deuteriooxy-methyl | 58456-46-5

• 英文名称: deuteriooxy-methyl
• 英文别名: Methanol-d-Radikal；(~2~H)Hydroxymethyl
• CAS: 58456-46-5
• 化学式: CH₃O
• 分子量: 32.0263
• InChiKey: CBOIHMRHGLHBPB-VMNATFBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 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：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  氘代甲醇-d 在 D 作用下， 以 高氯酸 、 重水 为溶剂， 生成 deuteriooxy-methyl
  参考文献：
  名称：

  Kinetic Isotope Effects in H and D Abstraction Reactions from Alcohols by D Atoms in Aqueous Solution

  摘要：

  Electron paramagnetic resonance free induction decay attenuation measurements were performed in the range of liquid D2O for the reactions of D atoms with undeuterated and deuterated alcohols. Excellent Arrhenius behavior represented by log(k/M-1 s(-1)) = (10.97 +/- 0.14) - [(24.7 +/- 0.8) kJ mol(-1)/2.303RT)] for CH3OD, log(k/M-1 s(-1)) = (11.09 +/- 0.12) - [(20.8 +/- 0.6) kJ mol(-1)/2.303RT)] for CH3CH2OD, log(k/M-1 s(-1)) = (11.45 +/- 0.10) - [(28.4 +/- 0.6) kJ mol(-1)/2.303RT)] for CD3CD2OD, log(k/M-1 s(-1)) = (11.32 +/- 0.15) - [(21.3 +/- 0.8) kJ mol(-1)/2.303RT)] for CH3CH2CH2OD, log(k/M-1 s(-1)) (11.60 +/- 0.06) - [(21.2 +/- 0.3) kJ mol(-1)/2.303RT)] for(CH3)(2)C(H)OD, log(k/M-1 s(-1)) = (11.48 +/- 0.12) - [(24.7 +/- 0.7) kJ mol(-1)/2.303RT)] for(CD3)(2)C(D)OD, was found in all cases. Compared with the gas phase, the reactions exhibit slightly higher activation energies, in agreement with expectation for solvation based on a predicted decrease of the dipole moment from the reactant alcohol to the transition state. A pronounced increase in Arrhenius preexponential factors is attributed mostly to equilibrium solvation of the D atom, but a significant difference between H2O and D2O suggests contributions of a dynamic solvent effect.

  DOI：

  10.1021/jp981936l

文献信息

• Bond selectivity in the reaction of NH(<i>a</i> ¹Δ) with methanol
  作者：Satoru Okada、Atsumu Tezaki、Katsuyoshi Yamasaki、Hiroyuki Matsui

  DOI：10.1063/1.465086

  日期：1993.6

  Reaction of NH(a 1Δ) with methanol has been studied by a flash photolysis of HNCO at 193 nm at room temperature (298±2 K). Time dependence and relative concentrations for NH, NH2, NHD, CH3O, H, and D are monitored by a laser induced fluorescence (LIF) technique. From the pseudo-first-order analysis of NH(a 1Δ) decay rate, the rate constants for the reactions NH(a 1Δ)+CH3OH→ products (1), and NH(a 1Δ)+CH3OD→products (2) have been determined to be k1=(1.37±0.10)×10−10 cm3 molecule−1 s−1 in the pressure range of 3–20 Torr Ar or 5 Torr He, and k2=(1.33±0.05)×10−10 cm3 molecule−1 s−1 at the pressure of 5 Torr He, respectively. By comparing the LIF intensity of NH(X 3Σ−) in reaction (1) with that in NH(a 1Δ)+Xe reaction system, the contribution of physical quenching in reaction (1) has been evaluated to be less than 2.4%. Also by comparing the LIF intensities of NHD and NH2 in reaction (2) with those in NH(a 1Δ)+D2/H2 reaction systems, the branching ratio between the pathways producing NHD (2b) and NH2 (2c) has been determined to be k(2b)/k(2c)=23±9. It is elucidated that the insertion of NH(a 1Δ) into O–D bond of CH3OD is completely predominant over C–H bond; i.e., the O–D bond is about 69 times more reactive toward insertion of NH(a 1Δ) than a single C–H bond.
• The Reactions of Fluorine Atoms with Normal and Deuterated Methanols
  作者：Tayyaba Khatoon、K. Hoyermann

  DOI：10.1002/bbpc.198800169

  日期：1988.6

  AbstractThe reactions of fluorine atoms with normal and deuterated methanols have been studied at low pressure using a fast discharge flow reactor. Samples were withdrawn continuously via a molecular beam sampling system and were analyzed by a mass‐spectrometer. — The rate constants have been determined relative to the reactionmagnified imagefor the reactions (1)–(4) were found as k1a/k1b = 0.40/0.60; k2a/k2b = 0.37/0.63; k3a/k3b = 0.39/0.61; and k4a/k4b = 0.36/0.64.