCCl2, HCCl2+, and the same negatively charged species are stabilized in significant concentration. Studies of chloroform samples enriched in carbon-13 and of DCCl3 samples have provided support for these identifications and have yielded data necessary for obtaining several of the force constants of these species. The infrared spectrum of the negatively charged species can most satisfactorily be explained by postulating that dissociative electron attachment to chloroform occurs, resulting in the stabilization of HCCl2− in the matrix environment.

  DOI：

  10.1063/1.1675449

文献信息

• Gas-Phase Carbene Radical Anions: New Mechanistic Insights
  作者：Stephanie M. Villano、Nicole Eyet、W. Carl Lineberger、Veronica M. Bierbaum

  DOI：10.1021/ja801819b

  日期：2008.6.1

  The gas-phase reactivity of the CHCl*- anion has been investigated with a series of halomethanes (CCl4, CHCl3, CH2Cl2, and CH3Cl) using a FA-SIFT instrument. Results show that this anion primarily reacts via substitution and by proton transfer. In addition, the reactions of CHCl*- with CHCl3 and CH2Cl2 form minor amounts of Cl2*- and Cl-. The isotopic distribution of these two products is consistent

  已使用 FA-SIFT 仪器研究了 CHCl*- 阴离子与一系列卤代甲烷（CCl4、CHCl3、CH2Cl2 和 CH3Cl）的气相反应性。结果表明，该阴离子主要通过取代和质子转移进行反应。此外，CHCl*- 与 和 的反应会形成少量的 Cl2*- 和 Cl-。这两种产物的同位素分布与插入消除机制一致，其中阴离子插入 C-Cl 键形成不稳定的中间体，从而消除 Cl2*- 或 Cl- 和 Cl*。已知中性和阳离子卡宾插入单键；然而，这是对卡宾阴离子的这种反应性的首次观察。
• Competing electron transfer, proton abstraction and nucleophilic substitutions in gas-phase reactions of (radical) anions with chloro- and bromomethanes
  作者：P. O. Staneke、G. Groothuis、S. Ingemann、N. M. M. Nibbering

  DOI：10.1002/(sici)1099-1395(199607)9:7<471::aid-poc807>3.0.co;2-i

  日期：1996.7

  The product ion distributions and rates of the gas-phase reactions of two series of (radical) anions with chloro- and bromomethanes (CH3Cl, CH2Cl2, CHCl3, CCl4, CH3Br, CH2Br2, CHBr3 and CBr4) were determined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The first series consists of anions (HO-, CH3O-, C2H5O-, C3H7O- and CH3S-), for which the corresponding neutral radicals have a relatively high electron affinity (EA > 150 kJ mol(-1)). The second series consists of (radical) anions (CH2S-., CH2 = CHCH2-, CH2 = C(CH3)CH2-, C6H4-. and C6H5-), for which the corresponding neutral species have a relatively low electron affinity (EA less than or equal to 100 kJ mol(-1)). These (radical) anions react mainly with the halomethanes to afford (i) halide ions, (ii) halomethyl anions with the same number of halogen atoms as in the parent halomethane and (iii) halomethyl anions with one halogen atom less than the parent substrate. The last process involves nucleophilic attack on a halogen atom and is particularly important in the reactions with substrates containing three or four halogen atoms. The halide ions may arise by a number of different pathways, such as S(N)2 substitution, alpha-elimination, halogen attack followed by dissociation of the thus formed halomethyl anion and overall dissociative electron transfer. The S(N)2 process is held responsible for the formation of halide ions in the reactions with monohalomethanes, whereas alpha-elimination is likely to be of importance only for the reactions with trichloro- and tribromomethanes. Attack on a halogen atom followed by dissociation of the ion generated initially is likely to be important if CCl4 or CBr4 is the substrate. Electron transfer is only a dominant pathway in the reactions of the CH2S-. ion with the halomethanes. The occurrence of electron transfer in the reactions of this ion with CHCl3, CCl4 and CHBr3 is evidenced by the formation of minor amounts of stable halomethane radical anions in addition to the generation of CH2SCl- or CH2SBr- ions and abundant halide ions. The interplay between the various possible reactions is discussed on the basis of thermodynamic considerations and the rates of the overall processes.
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: C: MVol.D2, 3.12.3, page 81 - 81
  作者：

  DOI：——

  日期：——