3-ethyl-isoxazole-4,5-dicarboxylic acid dimethyl ester | 53847-50-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3-ethyl-isoxazole-4,5-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 3-ethyl-1,2-oxazole-4,5-dicarboxylate
• CAS: 53847-50-0
• 化学式: C₉H₁₁NO₅
• 分子量: 213.19
• InChiKey: SWQXBIWFQCLEGG-UHFFFAOYSA-N

物化性质

• 沸点：
  120-128 °C(Press: 6 Torr)
• 密度：
  1.224±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  78.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-ethyl-isoxazole-4,5-dicarboxylic acid dimethyl ester 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 5-tert-butylcarbamoyl-3-ethyl-isoxazole-4-carboxylic acid
  参考文献：
  名称：

  Synthesis and herbicidal activity of isoxazoledicarboxylic acid derivatives

  摘要：

  AbstractStarting from bulk chemicals, novel isoxazoledicarboxylic acid esters were prepared and converted to the corresponding dicarboxylic acid mono‐amides in a few reaction steps and in high overall yields. Key intermediates for the cycloaddition step were chlorooximinoacetates or amides as nitrile oxide equivalents, prepared in one‐pot reactions from diketene or acetoacetic acid esters. Isoxazoledicarboxylic acid monoamides combined good herbicidal activity with chemical flexibility. They were characterized as inhibitors of photosynthesis. Particularly, they affected the photosynthetic electron transport in photosystem II and the rate of carbon dioxide assimilation. Applied post‐emergence, the new compounds were found to control a broad spectrum of key weeds in corn. Excellent activity was found on Abutilon theophrasti (L.) Medik., Amaranthus retroflexus L., Chenopodium album L., Ipomoea spp., Polygonum persicaria L., Solanum nigrum L. and Xanthium strumarium L. with rates between 0.2 and 0.5 kg ha−1. As a side‐effect, the compounds also showed activity against grass weeds. The compounds are excellent tank‐mix partners, e.g. for sulfonyl‐ureas, to complete the weed spectrum (Chenopodium album L., Solanum nigrum L.) and/or to reduce the risk of developing herbicide‐resistant weeds.

  DOI：

  10.1002/ps.2780440104
• 作为产物：
  描述：

  propionaldehyde oxime 、 丁炔二酸二甲酯 在 sodium hypochlorite 作用下， 生成 3-ethyl-isoxazole-4,5-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Synthesis and herbicidal activity of isoxazoledicarboxylic acid derivatives

  摘要：

  AbstractStarting from bulk chemicals, novel isoxazoledicarboxylic acid esters were prepared and converted to the corresponding dicarboxylic acid mono‐amides in a few reaction steps and in high overall yields. Key intermediates for the cycloaddition step were chlorooximinoacetates or amides as nitrile oxide equivalents, prepared in one‐pot reactions from diketene or acetoacetic acid esters. Isoxazoledicarboxylic acid monoamides combined good herbicidal activity with chemical flexibility. They were characterized as inhibitors of photosynthesis. Particularly, they affected the photosynthetic electron transport in photosystem II and the rate of carbon dioxide assimilation. Applied post‐emergence, the new compounds were found to control a broad spectrum of key weeds in corn. Excellent activity was found on Abutilon theophrasti (L.) Medik., Amaranthus retroflexus L., Chenopodium album L., Ipomoea spp., Polygonum persicaria L., Solanum nigrum L. and Xanthium strumarium L. with rates between 0.2 and 0.5 kg ha−1. As a side‐effect, the compounds also showed activity against grass weeds. The compounds are excellent tank‐mix partners, e.g. for sulfonyl‐ureas, to complete the weed spectrum (Chenopodium album L., Solanum nigrum L.) and/or to reduce the risk of developing herbicide‐resistant weeds.

