monomalonyl malonate | 173040-78-3

• 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: monomalonyl malonate
• 英文别名: 2-(2-Carboxyacetyl)oxypropanedioic acid
• CAS: 173040-78-3
• 化学式: C₆H₆O₈
• 分子量: 206.109
• InChiKey: WHZMDUVUQJBHKE-UHFFFAOYSA-N

物化性质

• 沸点：
  586.1±50.0 °C(Predicted)
• 密度：
  1.787±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  138
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  monomalonyl malonate 在 氢氧化钾 作用下， 生成 丙醇二酸 、 丙二酸
  参考文献：
  名称：

  HPLC Studies on the Organic Subset of the Oscillatory BZ Reaction. 2. Two Different Types of Malonyl Radicals in the Ce⁴⁺−Malonic Acid Reaction

  摘要：

  Applying combined HPLC and NMR techniques, it was found that, besides the already known 1,1,2,2-ethanetetracarboxylic acid (ETA), monomalonyl malonate (MAMA) is also a product of the Ce4+-malonic acid reaction. This is indirect evidence that two different types of organic radicals are formed in the reaction: the alkyl and the carboxylato malonyl radicals. While ETA is a recombination product of two alkyl radicals, MAMA is formed in the recombination of one alkyl and one carboxylato radical.

  DOI：

  10.1021/jp952492l
• 作为产物：
  描述：

  丙醇二酸 、 丙二酸 在 phosphorus pentoxide 作用下， 生成 monomalonyl malonate
  参考文献：
  名称：

  在终止丙二酸和乙酸水溶液中的α-羧甲基自由基中，介观异构的重要性。

  摘要：

  在无双氧的丙二酸和乙酸水溶液中。α-羧甲基自由基是通过辐射产生的OH自由基从母体化合物中提取氢而产生的。从CO2- / CO2H基团中脱除H并进行脱羧反应的重要性不高（<或= 5％）。α-羧甲基基团通过重组终止。观察到两种类型的重组产物，其特征在于形成CC键或CO键。α-羧甲基自由基是介观体系。它们的介观状态取决于质子化状态，并决定了它们所产生的CC连接脱CO二聚体与CO连接脱氢二聚体的比例。

  DOI：

  10.1002/1521-3765(20010216)7:4<791::aid-chem791>3.0.co;2-2

文献信息

• Chemical mechanism of the radical feedback loop in the classical BZ reaction. Malonyl bromite and oxalic acid as flow-through intermediates
  作者：László Hegedüs、Horst-Dieter Försterling、Enikö Kókai、Krisztina Pelle、Gabriella Taba、Mária Wittmann、Zoltán Noszticzius

  DOI：10.1039/b004903o

  日期：——

  dibromomalonic acid intermediates. It is known that there are two negative feedback loops in the BZ reaction: one is ia bromide and the other ia organic free radicals. Oxalic acid and also CO2 are products of this second loop where organic radicals react with BrO2 radicals. The induction period was chosen for the present experimental studies because the above radical–radical reactions are most intense

  在经典的 Belousov-Zhabotinsky (BZ) 反应（硫酸介质中的丙二酸-溴酸盐-铈催化​​剂）的诱导期进行高压液相色谱 (HPLC) 和产生的 CO2 的测量。发现草酸是反应的流通中间体。用硫代巴比妥酸进行的独立定性测试证实了这一点。诱导期草酸浓度与溴丙二酸和二溴丙二酸中间体浓度一起增加。众所周知，BZ反应有两个负反馈回路：一个是溴化物，另一个是有机自由基。草酸和 CO2 是第二个循环的产物，其中有机自由基与 BrO2 自由基反应。为目前的实验研究选择诱导期是因为上述自由基 - 自由基反应在此期间最为强烈。基于实验结果，提出了激进反馈回路的机制建议。还开发了一种在 BZ 反应中积累以极低浓度存在的多价有机酸的方法。应用此和热分解方法，乙烯四羧酸（EETA）被鉴定为乙烷四羧酸（ETA）的氧化产物。
• Ce⁴⁺−Malonic Acid Reaction in the Presence of O₂. Reaction Channels Leading to Tartronic and Oxalic Acid Intermediates
  作者：László Hegedüs、Horst-Dieter Försterling、Mária Wittmann、Zoltán Noszticzius

