trimethyl isoxazole-3,4,5-tricarboxylate | 69337-37-7

• 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: trimethyl isoxazole-3,4,5-tricarboxylate
• 英文别名: Trimethyl 1,2-oxazole-3,4,5-tricarboxylate
• CAS: 69337-37-7
• 化学式: C₉H₉NO₇
• 分子量: 243.173
• InChiKey: AZHRTWKSKCMPAX-UHFFFAOYSA-N

物化性质

• 熔点：
  101-102 °C
• 沸点：
  297.6±35.0 °C(Predicted)
• 密度：
  1.357±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  丁炔二酸二甲酯 在 copper(II) nitrate trihydrate 作用下， 以 乙腈 为溶剂， 以35 %的产率得到trimethyl isoxazole-3,4,5-tricarboxylate
  参考文献：
  名称：

  硝酸铜介导的炔烃选择性键断裂：异恶唑的多样化合成†

  摘要：

  一种前所未有的硝酸铜介导的炔烃键断裂被开发用于异恶唑的模块化合成，其中CS键或C=C三键被选择性断裂。连接到 C=C 三键上的取代基可以不同地区分化学键断裂和反应途径。产品的各种转变说明了给定协议的有前景的应用。

  DOI：

  10.1002/cjoc.202300431

文献信息

• A Convenient Preparative Method of Nitrile Oxides by the Dehydration of Primary Nitro Compounds with Ethyl Chloroformate or Benzenesulfonyl Chloride in the Presence of Triethylamine
  作者：Tomio Shimizu、Yoshiyuki Hayashi、Hiroshi Shibafuchi、Kazuhiro Teramura

  DOI：10.1246/bcsj.59.2827

  日期：1986.9

  nitrile oxides (MeOCOC≡N→O, PhC≡N→O, and EtC≡N→O) were effectively generated in situ by dehydration of the corresponding primary nitro compounds (RCH2NO2) with PhSO2Cl or ClCOOEt in the presence of triethylamine. Various cycloadducts were prepared by the reaction of them with dipolarophiles. Some advantages of these methods are described in comparison with other known methods.

  在三乙胺的存在下，通过用 PhSO2Cl 或 ClCOOEt 使相应的初级硝基化合物 (RCH2NO2) 脱水，原位有效地生成了三种腈氧化物（MeOCOC≡N→O、PhC≡N→O 和 EtC≡N→O）。各种环加合物是通过它们与偶极试剂反应制备的。与其他已知方法相比，描述了这些方法的一些优点。
• A New Synthetic Method of Alkyl Carbonocyanidate<i>N</i>-Oxides
  作者：Tomio Shimizu、Yoshiyuki Hayashi、Kazuhiro Teramura

  DOI：10.1246/bcsj.58.2519

  日期：1985.9

  A thermal decomposition of dimethyl nitromalonate to bis(carbomethoxy)furoxan was observed at about 170 °C. In the presence of dipolarophiles, an intermediate, methyl carbonocyanidate N-oxide MeOCOC≡N→O, could be trapped as cycloadducts in good yields by the 1,3-dipolar cycloaddition. Treatment of dimethyl nitromalonate in mesitylene at the refluxing temperature resulted in a formation of methyl 2-(hydroxyimino)-2-(2,4,6-trimethylphenyl)acetate.

  在约170°C下，观察到了二甲基硝基丙二酸酯的热分解反应，生成了双(羧甲酯)呋喃唑烷。在存在偶极亲电试剂的情况下，可以通过1,3-偶极环加成反应以良好产率捕获作为环加合物的中间体，即甲基碳二腈N-氧化物MeOCOC≡N→O。将二甲基硝基丙二酸酯在均三甲苯中回流处理，导致了甲基2-(羟基亚氨基)-2-(2,4,6-三甲基苯基)乙酸酯的形成。
• Synthesis of five-membered heterocycles containing a nitrogen-oxygen bond via O-acylation of aliphatic nitro compounds.
  作者：KAZUHO HARADA、EISUKE KAJI、SHONOSUKE ZEN

  DOI：10.1248/cpb.28.3296

  日期：——

  O-Acylation of primary aliphatic nitro compounds with acid chlorides in N, N-dimethylacetamide led to the formation of nitrile oxides, which cyclized in situ with olefinic dipolarophiles in a 1, 3-dipolar cycloaddition mode to afford 2-isoxazoline derivatives. Optimum reaction conditions were investigated, and the use of several types of dipolarophiles, such as acetylenes, Schiff bases, aromatic nitriles, and ketones, in this cycloaddition resulted in the formation of the corresponding cycloadducts, namely isoxazoles, 1, 2, 4-oxadiazolines, 1, 2, 4-oxadiazoles, and 1, 4, 2-dioxazoles, respectively, in reasonable yields.

  初级脂肪族硝基化合物与酸氯化物在N,N-二甲基乙酰胺中进行O-酰化反应，形成了腈氧化物，这些腈氧化物与烯烃类双极试剂在1,3-双极环加成模式下原位环化，生成了2-异噁唑啉衍生物。研究了最佳反应条件，使用多种类型的双极试剂，如炔烃、施夫碱、芳香族腈和酮类，进行这一环加成反应，分别合理产率地生成了相应的环加成产物，即异噁唑、1,2,4-噁二唑啉、1,2,4-噁二唑以及1,4,2-二噁唑。
• Synthesis of isoxazole derivatives by means of O-acylation of aliphatic nitro compounds in the presence of acetylenic compounds.
  作者：EISUKE KAJI、KAZUHO HARADA、SHONOSUKE ZEN

  DOI：10.1248/cpb.26.3254

  日期：——

  O-Acylation of some aliphatic nitro compounds or their alkali metal salts with acid chlorides in N, N-dimethylacetamide in the presence of acetylenic compounds afforded isoxazole derivatives in fairly good yield. The reaction is shown to arise from 1, 3-dipolar cycloaddition of acetylenic compounds to the nitrile oxide intermediates which would resulted from the fragmentation of the initially formed O-acylated product.

  一些脂肪族硝基化合物或其碱金属盐在N,N-二甲基乙酰胺中与酸氯化物和炔烃化合物反应，进行了O-酰化，获得了相当好的产率的异噁唑衍生物。该反应被证明是由于炔烃化合物与由最初形成的O-酰化产品裂解生成的腈氧化物中间体之间的1,3-偶极环加成反应所引起的。
• A synthesis of isoxazoles through the reaction of activated acetylenes and alkyl 2-nitroethanoates in the presence of triphenylphosphine
  作者：Issa Yavari、Loghman Moradi

  DOI：10.1016/j.tetlet.2005.12.112

  日期：2006.3

  The reaction of dialkyl acetylenedicarboxylates or dibenzoylacetylene with alkyl 2-nitroethanoates in the presence of triphenylphosphine leads to functionalized isoxazoles in good yields.

  在三苯基膦的存在下，乙炔二羧酸二烷基酯或二苯甲酰基乙炔与2-硝基乙酸烷基酯的反应以良好的收率得到官能化的异恶唑。