甘氨酸离子 | 23297-34-9

• 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
• 中文名称: 甘氨酸离子
• 英文名称: glycinate
• 英文别名: glycinate ion；glycine anion；glycine(1-)；glycine; deprotonated form；2-aminoacetate
• CAS: 23297-34-9
• 化学式: C₂H₄NO₂
• 分子量: 74.0593
• InChiKey: DHMQDGOQFOQNFH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.8
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甘氨酸离子 在 三氟乙基醇-OD 作用下， 生成 glycinate-N,N-d2
  参考文献：
  名称：

  气相中去质子化氨基酸和肽的氢-氘交换和选择性标记

  摘要：

  研究了去质子化氨基酸和小肽的氢-氘交换反应。可以在赖氨酸的 α-氨基（4 个不稳定氢中的 2 个与 CF3CH2OD 交换）和精氨酸的胍侧链（6 个不稳定氢中的 3 个与 CH3CH2OD 和 C6H5CH2OD 交换）进行选择性标记。还完成了肽的差异标记，H/D 交换的程度取决于存在的氨基酸以及它们在链中的顺序。

  DOI：

  10.1021/ja076599l
• 作为产物：
  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

文献信息

• Electrophilic reactivity of the triphenylmethyl carbocation in aqueous solutions
  作者：Robert A. McClelland、Narinder. Banait、Steen. Steenken

  DOI：10.1021/ja00282a029

  日期：1986.10

  formation du cation tricyclium et etude de sa reactivite vis-a-vis de nucleophiles neutres et ioniques

  形成du cation tricyclium etude de sa reactive vis-a-vis de nucleophiles neutres et ioniques
• 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，
• The Stereochemistry and Reactivity of Metal-Schiff Base Complexes. VII. Contribution of Hydrophobic Interligand Interaction to Chiral Recognition of Phenylalaninate and Tryptophanate with (1<i>R</i>,2<i>R</i>)-<i>N</i>,<i>N</i>′-Disalicylidene-1,2-cyclohexanediaminecobalt(III) Complex
  作者：Yuki Fujii、Yuzo Yoshikawa、Masato Syoji、Homare Shinohara

  DOI：10.1246/bcsj.63.138

  日期：1990.1

  The stability constants, K1, of Δ-β2-diastereomers of mixed ligand cobalt(III) complexes with a chiral quadridentate Schiff base (sal-(R,R)-chxn), derived from salicylaldehyde and (R,R)-1,2-cyclohexanediamine, and d- or l-amino acidate (aa−=gly, ala, val, leu, thr, phe, trp, pro, asp, asn, and glu) were determined spectrophotometrically in water–methanol (2:3 by volume) containing acetate buffer (0.3 mol dm−3) at 22°C: trans-[Cosal-(R,R)-chxn}(H2O)2]++aa−\oversetK1\ightleftharpoonsΔ-β2-[Cosal-(R,R)-chxn}(aa)]. The K1 values range from 5.6×106 to 1.2×109 mol−1 dm3 and obey a linear free energy relationship except for d-phe, d-trp, d-asp, d-asn, and d-pro. In the cases of d-phe, d-trp, d-asp, and d-asn, their stability constants are 5–30 times as high as those for the corresponding l-aa. Extraordinary stabilization of the d-phe and d-trp complexes is discussed in terms of the interligand stacking of the aromatic rings between the Schiff base ligand and a side chain of amino acidate on the basis of conformational analysis and 1H NMR spectra.

  Δ-β2-型混配体钴(III)配合物的稳定常数K1是通过光谱法在22°C下，在含有乙酸盐缓冲液(0.3 mol dm−3)的水-甲醇(2:3体积比)混合溶液中测定的。这些配合物由手性四齿席夫碱(sal-(R,R)-chxn)和d-或l-氨基酸根(aa− = gly、ala、val、leu、thr、phe、trp、pro、asp、asn和glu)组成。sal-(R,R)-chxn是由水杨醛和(R,R)-1,2-环己二胺衍生而来。 K1值范围在5.6×106到1.2×109 mol−1 dm3之间，除了d-phe、d-trp、d-asp、d-asn和d-pro外，都符合线性自由能关系。对于d-phe、d-trp、d-asp和d-asn，它们的稳定常数是相应l-氨基酸的5-30倍。 基于构象分析和1H NMR光谱，文章讨论了d-phe和d-trp配合物的特殊稳定性，认为这与席夫碱配体和氨基酸侧链之间的芳香环层间堆积有关。
• Mechanisms of Acid Decomposition of Dithiocarbamates. 2. Efficiency of the Intramolecular General Acid Catalysis
  作者：Eduardo Humeres、Nito A. Debacher、M. Marta de S. Sierra

  DOI：10.1021/jo981382i

  日期：1999.3.1

  M. The acid decomposition of the dithiocarbamic conjugate acid of EbisDTC anion proceeds through a fast N-protonation and a slower C-N breakdown. The intramolecular general acid catalysis rate constant is (8.2 +/- 2.8) x 10(6) s(-)(1), but the efficiency of this fast proton transfer is only (14.3 +/- 4.9) M. The intramolecular general acid catalysis of the free acid forms of the carboxylic and dithiocarbamic

  研究了乙二（二硫代氨基甲酸酯）（EbisDTC）和甘氨酸二硫代羧酸酯（glyDTC）在25°C的水中H（o）-5至pH 5的酸分解作用。根据LFER计算出所有相关物种的酸解离常数以及pH值曲线。根据反应性物种的母体胺的pK（a），两种化合物都通过二硫代氨基甲酸酯阴离子和两性离子中间体分解。glyDTC阴离子的羧酸共轭酸的分子间N质子化速率常数为12.6 M（-）（1）s（-）（1），比CN分解慢。该物质还通过分子内一般酸催化的机理裂解，其中N质子化的速率常数为（7.1 +/- 4.2）x 10（3）s（-）（1），质子转移步骤的效率通过有效摩尔比测量为（5.6 +/- 3。3）x 10（2）M。EbisDTC阴离子的二硫代氨基甲酸共轭酸的酸分解通过快速的N质子化和较慢的CN分解而进行。分子内一般酸的催​​化速率常数为（8.2 +/- 2.8）x 10（6）s（-）（1），但是这种快速质子转移的效率仅为（14
• NMR Relaxation studies in solution of transition metal complexes. 3. Equilibrium dynamics in aqueous solution of copper(II)-bipyridyl-glycine system
  作者：F. Debreczeni、I. Nagypál

  DOI：10.1016/s0020-1693(00)86961-3

  日期：1982.1

  processes and the paramagnetic relaxation involving the mixed ligand copper(II)-bipyridyl-glycine complex have been determined by measuring the T 2 relaxation time of the water protons. It was found that the kinetic activity of the CubipyG + mixed complex against the ligand exchange process is not significantly different from that of the CuG 2 parent complex. An extremely high rate constant was found for the

  摘要通过测量水质子的T 2弛豫时间，确定了混合的配体铜（II）-联吡啶-甘氨酸配合物的配体交换过程的速率常数和顺磁弛豫。发现CubipyG +混合复合物对配体交换过程的动力学活性与CuG 2母体复合物的动力学活性没有显着差异。发现该反应的速率常数非常高（k -6 = 7.1 10 8 M -1 sec -1），即，稳定混合复合物的动力学背景是顺式八面体Cubipy 2+ 2络合物的不稳定性。与CuG 2相比，混合配合物的T 2B降低表明，稳定不仅反映在CuO键上，而且反映在CuN键上。