oxalic monoperacid | 90350-91-7

• 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: oxalic monoperacid
• 英文别名: Peroxyoxalsaure；2-hydroperoxy-2-oxoacetic acid
• CAS: 90350-91-7
• 化学式: C₂H₂O₅
• 分子量: 106.035
• InChiKey: SQERDRRMCKKWIL-UHFFFAOYSA-N

物化性质

• 沸点：
  326.9±25.0 °C(Predicted)
• 密度：
  1.854±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  83.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  中草酸 在 甲酸 、 氧气 、 一氧化二氮 作用下， 生成 二氧化碳 、 oxalic monoperacid
  参考文献：
  名称：

  O2.cntdot.- Addition to ketomalonate leads to decarboxylation: a chain reaction in oxygenated aqueous solution

  摘要：

  Superoxide radical anion, O2.-, was generated radiolytically in oxygenated aqueous formate solutions. In its reaction with ketomalonate ion, oxalic monoperacid and carbon dioxide are formed via a chain reaction. The chain length increases linearly with (dose rate)-1/2, i.e. (rate of O2.- generation)-1/2, as well as ketomalonate concentration. Typically, at a dose rate of 0.055 Gy s-1 and a ketomalonate concentration of 8 X 10(-3) mol dm-3 at pH 10 (formate concentration 0.1 mol dm-3), G(CO2) = 150 X 10(-7) mol J-1 is found. It is suggested that the propagation steps of this unexpected chain reaction are addition of O2.- to the keto group of the ketomalonate ion, followed by fragmentation of this adduct into oxalic monoperacid and CO2.-, the latter reducing O2 and so regenerating O2.-. A propagation rate constant of about 150 dm3 mol-1 s-1 has been estimated.

  DOI：

  10.1021/ja00018a033

文献信息

• Oxidation of Hydroxymalonic Acid by OH Radicals in the Presence and in the Absence of Molecular Oxygen. A Pulse-Radiolysis and Product Study
  作者：Man Nien Schuchmann、Heinz-Peter Schuchmann、Clemens von Sonntag

  DOI：10.1021/j100022a026

  日期：1995.6

  The rate constants of the reaction of (OH)-O-./O-.- with hydroxymalonic acid (1) have been determined at various pH, the OH radical being generated pulse-radiolytically. This reaction involves the abstraction of an H atom at C(2), i.e., the formation of the alpha-hydroxyalkyl radical (2), and is fastest in the pH range from 6 to 10 (k = 4.4 x 10(8) dm(3) mol(-1) s(-1)) where hydroxymalonic acid exists as the dianion. The pK(a) values of the carboxyl functions of radical 2 have been found to be 1.9 and 4.8, similar to, or slightly higher than, those of the parent compound (1.89 and 4.28 at 25 degrees C). However, the pK(a) of the alcohol function of radical 2 (found to be 12.9) is several units lower than that of the parent compound. In the presence of oxygen, radical 2 is rapidly converted into the corresponding peroxyl radical 3 (k = 1.6 x 10(9) dm(3) mol(-1) s(-1)). The alpha-hydroxyperoxy radical (3) eliminates HO2. with a rate constant of 1.1 x 10(4) s(-1) to give ketomalonic acid. In the alkoxide form, peroxyl radical 3 eliminates O-2(.-) faster (8.9 x 10(4) s(-1)). The pK(a) of the alcohol function in 3 has been estimated at 9.8, much lower than that of radical 2. In the gamma-radiolysis of hydroxymalonic acid in N2O/O-2-saturated solutions, product ratios change with pH. At pH 3, the main products (4:1 v/v) are ketomalonic acid (G = 5.1 x 10(-7) mol J(-1)) and hydrogen peroxide. At pH 10 oxalic monoperacid and carbon dioxide become major products. These products are formed in a (slow) chain reaction involving ketomalonic acid and the superoxide radical. Ketomalonic acid also reacts with the product hydrogen peroxide (k = 5 x 10(-3) dm(3) mol(-1) s(-1)), yielding peroxides which, depending on pH, can be present in different states of protonation.