Methylamin-Radikal | 15622-51-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Methylamin-Radikal
• 英文别名: Methyl amino radical
• CAS: 15622-51-2
• 化学式: CH₄N
• 分子量: 30.0495
• InChiKey: YKPQUSLRUFLVDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  Methylamin-Radikal 、 hydroquinone anion 以 水 为溶剂， 生成 4-hydroxycyclohexa-2,5-dien-1-one, sodium salt
  参考文献：
  名称：

  •OH自由基在水溶液中从正和碳氘代乙醇和甲胺中提取氢的动力学同位素效应

  摘要：

  已经确定了 •OH 自由基在 H2O 溶液中与乙醇（CH3CH2OH 和 CD3CD2OH）和甲胺（CH3NH2 和 CD3NH2）反应的各种途径的选择性 H/D 动力学同位素效应 (KIE)。KIE 已经从总体速率常数和在与这些化合物的 •OH 反应中生成单个初级自由基的产率进行了评估。用于产率测定的分析方法是使用合适的清除剂进行氧化还原滴定，即甲基紫精和 Fe(CN)63- 用于还原自由基（CH3C•HOH/CD3C•DOH 和•CH2NH2/•CD2NH2）以及 I- 和对苯二酚对于氧化自由基（CH3CH2O•/CD3CD2O• 和•NHCH3/•NHCD3）。除了相对于总有效•OH 的产率之外，获得的数值结果还包括大多数这些清除反应的绝对速率常数。对于酒精，主要过程（几乎 90%）是从 Cα 键中提取 H/D，KIE = 1.96。对于甲胺，只有 37% (H) 和 26% (D)

  DOI：

  10.1021/jp027790e
• 作为产物：
  描述：

  甲基氨基磺酰氯 在 三乙基硅烷 、 二叔丁基过氧化物 作用下， 以 乙醚 为溶剂， 生成 Methylamin-Radikal 、
  参考文献：
  名称：

  Chatgilialoglu, Chryssostomos; Gilbert, Bruce C.; Norman, Richard O. C., Journal of Chemical Research, Miniprint, 1980, # 6, p. 2610 - 2623

  摘要：

  DOI：

文献信息

• Oxide Radical Anion Reactivity with Aliphatic Amino Compounds in Aqueous Solution:  Comparison of H−Atom Abstraction from C−H and N−H Groups by ^•O^- and ^•OH Radicals
  作者：David A. Armstrong、Klaus-Dieter Asmus、Marija Bonifačic

  DOI：10.1021/jp031193q

  日期：2004.3.1

  α-C-centered radicals appear to be formed only by direct H abstraction reactions. In line with this, the ratios of the overall rates of H abstraction from N−H and C−H, kN(-H•)/kC(-H•), for •O- reacting with different amino compounds decrease with C−H bond dissociation enthalpy (BDE) and thus follow the pattern expected for direct abstraction reactions. In contrast to •O-, the conjugate •OH radical produces

  单电子氧化剂通过电子转移 (ET) 与 H2N-CHRR' 氨基化合物反应，并直接从 N-H 和 C-H 中提取 H，分别得到铵 (+•NH2CHRR')、胺基 (•NH-CHRR' ) 和以 α-C 为中心的自由基 (H2N-•CRR')。在 pH ≥ 13 的条件下，研究了这些物质与甘氨酸 (Gly-)、丙氨酸 (Ala-) 和 α-甲基丙氨酸 (MeAla-) 的阴离子以及甲胺 (MeNH2) 的 •O- 反应的产率。结果表示 ET 过程可以忽略不计。胺基和以α-C 为中心的自由基似乎只能通过直接的夺氢反应形成。与此一致，对于 •O- 与不同的氨基化合物反应，从 N-H 和 C-H 中提取 H 的总比率 kN(-H•)/kC(-H•) 随 C- 降低H 键解离焓 (BDE)，因此遵循直接提取反应的预期模式。与•O-相反，
• Reactions of N(2 2D) with methane and deuterated methanes
  作者：Hironobu Umemoto、Takanobu Nakae、Hideomi Hashimoto、Koichi Kongo、Masahiro Kawasaki

  DOI：10.1063/1.477206

  日期：1998.10.8

  NH radicals and H atoms were identified as products in the reaction of N(2D) with CH4. The absolute yields of NH and H were determined to be 0.3±0.1 and 0.8±0.2, respectively. The rotational state distributions of NH (v″=0) for CH4 and partially deuterated methanes, CHnD4−n (n=1–3), are single modal and peak at N″=13±2, while the vibrational population ratios, NH (v″=1)/NH (v″=0), are 0.6. The rotational energy distribution of ND (v″=0) from CD4 is similar to that for NH (v″=0). The ND (v″=1)/ND (v″=0) ratio is 0.6. Doppler profiles of H and D atoms were measured to evaluate the energy released to the translational mode. It was between 72 and 85 kJ mol−1, suggesting the following H atom production mechanism: N(2D)+CH4→H+CH2NH. The H+CH3N channel is minor. In the reactions with partially deuterated methanes, the isotopic ratios, [H]/[D] and [NH]/[ND], are larger than the stoichiometric ratios in the reactant methanes. These results suggest that C–H bonds are more reactive to N(2D) than C–D bonds, while H atoms are ejected more preferentially than D atoms.
• Competing Bond Fission and Molecular Elimination Channels in the Photodissociation of CH3NH2 at 222 nm
  作者：G. C. G. Waschewsky、D. C. Kitchen、P. W. Browning、L. J. Butler

