2-(氯氨基)乙酸 | 35065-59-9

• 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: 2-(氯氨基)乙酸
• 英文名称: N-chloroglycine
• 英文别名: glycine chloramine；N-chloroglycin；chloroglycine；N-chloro-glycine；Chloramino-essigsaeure；N-Chlor-glycin；2-(chloroamino)acetic acid
• CAS: 35065-59-9
• 化学式: C₂H₄ClNO₂
• 分子量: 109.512
• InChiKey: YKCPTPSKQFNDHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.6
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(氯氨基)乙酸 在 hydroxide 作用下， 以 水 为溶剂， 生成 乙醛酸
  参考文献：
  名称：

  Concerted base-promoted elimination in the decomposition ofN-halo amino acids

  摘要：

  N-Chloroamino acids are unstable in aqueous solution and decompose through different pathways depending on the reaction conditions, yielding precursors of carcinogenic and/or mutagenic compounds, One of these pathways is a 1,2-elimination process, which has scarcely received any attention and for which no systematic analysis is available, The process is first order relative to the N-chloroamino acid and to that of hydroxide ion, The use of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoropropan-2-ol buffer solutions established that the process is general-base catalysed, The reaction rate is affected by the presence of a methyl group on the nitrogen atom and the nature of the leaving group, The results show an important steric effect due to the alkyl substituents on the alpha-carbon. With bulky alkyl substituents on the a-carbon, and in particular in the case of N-alkylamino acids, the catalytic effect increases as the base strength decreases. To characterize the transition state, Bronsted's beta and beta(lg) were used. A More O'Ferrall-Jencks diagram shows the transition state structure changing from carbanion like to nitrenium-like, a large perpendicular effect being evident, The reaction proceeds through a concerted mechanism A(xh)D(H)D(N) instead of the stepwise A(xh)D(H) double dagger+D-N proposed earlier.

  DOI：

  10.1002/(sici)1099-1395(199608)9:8<552::aid-poc820>3.0.co;2-r
• 作为产物：
  描述：

  聚甘氨酸 在 sodium perchlorate 作用下， 生成 2-(氯氨基)乙酸
  参考文献：
  名称：

  碱性水溶液中N-氯甘氨酸的分解：动力学和机理

  摘要：

  在非常碱性的条件下（[OH – ] = 0.01–0.10 M）研究了N-氯甘氨酸（MCG）的分解动力学和机理。吸光度的变化与在220-350 nm波长范围内的两个连续的一阶过程一致。第一反应是线性地依赖于[OH - ]，并通过在平衡步骤（形成从MCG碳负离子的解释ķ OH），并从该中间氯离子的后续损耗：ķ OBS1 = ķ OH ķ 1 =（6.4 ±0.1）×10 –2 M –1 s –1，I = 1.0 M（NaClO 4），且T = 25.0°C。第二个过程分配给N-草酰甘氨酸的一阶分解，该分解也作为该系统的中间体形成：k obs2 =（1.2±0.1）×10 –3 s –1。为了确定并跟踪反应物，中间体和产物的浓度变化，进行了系统的1 H和13 C NMR测量。证实了分解是通过乙醛酸根离子的形成而进行的，并产生N。-甲酰基甘氨酸作为终产物。该化合物可长时间稳定，但最终会水解成甲酸

  DOI：

  10.1021/acs.chemrestox.5b00084

文献信息

• Reactions of chlorination with<i>tert</i>-butyl hypochlorite (^TBuOCl)
  作者：Cristina Pastoriza、Juan Manuel Antelo、Juan Crugeiras

  DOI：10.1002/poc.3377

  日期：2014.12

  The chlorination reactions of nitrogenous organic compounds (2,2,2‐trifluoroethylamine, benzylamine, glycine, and dimethylamine) by tert‐butyl hypochlorite (tBuOCl) were studied at 25 °C, ionic strength 0.5 M and under isolation conditions. The kinetic results obtained in the formation processes of the corresponding N‐chloramines in acid medium (pH = 5–7) are summarized in this paper. Kinetic studies

  研究了含氮有机化合物（2,2,2-三氟乙胺，苄胺，甘氨酸和二甲胺）在25°C，离子强度0.5 M和隔离条件下于次氯酸叔丁酯（t BuOCl）的氯化反应。本文总结了在酸性介质（pH = 5-7）中相应的N-氯胺形成过程中获得的动力学结果。动力学研究表明相对于t而言是一阶的BuOCl浓度。相对于含氮化合物的浓度，涉及苄胺，甘氨酸和二甲胺的氯化反应均为一阶，相对于质子浓度而言约为一阶。与2,2,2-三氟乙胺的反应更加复杂，并且相对于胺的反应顺序随pH的变化而变化。版权所有©2014 John Wiley＆Sons，Ltd.
• Ability of Hypochlorous Acid and <i>N</i>-Chloramines to Chlorinate DNA and Its Constituents
  作者：Naomi R. Stanley、David I. Pattison、Clare L. Hawkins

