aminomethyl | 10507-29-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: aminomethyl
• 英文别名: aminomethyl radical；Methylene, 1-amino-
• CAS: 10507-29-6
• 化学式: CH₄N
• 分子量: 30.0495
• InChiKey: XXJGBENTLXFVFI-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：
  0.0
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  aminomethyl 在 paraquat dichloride 作用下， 生成 亚甲基亚胺
  参考文献：
  名称：

  Glycine Decarboxylation:  The Free Radical Mechanism

  摘要：

  Radiation chemical methods were used to investigate the reactions of glycine anions, H2NCH2CO2-(Gly(-)), with (OH)-O-., (CH3)(2)(COH)-O-., and (CH3)-C-. radicals. A major and most significant product from all of these processes is CO2. Pulse-radiolysis revealed that the initial step in the (OH)-O-.-induced mechanism is oxidation of the amino group, producing (+H2N.)-CH2-CO2- and HN.-CH2-CO2- with yields of 63% and 37%, respectively. The amino radical cation, (+H2N.)-CH2-CO2-, suffers fast (less than or equal to 100 ns) fragmentation into CO2 + (CH2NH2)-C-.. The other primary radical, HN.-CH2-CO2-, can also be converted into the decarboxylating (+H2N.)-CH2-CO2- by reaction with proton donors such as phosphate (H2PO4-/k = 7.4 x 10(7) M-1 s(-1), and HPO42-/k = 2.5 x 10(5) M-1 s(-1)) or the glycine zwitterion, Gly(+/-) (k = 3.9 x 10(5) M-1 s(-1)), but only on a much longer (typically mu s to ms) time scale (k approximate to 4 x 10(5) M-1 s(-1)). Competitively, the HN.-CH2-CO2- transforms into a carbon-centered radical H2N-(CH)-H-.-CO2- either by an intramolecular 1,2-H-atom shift (k = (1.2 +/- 1.0) x 10(3) s(-1)) or by bimolecular reaction with Gly(-) (k = (3.0 +/- 0.2) x 10(4) M-1 s(-1)). Both C-centered radicals, H2N-(CH)-H-.-CO2- and (CH2NH2)-C-., are reductants as verified through their reactions with Fe(CN)(6)(3-) and methyl viologen (MV2+) in pulse-radiolysis experiments (k approximate to 4 x 10(9) M-1 s(-1)). The eventual complete transformation of all primary radicals into H2N-(CH)-H-.-CO2- and (CH2NH2)-C-. was further substantiated by gamma-radiolytic reduction of Fe(CN)(6)(3-). In the presence of suitable electron donors, the HN.-CH2-CO2- radical acts as an oxidant. This was demonstrated through its reaction with hydroquinone (k = (7.4 +/- 0.5) x 10(7) M-1 s(-1)).Although the C-centered H2N-(CH)-H-.-CO2- radical is not generated in a direct H-atom abstraction by (OH)-O-., this radical appears to be the exclusive product in the reaction of Gly(-) with (CH3)(2)(COH)-O-., (CH2NH2)-C-., and (CH3)-C-. (k approximate to 10(2) M-1 s(-1)). A most significant finding is that H2N-(CH)-H-.-CO2- can be converted into the decarboxylating N-centered radical cation (+H2N.)-CH2-CO2- by reaction with proton donors such as Gly(+/-) (k approximate to 3 x 10(3) M-1 s(-1)) or phosphate and thus also becomes a source of CO2. The (CH2NH2)-C-.-induced route establishes, in fact, a chain mechanism which could be proven through dose rate effect experiments and suppression of the chain upon addition of Fe(CN)(6)(3-) or MV2+ as a scavenger for the reducing precursor radicals. The possible initiation of amino acid decarboxylation by C-centered radicals and the assistance of proton donors at various stages within the overall mechanism are considered to be of general significance and interest in chemical and biological systems.