  DOI：10.1021/j100009a022

  日期：1995.3

  This paper presents the first experimental investigation under collisionless conditions of the competing photodissociation channels of methylamine excited in the first ultraviolet absorption band. Measurement of the nascent photofragments' velocity distributions and preliminary measurements of some photofragments' angular distributions evidence four significant dissociation channels at 222 nm: N-H, C-N, and C-H bond fission and H-2 elimination. The data, taken on photofragments from both methylamine and methylamine-d(2), elucidate the mechanism for each competing reaction. Measurement of the emission spectrum of methylamine excited at 222 nm gives complementary information, evidencing a progression in the amino wag (or inversion) and combination bands with one quantum in the methyl (umbrella) deformation or with two quanta in the amino torsion vibration. The emission spectrum reflects the forces in the Franck-Condon region which move the molecule toward a ciscoid geometry. The photofragment kinetic energy distributions measured for CH3ND2 show that hydrogen elimination occurs via a four-center transition state to produce HD and partitions considerable energy to relative product translation. The reaction coordinates for N-H and C-N fission are analyzed in comparison to that for ammonia dissociation from the (A) over tilde state and with reference to a initio calculations of cuts along the excited state potential energy surface of methylamine which show these reactions traverse a small barrier in the excited state from a Rydberg/valence avoided crossing and then encounter a conical intersection in the exit channel. The measured kinetic energy distribution of the C-N bond fission photofragments indicates that the NH2 (ND2) product is formed in the (A) over tilde (2)A(1) state; the C-N fission reactive trajectories thus remain on the upper adiabat as they traverse the conical intersection. The mechanism for C-H bond fission is less clear; most of the kinetic energy distribution indicates the reaction evolves on a potential energy surface with no barrier to the reverse reaction, consistent with dissociation along the excited state surface or upon internal conversion to the ground state, but some of the distribution reflects more substantial partitioning to relative translation, indicating that some molecules may dissociate via a repulsive triplet surface. In general, the photofragment angular distributions were anisotropic, but the measured beta approximate to -0.4 +/- 0.4 for C-N bond fission indicates dissociation is not instantaneous on the time scale of molecular rotation. We end with analyzing why in methylamine three other primary dissociation channels effectively compete with N-H fission while in CH3OH and CH3SH primarily O-H and S-H fission, respectively, dominate.
• Xu, Guoying; Herman, Jan A.; Wojcik, Leszek, Canadian Journal of Chemistry, 1990, vol. 68, # 4, p. 570 - 574
  作者：Xu, Guoying、Herman, Jan A.、Wojcik, Leszek

  DOI：——

  日期：——
• Kinetic Isotope Effect for Hydrogen Abstraction by ^•OH Radicals from Normal and Carbon-Deuterated Ethyl Alcohol and Methylamine in Aqueous Solutions
  作者：Marija Bonifačić、David A. Armstrong、Igor Štefanić、Klaus-Dieter Asmus

  DOI：10.1021/jp027790e

  日期：2003.7.1

  Selective H/D kinetic isotope effects (KIEs) have been determined for the various routes by which •OH radicals react with ethanol (CH3CH2OH and CD3CD2OH) and methylamine (CH3NH2 and CD3NH2) in H2O solutions. The KIEs have been evaluated from overall rate constants and the yields in which the individual primary radicals were generated in the •OH reaction with these compounds. The analytical method applied

  已经确定了 •OH 自由基在 H2O 溶液中与乙醇（CH3CH2OH 和 CD3CD2OH）和甲胺（CH3NH2 和 CD3NH2）反应的各种途径的选择性 H/D 动力学同位素效应 (KIE)。KIE 已经从总体速率常数和在与这些化合物的 •OH 反应中生成单个初级自由基的产率进行了评估。用于产率测定的分析方法是使用合适的清除剂进行氧化还原滴定，即甲基紫精和 Fe(CN)63- 用于还原自由基（CH3C•HOH/CD3C•DOH 和•CH2NH2/•CD2NH2）以及 I- 和对苯二酚对于氧化自由基（CH3CH2O•/CD3CD2O• 和•NHCH3/•NHCD3）。除了相对于总有效•OH 的产率之外，获得的数值结果还包括大多数这些清除反应的绝对速率常数。对于酒精，主要过程（几乎 90%）是从 Cα 键中提取 H/D，KIE = 1.96。对于甲胺，只有 37% (H) 和 26% (D)