oxalic dichloride | 79-37-8

• 物质功能分类: 化学农药原药 - 杀虫剂中间体
• 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 dichloride
• 英文别名: oxalyl chloride；Dichloro oxalate
• CAS: 79-37-8
• 化学式: C₂Cl₂O₄
• 分子量: 158.926
• InChiKey: VGUTVQSGZRAZED-UHFFFAOYSA-N

物化性质

• 熔点：
  -10--8 °C (lit.)
• 沸点：
  62-65 °C (lit.)
• 密度：
  1.5 g/mL at 20 °C (lit.)
• 蒸气密度：
  4.4 (vs air)
• 闪点：
  176-178°C
• 溶解度：
  氯仿（可溶）、乙酸乙酯
• 暴露限值：
  ACGIH: TWA 50 ppmOSHA: TWA 25 ppm; STEL 125 ppmNIOSH: IDLH 2300 ppm
• 介电常数：
  3.5（21℃）

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• TSCA：
  Yes
• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S23,S24/25,S26,S36/37/39,S43,S45,S8
• 危险类别码：
  R14,R40,R29,R23/24/25,R34
• WGK Germany：
  2
• 海关编码：
  2942000000
• 危险品运输编号：
  UN 2927 6.1/PG 2
• 危险类别：
  8
• RTECS号：
  KI2950000
• 包装等级：
  II
• 危险标志：
  GHS05,GHS06
• 危险性描述：
  H314,H331,H335
• 危险性防范说明：
  P261,P280,P305 + P351 + P338,P310

制备方法与用途

草酰氯

草酰氯是一种重要的合成中间体，在医药、农药和涂料等领域均有广泛应用。在医药方面，它用于合成抗生素；在农药工业中，则是合成超高效磺酰脲类除草剂苄黄隆及植物生长调节剂等的原料。

化学性质

草酰氯为无色发烟液体，熔点为-12℃，沸点63～64℃，相对密度1.488。它能溶于氯仿、甲苯、四氢呋喃和乙醚等有机溶剂中，并且与水或醇接触时会剧烈分解。

用途

草酰氯（又称乙二酰氯）主要用于农药的生产，是合成苯甲酰脲类杀虫剂氟铃脲和杀铃脲以及磺酰脲类除草剂如甲磺隆、苄嘧磺隆、吡嘧磺隆等的重要中间体。此外，它还广泛应用于医药领域作为合成抗生素的原料。

军事用途

通常情况下，草酰氯用作军事毒气，并且在有机合成中可用作氯化剂。

有机合成与工业应用

草酰氯主要用于合成有机氯化物和农药中间体。它也是磺酰脲类除草剂、杀虫剂及医药化学合成的重要原料。同时，在聚酰胺、化学冷光剂、液晶等化工行业中，草酰氯用作优质酰化剂。

分析试剂

草酰氯还用于有机合成的加氯剂，并作为分析试剂使用。

生产方法

草酰氯由无水草酸与五氯化磷反应制得。具体步骤为：将五氯化磷与无水草酸混合均匀后，加热至64℃左右，直至几乎不再释放氯化氢气体，所得粗品通过精馏处理即可得到高纯度的草酰氯。

反应信息

• 作为反应物：
  描述：

  叔丁基过氧化氢 、 oxalic dichloride 在 吡啶 作用下， 以 Petroleum ether 为溶剂， 反应 0.5h， 以45%的产率得到二-叔-丁基过氧草酸酯
  参考文献：
  名称：

  Oxidation of HMG‐CoA Reductase Inhibitors by tert‐Butoxyl and 1,1‐Diphenyl‐2‐picrylhydrazyl Radicals: Model Reactions for Predicting Oxidatively Sensitive Compounds During Preformulation

