甲基3-(乙酰氧基)-3-丁烯酸酯 | 2381-08-0

• 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: 甲基3-(乙酰氧基)-3-丁烯酸酯
• 英文名称: Alanin-3-sulfinsaeure
• 英文别名: Cysteinsulfinsaeure；2-azaniumyl-3-sulfinopropanoate
• CAS: 2381-08-0
• 化学式: C₃H₇NO₄S
• 分子量: 153.159
• InChiKey: ADVPTQAUNPRNPO-UHFFFAOYSA-N

物化性质

• 沸点：
  492.8±55.0 °C(Predicted)
• 密度：
  1.828±0.06 g/cm3(Predicted)
• 溶解度：
  >23 [ug/mL]
• 碰撞截面：
  133.7 Ų [M+H]+ [CCS Type: DT, Method: single field calibrated with ESI Low Concentration Tuning Mix (Agilent)]

计算性质

• 辛醇/水分配系数(LogP)：
  -4.2
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  120
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  hexammine cobalt(III) chloride 、 甲基3-(乙酰氧基)-3-丁烯酸酯 以 not given 为溶剂， 生成 {Coa6}{Co(C3H5NO4S)3}*4H2O
  参考文献：
  名称：

  A New Complex of Cobalt and Cysteine and its Behavior with Hydrogen Peroxide

  摘要：

  DOI：

  10.1021/ja01335a049
• 作为产物：
  描述：

  DL-胱氨酸 生成 甲基3-(乙酰氧基)-3-丁烯酸酯
  参考文献：
  名称：

  在神经药理学活性氨基酸的构效关系研究中的进一步合成。

  摘要：

  DOI：

  10.1021/jm00330a020
• 作为试剂：
  描述：

  dilithium 4-propyl-2-oxoglutarate 在 甲基3-(乙酰氧基)-3-丁烯酸酯 、 谷氨酸草乙酸氨基转移酶(猪心脏) 、 磷酸吡哆醛 作用下， 反应 24.0h， 以62%的产率得到(2S,4R)-4-propyl-glutamic acid
  参考文献：
  名称：

  A new access to alkyl-α-ketoglutaric acids, precursors of glutamic acid analogues by enzymatic transamination. Application to the synthesis of (2S,4R)-4-propyl-glutamic acid

  摘要：

  4-Alkyl-2-alkylidene-glutaric acids are easily obtained by a Claisen-Johnson rearrangement, providing a short access to 4-alkyl-alpha-ketoglutaric acids. These compounds are substrates of the glutamic oxalacetic transaminase (GOT), allowing the enzymatic synthesis of biologically important analogues of L-glutamate. A new analogue, (2S,4R)-4-propyl-glutamic acid, is described. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01302-7

文献信息

• Kinetics and Mechanism for the Reaction of Cysteine with Hydrogen Peroxide in Amorphous Polyvinylpyrrolidone Lyophiles
  作者：Dayong Luo、Bradley D. Anderson

  DOI：10.1007/s11095-006-9052-z

  日期：2006.10.4

  PURPOSE: Peroxide impurities play a critical role in drug oxidation. In metal-free aqueous solutions, hydrogen peroxide (H(2)O(2)) induced thiol oxidation involves a bimolecular nucleophilic reaction to form a reactive sulfenic acid intermediate (RSOH), which reacts with a second thiol to form a disulfide (RSSR). This study examines the reaction of cysteine (CSH) and H(2)O(2) in amorphous polyvinylpyrrolidone

