N-chloroglycylglycine | 53090-33-8

• 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: N-chloroglycylglycine
• 英文别名: (N-Cl)-Gly-Gly；2-[[2-(Chloroamino)acetyl]amino]acetic acid
• CAS: 53090-33-8
• 化学式: C₄H₇ClN₂O₃
• 分子量: 166.564
• InChiKey: ILKNHLINVXNMPC-UHFFFAOYSA-N

物化性质

• 密度：
  1.444±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.3
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  78.4
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-chloroglycylglycine 在 三氧化硫 作用下， 以 various solvent(s) 为溶剂， 生成 双甘肽
  参考文献：
  名称：

  Rates of Reduction of N-Chlorinated Peptides by Sulfite:  Relevance to Incomplete Dechlorination of Wastewaters

  摘要：

  Biologically induced fragmentation of proteins during wastewater treatment produces peptides, which form long-lasting organic chloramines when the water is disinfected with Cl-2. To protect aquatic wildlife from residual chlorine, including chloramines, wastewaters are often treated with sulfur dioxide or sulfite salts. This strategy incompletely eliminates residual chlorine species. Here we report that dechlorination rate constants of N-chloropeptides are 1-2 order of magnitude smaller than those for NH2Cl and some aliphatic organic chloramines. Slow rates explain the prevalence of N-chloropeptides in dechlorinated wastewaters after faster reacting chlorine species have been eliminated. Dechlorination is subject to general acid catalysis. For N-chlorinated leucylalanine, the rate law above pH 6 in phosphate buffer at 25 degrees C and I approximate to 0.1 M is as follows: rate = (9.92 +/- 0.41 x 10(3)[H2PO4-] + 5.70 +/- 0.52 x 10(8)[H3O+] + 5.3 +/- 0.2)[SO32-][Cl-Leu-Ala] (concentrations in M, time in s). Rate constants for other peptides appear to be of similar magnitude; variations in the acid-catalyzed terms among different hydrophobic peptides correlate with solvation energies of side chains. The kinetic data suggest that reducing N-chloropeptides in wastewaters by 75% or more will require reaction times generally >0.5 h at environmentally acceptable S-IV doses and pH values.

  DOI：

  10.1021/es9707365
• 作为产物：
  描述：

  双甘肽 在 potassium chloride 、 次氯酸 作用下， 以 水 为溶剂， 生成 N-chloroglycylglycine
  参考文献：
  名称：

  二肽的细胞内氧化。氨基末端残基非常快速的卤化

  摘要：

  肽类 与水溶液进行非常快速的卤化反应 卤素。该过程是通过脂族亲电取代反应完成的，其双分子速率常数约为。10 7 M -1 s -1。形成的产物为N-卤代-肽，即，卤化过程发生在氮原子 在 氨基-氨基酸残基的末端部分。[卤化剂] / [二肽]≤1，未发现任何分析或动力学证据 卤化 在 肽键或在羧基末端残基的氧原子上。细胞内氧化作用 的 肽到N -halo-肽通过体内机制来减少由细胞内氧化剂引起的氧化应激。

  DOI：

  10.1039/b007208g

文献信息

• Intracellular Oxidation of Dipeptides. Base-Promoted Elimination from <i>N</i>-Halodipeptides to 2-[<i>N</i>-Alkyl-<i>N</i>-(2-<i>N</i>-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic Acids
  作者：X. L. Armesto、M. Canle L.、M. I. Fernández、M. V. García、S. Rodríguez、J. A. Santaballa

  DOI：10.1021/jo001336u

  日期：2001.8.1

  via the formation of the corresponding (N-X)-dipeptides, that then undergo base-promoted elimination to yield intermediate 2-[N-alkyl-N-(2-N-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic acids, which subsequently hydrolyze. Such an elimination process is general-base catalyzed, with Brønsted beta values ranging from 0.26 to 0.31, which suggests an essentially constant degree of proton transfer