  DOI：10.1021/jp001005l

  日期：2000.11.1

  The effect of oxygen on the Ce4+-malonic acid reaction was studied in a semibatch reactor. That effect is important for the Belousov-Zhabotinsky (BZ) chemical oscillator. The Ce4+ reagent inflow and consequently the rate of the reaction itself was controlled by a peristaltic pump. The reaction products were analyzed by HPLC. With this technique two major oxidation pathways were identified. One is significant at high Ce4+ inflow rates only; the product of this channel is tartronic acid. The other pathway leading to oxalic acid is active at all flow rates but dominant when the feed is slow. A great part of oxalic acid is oxidized further to carbon dioxide and water. A reaction mechanism compatible with these findings is presented. A key step of this mechanism is the fate of the peroxymalonyl radical which is the first intermediate for both channels. It is proposed that at high Ce4+ concentrations a fast reaction of this intermediate with Ce4+ leads to tartronic acid. At low Ce4+ concentrations. however, the peroxymalonyl radical has a longer lifetime to decarboxylate before reacting with a second Ce4+ and giving oxalic acid this way. Two mechanistic schemes proposed fur this low Ce4+ channel were tested with further HPLC and kinetic experiments. From the high and low Ce4+ channels it is only the low one which plays a significant role in oxygen-perturbed BZ systems, The effect of that channel and its intermediates on BZ oscillators is discussed briefly.
• HPLC Studies on the Photochemical Formation of Free Radicals from Malonic Acid
  作者：Istvan Szalai、Horst-Dieter Försterling、Zoltan Noszticzius

  DOI：10.1021/jp980448a

  日期：1998.4.1

  In the Belousov Zhabotinsky reaction, malonyl radicals formed during the oxidation of malonic acid by Ce(4+) play an important role in the mechanism of the negative feedback loop. In the past, we have analyzed the end products in the Ce(4+)-malonic acid reaction applying HPLC technique. For comparison, we generated malonyl radicals by UV irradiation of solutions of malonic acid and we identified the reaction products. Two of these are the same as in the Ce(4+)-malonic acid reaction, but some additional products are also formed. To explain our experimental results, a new reaction path is proposed where malonyl radicals and hydrogen atoms are the first intermediates in the photochemical decomposition of the malonic acid. Mechanistic differences between this photochemical decomposition and the Ce(4+)-malonic acid reaction are also discussed.
• HPLC Studies on the Organic Subset of the Oscillatory BZ Reaction. 2. Two Different Types of Malonyl Radicals in the Ce⁴⁺−Malonic Acid Reaction
  作者：Atchara Sirimungkala、Horst-Dieter Försterling、Zoltan Noszticzius

  DOI：10.1021/jp952492l

  日期：1996.1.1

  Applying combined HPLC and NMR techniques, it was found that, besides the already known 1,1,2,2-ethanetetracarboxylic acid (ETA), monomalonyl malonate (MAMA) is also a product of the Ce4+-malonic acid reaction. This is indirect evidence that two different types of organic radicals are formed in the reaction: the alkyl and the carboxylato malonyl radicals. While ETA is a recombination product of two alkyl radicals, MAMA is formed in the recombination of one alkyl and one carboxylato radical.
• The Importance of Mesomerism in the Termination ofα-Carboxymethyl Radicals from Aqueous Malonic and Acetic Acids
  作者：Wen-Feng Wang、Man Nien Schuchmann、Heinz-Peter Schuchmann、Clemens von Sonntag

  DOI：10.1002/1521-3765(20010216)7:4<791::aid-chem791>3.0.co;2-2

  日期：2001.2.16

  In the dioxygen-free aqueous malonic and acetic acid systems. alpha-carboxymethyl radicals are produced through hydrogen abstraction from the parent compound by radiolytically generated OH radicals. H abstraction from the CO2-/CO2H group followed by decarboxylation is a process of small importance (< or = 5%). The alpha-carboxymethyl radicals terminate by recombination. Two types of recombination product

  在无双氧的丙二酸和乙酸水溶液中。α-羧甲基自由基是通过辐射产生的OH自由基从母体化合物中提取氢而产生的。从CO2- / CO2H基团中脱除H并进行脱羧反应的重要性不高（<或= 5％）。α-羧甲基基团通过重组终止。观察到两种类型的重组产物，其特征在于形成CC键或CO键。α-羧甲基自由基是介观体系。它们的介观状态取决于质子化状态，并决定了它们所产生的CC连接脱CO二聚体与CO连接脱氢二聚体的比例。