  目的：过氧化物杂质在药物氧化中起关键作用。在无金属的水溶液中，过氧化氢（H（2）O（2））诱导的硫醇氧化涉及双分子亲核反应以形成反应性磺酸中间体（RSOH），该中间体与第二硫醇反应形成二硫键（RSSR） ）。这项研究检查了半胱氨酸（CSH）和H（2）O（2）在无定形聚乙烯吡咯烷酮（PVP）冻干物中的反应，以探索溶液机制与无定形玻璃中反应性的可能相关性。材料与方法：采用旨在将冻干过程中的反应减至最少的方法，制备了包含CSH和H（2）O（2）在不同初始pH和反应物浓度下的无定形PVP冻干剂。在25℃下厌氧地进行动力学研究，并通过HPLC监测反应物和产物。对产物进行表征，并将动力学数据拟合到根据溶液机理改编的模型。结果：水溶液和无定形PVP在反应中的主要区别是：（1）虽然溶液中仅形成胱氨酸（CSSC），但有三种降解物-半胱氨酸亚磺酸（CSO（2）H），半胱氨酸磺酸（CSO（3）） H）和胱氨酸（CSSC）-以无定形PVP形式形成;
• Antioxidant Chemistry:  Oxidation of <scp>l</scp>-Cysteine and Its Metabolites by Chlorite and Chlorine Dioxide
  作者：James Darkwa、Rotimi Olojo、Edward Chikwana、Reuben H. Simoyi

  DOI：10.1021/jp049748k

  日期：2004.7.1

  The oxidation of l-cysteine and its metabolites cystine and l-cysteinesulfinic acid by chlorite and chlorine dioxide has been studied in unbuffered neutral and slightly acidic media. The stoichiometry of the oxidation of l-cysteine was deduced to be 3ClO2- + 2H2NCH(COOH)CH2SH → 3Cl- + 2H2NCH(COOH)CH2SO3H with the final product as cysteic acid. The stoichiometry of the chlorite−cysteinesulfinic acid

  已经在无缓冲的中性和微​​酸性介质中研究了亚氯酸盐和二氧化氯对 l-半胱氨酸及其代谢物胱氨酸和 l-半胱氨酸亚磺酸的氧化。L-半胱氨酸氧化的化学计量推论为 3ClO2- + 2H2NCH(COOH)CH2SH → 3Cl- + 2H2NCH(COOH)CH2SO3H，最终产物为半胱氨酸。亚氯酸盐-半胱氨酸亚磺酸的化学计量比为 1:2，ClO2- + 2H2NCH(COOH)CH2SO2H → Cl- + 2H2NCH(COOH)CH2SO3H。没有经过半胱氨酸的进一步氧化，并且没有硫酸盐形成的证据表明碳-硫键的断裂。该反应在二氧化氯形成中是低振荡的。在氧化剂过量的情况下，该反应的特点是诱导期短，然后快速和自催化地形成二氧化氯。二氧化氯由中间体 HOCl 与过量亚氯酸盐反应形成：2ClO2- + 2HOCl + H+ → 2ClO2(aq) + Cl- + H2O。低聚...
• Antioxidant chemistry Reactivity and oxidation of DL-cysteine by some common oxidants
  作者：James Darkwa、Claudius Mundoma and Reuben H. Simoyi

  DOI：10.1039/a708863i

  日期：——

  The reactivity of DL-cysteine, a physiologically important aminothiol, was studied by reacting it with several well known oxidants.No activity was observed on the amino and carboxyl groups. The only reactivity of physiological significance was at the sulfur centre. Reactions of cysteine with hydrogen peroxide show that the thiol group is capable of mopping up free radicals by forming thyl radicals, as expected in its role as an antioxidant. A four-electron oxidation of cysteine gave reasonably stable cysteine sulfinic acid. Oxidants in the form of peracids do oxidize cysteine only as far as the sulfinic acid. Stronger oxidizing agents can oxidize cysteine as far as the cysteine sulfonic acid. No further oxidation can be detected as the C–S bond is not cleaved. The inertness of the amino group in cysteine makes it incapable of reversibly mopping up the dangerous oxyhalogens HOCl and HOBr which are produced by myeloperoxidase-catalysed oxidation of halides by hydrogen peroxide, as is the case with taurine. A detailed mechanism, together with a computer simulation study of the oxidation of cysteine by acidified bromate, is proposed.