  肽的细胞内氧化的可能方式之一是通过形成相应的（NX）-二肽，然后对其进行碱促进的消除，以生成中间体2- [N-烷基-N-（2-N-烷基亚氨基-2） -烷基乙酰基）氨基] -2，2-二烷基乙酸，其随后水解。这种消除过程是通用碱催化的，布朗斯台德β值在0.26到0.31之间，这表明质子在TS处的转移程度基本恒定。对于（NX）-二肽，比率k（N-Br）/ k（N-Cl）为2.5至15，表明在TS处NX键断裂程度的结构依赖性。β和k（N-Br）/ k（N-Cl）的值支持协调一致的异步A（xh）D（H）D（N）机制，其TS取决于反应物从类反应物变为类to起始二肽的结构。由于该反应需要抗平面性，因此离去基团与带有要被除去的H的C上的取代基之间的空间相互作用控制了反应速率。如空间交叉相互作用系数（p（ssy′）＝ 0.33）所示，这种空间相互作用是相当重要的。半经验计算表明，反应中心附近的大取代基意味着
• Armesto, Xose Luis; Lopez, Moises Canle; Garcia, Maria Victoria, Gazzetta Chimica Italiana, 1994, vol. 124, # 12, p. 519 - 524
  作者：Armesto, Xose Luis、Lopez, Moises Canle、Garcia, Maria Victoria、Losada, Manuel、Santaballa, Juan Arturo

  DOI：——

  日期：——
• Use of N-chloro-N-methyl-p-toluenesulfonamide in N-chlorination reactions
  作者：Cristina Pastoriza、Juan Manuel Antelo、Juan Crugeiras

  DOI：10.1002/poc.3127

  日期：2013.7

  Second-order rate constants (k2) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2,2,2-trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N-chloro-N-methyl-p-toluenesulfonamide (NCNMPT) in the formation reaction of N-chloramines in aqueous solution at 25 degrees C and ionic strength 0.5M. The series of nucleophiles considered is structurally very varied and covers five pKa units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N-chloramines more readily. Rate constants for the nucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N-methyl-N-nitroso-p-toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl+ atom. Copyright (c) 2013 John Wiley & Sons, Ltd.
• Rates of Reduction of N-Chlorinated Peptides by Sulfite:  Relevance to Incomplete Dechlorination of Wastewaters
  作者：James S. Jensen、George R. Helz

  DOI：10.1021/es9707365

  日期：1998.2.1

  Biologically induced fragmentation of proteins during wastewater treatment produces peptides, which form long-lasting organic chloramines when the water is disinfected with Cl-2. To protect aquatic wildlife from residual chlorine, including chloramines, wastewaters are often treated with sulfur dioxide or sulfite salts. This strategy incompletely eliminates residual chlorine species. Here we report that dechlorination rate constants of N-chloropeptides are 1-2 order of magnitude smaller than those for NH2Cl and some aliphatic organic chloramines. Slow rates explain the prevalence of N-chloropeptides in dechlorinated wastewaters after faster reacting chlorine species have been eliminated. Dechlorination is subject to general acid catalysis. For N-chlorinated leucylalanine, the rate law above pH 6 in phosphate buffer at 25 degrees C and I approximate to 0.1 M is as follows: rate = (9.92 +/- 0.41 x 10(3)[H2PO4-] + 5.70 +/- 0.52 x 10(8)[H3O+] + 5.3 +/- 0.2)[SO32-][Cl-Leu-Ala] (concentrations in M, time in s). Rate constants for other peptides appear to be of similar magnitude; variations in the acid-catalyzed terms among different hydrophobic peptides correlate with solvation energies of side chains. The kinetic data suggest that reducing N-chloropeptides in wastewaters by 75% or more will require reaction times generally >0.5 h at environmentally acceptable S-IV doses and pH values.
• Intracellular oxidation of dipeptides. Very fast halogenation of the amino-terminal residue
  作者：Xosé Luis Armesto、Moisés Canle L.、M. Isabel Fernández、M. Victoria García、Santiago Rodríguez、J. Arturo Santaballa

  DOI：10.1039/b007208g

  日期：——

  aliphatic electrophilic substitution with bimolecular rate constants of ca. 107 M−1 s−1. The products formed are N-halo-peptides, i.e., the halogenation process takes place on the nitrogen atom at the amino-terminal moiety of the amino acid residue. At ratios [halogenating agent]/[dipeptide] ≤ 1, no analytical or kinetic evidence has been found of halogenation on the peptide bond or on the oxygen atom of

  肽类 与水溶液进行非常快速的卤化反应 卤素。该过程是通过脂族亲电取代反应完成的，其双分子速率常数约为。10 7 M -1 s -1。形成的产物为N-卤代-肽，即，卤化过程发生在氮原子 在 氨基-氨基酸残基的末端部分。[卤化剂] / [二肽]≤1，未发现任何分析或动力学证据 卤化 在 肽键或在羧基末端残基的氧原子上。细胞内氧化作用 的 肽到N -halo-肽通过体内机制来减少由细胞内氧化剂引起的氧化应激。