  DOI：10.1021/tx100188b

  日期：2010.7.19

  8-chloro-2′-deoxyguanosine (8CldG). With the nucleosides, 8CldG was the favored product in each case, and HOCl was the most efficient chlorinating agent. 5Cl(d)C was the most abundant product on exposure of the nucleotides and DNA to HOCl and His-C, with only low levels of chlorinated products observed with Lys-C, Gly-C, Tau-C, and Mono-C. 5CldC was also formed on exposure of smooth muscle cells to either HOCl

  髓过氧化物酶是活化吞噬细胞释放的血红素酶，负责产生强氧化剂次氯酸（HOCl）。尽管HOC1具有强力的杀菌特性，并且在人类免疫系统中起着重要的作用，但是这种氧化剂也会对组织造成损害，特别是在炎症条件下。慢性炎症与许多癌症的发生之间有很强的联系，这可能与HOCl和相关氧化剂（例如N-氯胺）破坏DNA的能力有关。然而，与HOCl相反，关于N-氯胺与DNA及其成分的反应性知之甚少。在这项研究中，我们研究了HOCl和各种N的能力。-氯胺在核苷，核苷酸，DNA和细胞系统中形成氯化基础产物。实验是用进行Ñ形成在-chloramines Ñ α乙酰基-组氨酸（His-C），Ñα-乙酰基赖氨酸（Lys-C），甘氨酸（Gly-C），牛磺酸（Tau-C）和氨（Mono-C）。用HOCl和His-C处理DNA和相关物质导致形成5-氯-2'-脱氧胞苷（5CldC），8-氯-2'-脱氧腺苷（8CldA）和8-氯-2'-脱氧鸟苷（
• Absolute rate constants for the formation of nitrogen-centred radicals from chloramines/amides and their reactions with antioxidants
  作者：David I. Pattison、Michael J. Davies、Klaus-Dieter Asmus

  DOI：10.1039/b202526d

  日期：——

  Pulse radiolysis techniques have been employed to investigate the one-electron reduction of a variety of chloramines and chloramides. These include models for the side-chain of Lys (6-aminohexanoic acid chloramine and α-N-acetyl-Lys chloramine), Gly chloramine, β-alanine chloramine and two models of protein backbone amides, the chloramides of cyclo-(Gly)2 and cyclo-(Ala)2. The molar absorption coefficients and stabilities of these chloramines/amides have been determined. The one-electron reduction of these chloramine/amide species by hydrated electrons occurs with second-order rate constants of the order of 109–1010 M−1 s−1, and results in cleavage of the N–Cl bonds to yield nitrogen-centred radicals and chloride ions (as measured by high performance ion chromatography). The reactivities of the nitrogen-centred radicals have been investigated with the readily oxidisable quenchers, hydroquinone and Trolox. These quenchers were used as models of the in vivo antioxidants, ubiquinol-10 and α-tocopherol, and react with second-order rate constants between 2 × 107 and 1 × 108 M−1 s−1. No evidence was obtained in these pulse radiolysis experiments for a rapid rearrangement of the oxidising nitrogen-centred radicals to reducing carbon-centred radicals, though such reactions have been indicated in previous EPR studies.

  利用脉冲辐射分解技术研究了多种氯胺和氯化物的单电子还原。其中包括 Lys 侧链模型（6-氨基己酸氯胺和α-N-乙酰-Lys 氯胺）、Gly 氯胺、β-丙氨酸氯胺和两种蛋白质骨架酰胺模型，即环-(Gly)2 和环-(Ala)2 的氯酰胺。测定了这些氯胺/酰胺的摩尔吸收系数和稳定性。水合电子对这些氯胺/酰胺物种的单电子还原以 109-1010 M-1 s-1 量级的二阶速率常数发生，并导致 N-Cl 键裂解，生成以氮为中心的自由基和氯离子（通过高效离子色谱法测量）。研究人员用容易氧化的淬灭剂对苯二酚和三氯氧烷研究了以氮为中心的自由基的反应活性。这些淬灭剂被用作体内抗氧化剂泛醌-10 和 α-生育酚的模型，其反应的二阶速率常数在 2 × 107 和 1 × 108 M-1 s-1 之间。在这些脉冲辐射分解实验中，没有证据表明氧化型氮中心自由基会迅速重新排列为还原型碳中心自由基，尽管在以前的 EPR 研究中曾出现过此类反应。
• α-amino acids chlorination in aqueous media
  作者：X.L. Armesto、M.L. Canle、J.A. Santaballa

  DOI：10.1016/s0040-4020(01)80525-1

  日期：1993.1

  The reaction of chlorination of alpha-amino acids for 6 < pH < 11 has been studied. The reaction is an aliphatic electrophilic substitution, the rate determining step being the transfer of the chlorine atom between the HOCl oxygen and the nitrogen of the alpha-amino acid free amino group.
• Awad, Riad; Hussain, Anwar; Crooks, Peter A., Journal of the Chemical Society. Perkin transactions II, 1990, # 7, p. 1233 - 1238
  作者：Awad, Riad、Hussain, Anwar、Crooks, Peter A.

  DOI：——

  日期：——