glycine aminyl radical | 65627-66-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: glycine aminyl radical
• CAS: 65627-66-9
• 化学式: C₂H₃NO₂
• 分子量: 73.0513
• InChiKey: IJOSUPPHLJKFPA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.98
• 重原子数：
  5.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.93
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  glycine aminyl radical 在 sodium hydroxide 、 对苯二酚 作用下， 生成 甘氨酸离子
  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：

  N-chloroglycine anion 以 phosphate buffer 为溶剂， 生成 glycine aminyl radical
  参考文献：
  名称：

  Hawkins, Clare L.; Davies, Michael J., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1998, # 9, p. 1937 - 1945

  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 ( -•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，