  DOI：

  10.1002/ps.2780440104

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。
• The Reaction of Primary Nitro Compounds with Dipolarophiles in the Presence of<i>p</i>-Toluenesulfonic Acid
  作者：Tomio Shimizu、Yoshiyuki Hayashi、Kazuhiro Teramura

  DOI：10.1246/bcsj.57.2531

  日期：1984.9

  were obtained from the reaction of primary nitro compounds [methyl nitroacetate, 2-nitro-1-phenylethanone, (nitromethyl)benzene, 1-nitropropane, and (phenylsulfonyl)nitromethane] with dipolarophiles in refluxing mesitylene in the presence of a small amount of p-toluenesulfonic acid. The formation of these products can be explained in terms of 1,3-dipolar cycloaddition of nitrile oxide generated by a

  3-取代的 2-异恶唑啉或异恶唑是从初级硝基化合物 [硝基乙酸甲酯、2-硝基-1-苯基乙酮、（硝基甲基）苯、1-硝基丙烷和（苯磺酰基）硝基甲烷]与偶极体在回流的均三甲苯中反应获得的存在少量对甲苯磺酸。这些产物的形成可以通过初级硝基化合物脱水产生的腈氧化物的 1,3-偶极环加成来解释。另一方面，4,5-十亚甲基-3-苯基磺酰基-2-异恶唑啉N-氧化物是从（苯基磺酰基）硝基甲烷与环十二烯的类似反应中获得的。异恶唑啉N-氧化物的形成可以基于3,4-双(苯基磺酰基)呋喃2-氧化物的中间体来解释。
• An investigation of the reaction of primary nitroalkanes with acetic anhydride/sodium acetate
  作者：A. McKillop、R.J. Kobylecki

  DOI：10.1016/s0040-4020(01)97248-5

  日期：1974.1

  Oxidation of primary nitroalkanes by acetic anhydride/sodium acetate has been found to be more complex than previously suspected. Phenylnitromethane, with acetic anhydride/sodium acetate at 60–80°, for example, gives a mixture of benzoic anhydride, triacethylhydroxylamine and acetanilide, through the mixed anhydride as a key intermediate. Evidence in support of this latter species has been obtained

  已发现用乙酸酐/乙酸钠氧化伯硝基链烷比以前怀疑的要复杂。例如，苯硝基甲烷与乙酸酐/乙酸钠在60-80°时通过混合酸酐作为关键中间体，可得到苯甲酸酐，三乙羟胺和乙酰苯胺的混合物。当以82％的收率形成3-苯基-4,5-二苯甲氧基异恶唑时，在乙炔二羧酸二甲酯作为1,3-双极性亲和剂的存在下进行氧化，获得了支持后一种物质的证据。已经以类似的方式制备了许多其他的3-烷基-和3-芳基-4，5-二芳基甲氧基异恶唑。
• Regioselective Addition of Grignard Reagents to Isoxazole-4,5-dicarboxylate Esters
  作者：Kevin J. Batchelor、W. Russell Bowman、Roy V. Davies、Michael H. Hockley、David J. Wilkins

  DOI：10.1039/a902259g

  日期：——

  Regioselective mono-addition of a range of Grignard reagents with the 5-esters of 3-methylisoxazole-4,5-diesters affords 5-keto derivatives instead of tertiary alcohols which is explained by the complexing ability of the isoxazole oxygen atom and by the electron withdrawing effect of the isoxazole ring.

  一系列格氏试剂与 3-甲基异恶唑-4,5-二酯的 5-酯的区域选择性单加成得到 5-酮衍生物而不是叔醇，这是由异恶唑氧原子和电子的络合能力解释的异恶唑环的撤消作用。
• SHIMIZU, TOMIO;HAYASHI, YOSHIYUKI;TERAMURA, KAZUHIRO, BULL. CHEM. SOC. JAP., 1984, 57, N 9, 2531-2534
  作者：SHIMIZU, TOMIO、HAYASHI, YOSHIYUKI、TERAMURA, KAZUHIRO

  DOI：——

  日期：——