  通过与几种众所周知的氧化剂反应，研究了对生理有重要意义的氨基硫醇--DL-半胱氨酸的反应性。唯一具有生理意义的反应是在硫中心。半胱氨酸与过氧化氢的反应表明，硫醇基团能够通过形成硫自由基来清除自由基，这也是半胱氨酸作为抗氧化剂的预期作用。半胱氨酸的四电子氧化反应产生了相当稳定的半胱氨酸亚硫酸。过酸形式的氧化剂只能将半胱氨酸氧化成亚硫酸。较强的氧化剂可将半胱氨酸氧化至半胱氨酸磺酸。由于 C-S 键没有裂解，因此无法检测到进一步的氧化。半胱氨酸中氨基的惰性使其无法可逆地吸收危险的氧卤素 HOCl 和 HOBr，这些氧卤素是髓过氧化物酶催化过氧化氢氧化卤化物产生的，牛磺酸的情况也是如此。本文提出了详细的机理，并对半胱氨酸被酸化溴酸盐氧化的过程进行了计算机模拟研究。
• Limited enzyme assay for aminotransferases
  申请人：Xytronyx, Inc.

  公开号：US05366870A1

  公开（公告）日：1994-11-22

  Method for determining the presence of an aminotransferase (AT.sub.1), other than aspartate aminotransferase (AST), in a biological sample. The method includes contacting the sample with an amino donor substrate for AT.sub.1, an amino acceptor substrate for AT.sub.1, cysteine sulfinic acid (CSA) in excess, a second aminotransferase (AT.sub.2), different from AT.sub.1, in excess, and an indicator for the presence of sulfite ions, under conditions in which the concentration of said AT.sub.1 can be determined by the amount of the indicator which forms a detectable signal.

  一种用于确定生物样本中存在一种非天冬氨酸氨基转移酶（AST）的氨基转移酶（AT.sub.1）的方法。该方法包括在过量的半胱氨酸亚磺酸（CSA）和不同于AT.sub.1的第二种氨基转移酶（AT.sub.2）的过量存在下，将样本与AT.sub.1的氨基供体底物，AT.sub.1的氨基受体底物和检测亚硫酸盐离子存在的指示剂接触，在浓度下，可以通过形成可检测信号的指示剂的数量来确定AT.sub.1的浓度。
• The Cysteine Dioxygenase Homologue from Pseudomonas aeruginosa Is a 3-Mercaptopropionate Dioxygenase
  作者：Egor P. Tchesnokov、Matthias Fellner、Eleni Siakkou、Torsten Kleffmann、Lois W. Martin、Sekotilani Aloi、Iain L. Lamont、Sigurd M. Wilbanks、Guy N.L. Jameson

  DOI：10.1074/jbc.m114.635672

  日期：2015.10

  Thiol dioxygenation is the initial oxidation step that commits a thiol to important catabolic or biosynthetic pathways. The reaction is catalyzed by a family of specific non-heme mononuclear iron proteins each of which is reported to react efficiently with only one substrate. This family of enzymes includes cysteine dioxygenase, cysteamine dioxygenase, mercaptosuccinate dioxygenase, and 3-mercaptopropionate dioxygenase. Using sequence alignment to infer cysteine dioxygenase activity, a cysteine dioxygenase homologue from Pseudomonas aeruginosa (p3MDO) has been identified. Mass spectrometry of P. aeruginosa under standard growth conditions showed that p3MDO is expressed in low levels, suggesting that this metabolic pathway is available to the organism. Purified recombinant p3MDO is able to oxidize both cysteine and 3-mercaptopropionic acid in vitro, with a marked preference for 3-mercaptopropionic acid. We therefore describe this enzyme as a 3-mercaptopropionate dioxygenase. Mossbauer spectroscopy suggests that substrate binding to the ferrous iron is through the thiol but indicates that each substrate could adopt different coordination geometries. Crystallographic comparison with mammalian cysteine dioxygenase shows that the overall active site geometry is conserved but suggests that the different substrate specificity can be related to replacement of an arginine by a glutamine in the active site.