  DOI：

  10.1021/ja9815428
• 作为产物：
  描述：

  甲胺 在 aqueous solvated electron 作用下， 以 水 为溶剂， 生成 aminomethyl
  参考文献：
  名称：

  氧化物自由基阴离子在水溶液中与脂肪族氨基化合物的反应性： •O- 和 •OH 自由基从 C-H 和 N-H 基团中提取 H-原子的比较

  摘要：

  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，

  DOI：

  10.1021/jp031193q

文献信息

• Time resolved FT EPR study of the decarboxylation following photo-induced electron transfer between α-amino acids and anthraquinone-2,6-disulfonic acid in aqueous solution
  作者：Jian-Ming Lü、L. M. Wu、J. Geimer、D. Beckert

  DOI：10.1039/b100931l

  日期：——

  Using laser photolysis of basic anaerobic aqueous solutions of α-glycine, L-α-alanine and α–aminoisobutyric acid containing anthraquinone-2,6-disulfonic acid the two spin-polarized (CIDEP) C•R1R2NH2 and NH2C•R1COO− radicals (R1, R2 = H or CH3) and the radical anion of anthraquinone-2,6-disulfonic acid were detected by time resolved Fourier transform electron paramagnetic resonance (FT EPR) spectroscopy

  使用激光光解 α-甘氨酸、L-α-丙氨酸和含有蒽醌-2,6-二磺酸的 α-氨基异丁酸的碱性厌氧水溶液，两个自旋极化 (CIDEP) C•R1R2NH2 和 NH2C•R1COO- 自由基 (通过时间分辨傅里叶变换电子顺磁共振(FT EPR)光谱法检测R1、R2 = H或CH3)和蒽醌-2,6-二磺酸的自由基阴离子。FT EPR 结果表明，α-甘氨酸、L-α-丙氨酸和 α-氨基异丁酸被蒽醌-2,6-二磺酸的自旋极化光激发三重态通过单电子转移和快速氧化脱羧。在竞争反应通道中，醌三重态通过氢转移从 α-甘氨酸和 α-丙氨酸衰变，产生 NH2C•R1COO- 自由基。
• 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.
• Effect of the protonation state of the amino group on the .cntdot.OH radical induced decarboxylation of amino acids in aqueous solution
  作者：Joerg Moenig、Rita Chapman、Klaus Dieter Asmus

  DOI：10.1021/j100260a037

  日期：1985.7
• Rate constants for reactions of substituted methyl radicals (CH2OCH3, CH2NH2, CH2I, and CH2CN) with O2
  作者：Akira Masaki、Shigeru Tsunashima、Nobuaki Washida

  DOI：10.1021/j100035a014

  日期：1995.8

  Reactions of the substituted methyl radicals CH2OCH3,CH2NH2,CH2I, and CH2CN with O-2 have been studied by a combination of pulsed laser photolysis and photoionization mass spectrometry. The reactivity is greatly enhanced by substituting one of the hydrogen atoms of a methyl radical with the electron-donating substituents, -OCH3 and -NH2. The rate constants obtained at 298 +/- 5 K were (6.5 +/- 0.7) x 10(-12) and (3.5 +/- 0.4) x 10(-11) in units of cm(3) molecule(-1) s(-1) for CH2OCH3 and CH2NH2, respectively, and no pressure dependence was observed between 0.6 and 6 Torr (80-800 Pa) of N-2 as a bath gas. The reactivity is reduced for CH2I and CH2CN, which have the electron-withdrawing substituents -I and -CN. The rate for the reaction of CH2I with O-2 was independent on the total pressure between 2 and 15 Torr (270-2000 Pa) of N-2, and the rate constant was determined to be (1.6 +/- 0.2) x 10(-12) cm(3) molecule(-1) s(-1). The rate constants of CH2CN with O-2 depended on the total pressure, and were (6.8-11.0) x 10(-15) cm(3) molecule(-1) s(-1) for total pressures 2-6 Torr (270-800 Pa) of N-2 + O-2. The reactivity of substituted methyl radicals is discussed by the correlation with ionization potentials and electronegativities of radicals.
• Reddy, G. Krishna; Reddy, T. Rayapa; Jagannadham, V., Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1989, vol. 28, # 1, p. 32 - 35
  作者：Reddy, G. Krishna、Reddy, T. Rayapa、Jagannadham, V.

  DOI：——

  日期：——