  摘要：

  Hydrogen atom abstraction rate constants for the reaction of tert-butoxyl and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical with the HMG-CoA reductase inhibitors lovastatin, simvastatin, and statins I-IV were measured. This series of diene-containing drugs is known to be prone to oxidation. The tert-butoxyl radical was generated by the thermolysis of di-tert-butylperoxyoxalate at 40 degreesC. A competitive kinetic method was used to determine the relative rate of hydrogen atom abstraction by tert-butoxyl radical to beta -scission. The absolute rate constants were calculated using the experimentally determined product ratios of t-butanol to acetone and the known rate of beta -scission of tert-butoxyl radical. The rate constants for the reaction with DPPN: radical were measured spectrophotometrically by monitoring the loss of DPPH radical as a function of substrate concentration. The rate constants correlate well with the structure of the molecules studied. These kinetic techniques allow for oxidatively sensitive compounds to be identified early in the drug development cycle. The tert-butoxyl radical, a strong hydrogen atom abstractor, is representative of the hydroxyl ( . OH) and alkoxyl ( . OR) radicals; in contrast the DPPH radical, a much weaker radical, is a good kinetic model for hydroperoxyl ( . OOH) and peroxyl ( . OOR) radicals. These kinetic methods can be used to quantitatively assess the lability of drug candidates towards reaction with oxygen-centered radicals at an early stage of development and facilitate the design of inhibiting strategies. (C) 2000 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 89:1518-1524, 2000.

  DOI：

  10.1002/1520-6017(200012)89:12<1518::aid-jps2>3.0.co;2-o
• 作为试剂：
  描述：

  环丙甲酸 、 5-amino-6-sulfanylpyrimidine-2,4-diol 在 oxalic dichloride 作用下， 反应 2.0h， 以53%的产率得到2-cyclopropyl-4H-[1,3]thiazolo[5,4-d]pyrimidine-5,7-dione
  参考文献：
  名称：

  [EN] IRAK INHIBITORS AND USES THEREOF
  [FR] INHIBITEURS D'IRAK ET LEURS UTILISATION

  摘要：

  本发明提供了化合物、其组合物以及使用它们的方法。

  公开号：

  WO2015048281A1

文献信息

• Steiner, Norbert; Nagel, Ulrich; Beck, Wolfgang, Chemische Berichte, 1988, vol. 121, p. 1759 - 1766
  作者：Steiner, Norbert、Nagel, Ulrich、Beck, Wolfgang

  DOI：——

  日期：——
• Oxidation of HMG‐CoA Reductase Inhibitors by tert‐Butoxyl and 1,1‐Diphenyl‐2‐picrylhydrazyl Radicals: Model Reactions for Predicting Oxidatively Sensitive Compounds During Preformulation
  作者：Shyam B. Karki、Varaporn Treemaneekarn、Michael J. Kaufman

  DOI：10.1002/1520-6017(200012)89:12<1518::aid-jps2>3.0.co;2-o

  日期：2000.12

  Hydrogen atom abstraction rate constants for the reaction of tert-butoxyl and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical with the HMG-CoA reductase inhibitors lovastatin, simvastatin, and statins I-IV were measured. This series of diene-containing drugs is known to be prone to oxidation. The tert-butoxyl radical was generated by the thermolysis of di-tert-butylperoxyoxalate at 40 degreesC. A competitive kinetic method was used to determine the relative rate of hydrogen atom abstraction by tert-butoxyl radical to beta -scission. The absolute rate constants were calculated using the experimentally determined product ratios of t-butanol to acetone and the known rate of beta -scission of tert-butoxyl radical. The rate constants for the reaction with DPPN: radical were measured spectrophotometrically by monitoring the loss of DPPH radical as a function of substrate concentration. The rate constants correlate well with the structure of the molecules studied. These kinetic techniques allow for oxidatively sensitive compounds to be identified early in the drug development cycle. The tert-butoxyl radical, a strong hydrogen atom abstractor, is representative of the hydroxyl ( . OH) and alkoxyl ( . OR) radicals; in contrast the DPPH radical, a much weaker radical, is a good kinetic model for hydroperoxyl ( . OOH) and peroxyl ( . OOR) radicals. These kinetic methods can be used to quantitatively assess the lability of drug candidates towards reaction with oxygen-centered radicals at an early stage of development and facilitate the design of inhibiting strategies. (C) 2000 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 89:1518-1524, 2000.