hydroxymethylium | 17691-31-5

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: hydroxymethylium
• 英文别名: Hydroxycarbonium (protonierter Formaldehyd)；protonierter Formaldehyd；formaldehyde; protonated form；hydroxycarbenium cation；Hydroxymethyl (1+)ion；methylideneoxidanium
• CAS: 17691-31-5
• 化学式: CH₃O
• 分子量: 31.0342
• InChiKey: WSFSSNUMVMOOMR-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  2
• 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：
  1
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  hydroxymethylium 以 gas 为溶剂， 生成 甲酰基阳离子 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Reaction dynamics of the four‐centered elimination CH₂OH⁺→CHO⁺+H₂: Measurement of kinetic energy release distribution and classical trajectory calculation

  摘要：

  Mass-analyzed ion kinetic energy (MIKE) spectrum of CHO+ generated in the unimolecular dissociation of CH2OH+ was measured. Kinetic energy release distribution (KERD) was evaluated by analyzing the spectrum according to the algorithm developed previously. The average kinetic energy release evaluated from the distribution was extraordinarily large, 1.63 eV, corresponding to 75% of the reverse barrier of the reaction. A global analytical potential energy surface was constructed such that the experimental energetics was represented and that various features in the ab initio potential energy surface were closely reproduced. Classical trajectory calculation was carried out with the global analytical potential energy surface to investigate the causes for the extraordinarily large kinetic energy release. Based on the detailed dynamical calculations, it was found that the strained bending forces at the transition state and strengthening of the CO bond from double to triple bond character were mainly responsible for such a significant kinetic energy release. In addition, the dissociation products H2 and CHO+ ion were found to be rotationally excited in the trajectory calculations. This was attributed to the asymmetry of the transition state and the release of asymmetric bending forces. Also, the bending vibrational modes of CHO+ and the H2 stretching mode, which are coupled with the bending coordinates, were found to be moderately excited.

  DOI：

  10.1063/1.471202
• 作为产物：
  描述：

  羟亚甲基自由基 在 peroxomonosulfate(1-) 作用下， 以 硫酸 为溶剂， 生成 hydroxymethylium
  参考文献：
  名称：

  Gilbert, Bruce C.; Stell, Jonathan K., Journal of the Chemical Society. Perkin transactions II, 1990, # 8, p. 1281 - 1288

  摘要：

  DOI：

文献信息

• Use of the vinyl group as an efficient protecting group for azole N- atoms: Synthesis of polyfunctionalized imidazoles and thieno[2,3-d] ⇌ [3,2-d]imidazole
  作者：David J. Hartley、Brian Iddon

  DOI：10.1016/s0040-4039(97)00957-x

  日期：1997.6

  2 → 5 → 4 via Br → MgBr and other exchange reactions. Efficient removal of the vinyl groups from the resulting polyfunctionalized imidazoles was achieved with ozone or potassium permanganate. An extension of this methodology has allowed the first synthesis of thieno[2,3-d] ⇌ [3,2-d]-imidazole.

  由2,4,5-三溴咪唑和1,2-二溴乙烷制得2,4,5-三溴-1-乙烯基咪唑，并通过Br→MgBr等交换反应以2→5→4的顺序选择性取代其Br原子反应。用臭氧或高锰酸钾可有效地从所得的多官能化咪唑中除去乙烯基。此方法的扩展允许首次合成噻吩并[2,3- d ]⇌[3,2- d ]-咪唑。
• Stereochemistry of sulfur-lithium and tin-lithium exchange reactions of functionalized cyclopropanes
  作者：Kazuhiko Tanaka、Keizaburo Minami、Ikuo Funaki、Hitomi Suzuki

  DOI：10.1016/s0040-4039(00)94684-7

  日期：1990.1

  Sulfur-lithium exchange reaction of 2-substituted-2-(phenylthio)cyclopropanecarboxamides by LDMAN in THF at −50 °C proceeded with invertion of configuration, leading to the predominant formation of trans-2-substituted cyclopropanes, while in tin-lithium exchange, the configuration was maintained at −78 °C.

  LDMAN在-50°C下于THF中进行LDMAN的2-取代-2-（苯硫基）环丙烷甲酰胺的硫-锂交换反应，发生构型反转，导致主要形成反式-2-取代的环丙烷，而在锡-锂交换中，该配置维持在-78°C。
• Thermoneutral isotope exchange reactions in proton-bound complexes of water with organic molecules: correlations with energetics of formation of the corresponding association ions
  作者：Sharon G. Lias

  DOI：10.1021/j150663a044

  日期：1984.9
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: C: MVol.C4, 2.2, page 27 - 28
  作者：

  DOI：——

  日期：——
• Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2
  作者：Young Min Rhee、Myung Soo Kim

  DOI：10.1063/1.477155

  日期：1998.10

  The deuterium isotope effect on the product energy partitioning in the title reaction was investigated both experimentally and theoretically. The measured kinetic energy release (KER) showed a significant dependence on the position of deuteration. A reliable potential energy surface of the reaction was constructed from ab initio results using the recently developed interpolation algorithm. The classical trajectory calculation on this surface well reproduced the experimental finding. Close inspection of the potential energy surface revealed that the isotope effect on KER and the product rotations arose from the alteration of the symmetry of the reaction path near the transition state induced by the mass change upon isotopic substitution. The product vibrations were found to be affected by the change in the coupling constants which also arose from the mass-dependent change in the reaction path. Possibility of the quantum mechanical tunneling was also considered. Tunneling-corrected classical trajectory results were in excellent agreement with the experimental ones, indicating that the reaction proceeds via barrier penetration below the threshold.