ethyl 5-isobutyl-2-methylfuran-3-carboxylate | 667866-77-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 英文名称: ethyl 5-isobutyl-2-methylfuran-3-carboxylate
• 英文别名: 3-Furancarboxylic acid, 2-methyl-5-(2-methylpropyl)-, ethyl ester；ethyl 2-methyl-5-(2-methylpropyl)furan-3-carboxylate
• CAS: 667866-77-5
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: QCAOPDLGNRCQCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  39.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 5-isobutyl-2-methylfuran-3-carboxylate 在 吡啶 、 lithium aluminium tetrahydride 、 氯化亚砜 作用下， 以 乙醚 、 苯 为溶剂， 反应 18.0h， 生成 5-isobutyl-2-methyl-3-(diethoxyphosphinoylmethyl)furan
  参考文献：
  名称：

  Specific Features of Reactions of Halomethyl Derivatives of 2-Isobutylfuran with Nucleophiles

  摘要：

  3,4-和3,5-双(氯甲基)-2-异丁基呋喃与亚磷酸二乙酯钠通过Michaelis-Becker反应方案反应形成膦酸酯，其产率很大程度上取决于呋喃环中卤甲基的位置。 3,4-双(氯甲基)-2-异丁基-5-甲基呋喃在类似条件下产生二膦酸酯，而在3,5-双(氯甲基)-2-异丁基呋喃中，α-氯甲基的磷酸化与脱氯化氢竞争，导致氯甲基化烯烃，优选第二种方法。进一步的磷酸化仅涉及烯烃的一个氯甲基。 5-(溴甲基)-2-异丁基呋喃-3-甲酸乙酯与乙酸钠反应生成取代产物，而其取代基位置相反的异构体仅消除溴化氢。在后一种情况下，乙酸盐仅作为次要产物形成。

  DOI：

  10.1007/s11176-005-0348-1

文献信息

• ——
  作者：L. M. Pevzner

  DOI：10.1023/a:1024700307233

  日期：——

  Ethyl 5-isobutyl-2-methylfuran-3-carboxylate is selectively brominated with N-bromosuccin-imide by the methyl group to give an unstable bromide. The latter on heating or in the presence of bases undergoes dehydrobromination accompanied by rearrangement, leading to a (2,2-dimethylvinyl)furan derivative. Phosphorylation of this bromide with trimethyl phosphite gives a 2-dimethoxyphosphorylmethyl derivative and a product containing the phosphonate group alpha to the isobutyl radical. Chloromethylation of the starting ester proceeds in the 4 position of the furan ring. The resulting chloride undergoes phosphorylation under conditions of the Michaelis-Becker reaction to give the corresponding 4-(dialkoxyphosphorylmethyl)furan, and under the action of trimethyl phosphite a mixture of the same phosphonate and a dehalogenation product having a dimethylvinyl fragment. Bromination of the 4-chloromethyl derivative with N-bromosuccinimide involves the 2-methyl group. The dihalide reacts with trimethyl phosphite by way of reduction of the bromomethyl group to give 4-chloromethyl- or 4-dimethoxyphosphorylmethyl derivatives, as well as analogous dehydrohalogenation products containing a 5-dimethylvinyl fragment. A scheme describing the sequence of formation of these products in the course of the reaction is offered.
• Specific Features of Reactions of Halomethyl Derivatives of 2-Isobutylfuran with Nucleophiles
  作者：L. M. Pevzner

  DOI：10.1007/s11176-005-0348-1

  日期：2005.6

  3,4- and 3,5-bis(chloromethyl)-2-isobutylfurans react with sodium diethyl phosphite by the Michaelis-Becker reaction scheme to form phosphonates whose yield significantly depends on the location of the halomethyl group in the furan ring. 3,4-Bis(chloromethyl)-2-isobutyl-5-methylfuran under analogous conditions gives a diphosphonate, while in 3,5-bis(chloromethyl)-2-isobutylfuran phosphorylation of the α-chloromethyl group competes with dehydrochlorination leading to a chloromethylated alkene, the second process being preferred. Further phosphorylation involves only one chloromethyl group of the alkene. Ethyl 5-(bromomethyl)-2-isobutylfuran-3-carboxylate reacts with sodium acetate to give a substitution product, while its isomer with the reverse location of the substituents eliminates hydrogen bromide exclusively. In the latter case, the acetate is formed only as a minor product.

  3,4-和3,5-双(氯甲基)-2-异丁基呋喃与亚磷酸二乙酯钠通过Michaelis-Becker反应方案反应形成膦酸酯，其产率很大程度上取决于呋喃环中卤甲基的位置。 3,4-双(氯甲基)-2-异丁基-5-甲基呋喃在类似条件下产生二膦酸酯，而在3,5-双(氯甲基)-2-异丁基呋喃中，α-氯甲基的磷酸化与脱氯化氢竞争，导致氯甲基化烯烃，优选第二种方法。进一步的磷酸化仅涉及烯烃的一个氯甲基。 5-(溴甲基)-2-异丁基呋喃-3-甲酸乙酯与乙酸钠反应生成取代产物，而其取代基位置相反的异构体仅消除溴化氢。在后一种情况下，乙酸盐仅作为次要产物形成。