ethyl 4-(chloromethyl)-2-(bromomethyl)-5-isobutylfuran-3-carboxylate | 667866-86-6

• 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 4-(chloromethyl)-2-(bromomethyl)-5-isobutylfuran-3-carboxylate
• 英文别名: Ethyl 4-(chloromethyl)-2-(bromomethyl)-5-i-butylfuran-3-carboxylate；ethyl 2-(bromomethyl)-4-(chloromethyl)-5-(2-methylpropyl)furan-3-carboxylate
• CAS: 667866-86-6
• 化学式: C₁₃H₁₈BrClO₃
• 分子量: 337.641
• InChiKey: DXJCZFQVCYEJCJ-UHFFFAOYSA-N

物化性质

• 沸点：
  406.7±45.0 °C(Predicted)
• 密度：
  1.350±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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 4-(chloromethyl)-2-(bromomethyl)-5-isobutylfuran-3-carboxylate 、 三甲氧基磷 生成 4-Chloromethyl-2-methyl-5-(2-methyl-propenyl)-furan-3-carboxylic acid ethyl ester 、 ethyl 4-(chloromethyl)-5-isobutyl-2-methylfuran-3-carboxylate 、 4-(Dimethoxy-phosphorylmethyl)-5-isobutyl-2-methyl-furan-3-carboxylic acid ethyl ester 、 4-(Dimethoxy-phosphorylmethyl)-2-methyl-5-(2-methyl-propenyl)-furan-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  摘要：

  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.

  DOI：

  10.1023/a:1024700307233
• 作为产物：
  描述：

  ethyl 4-(chloromethyl)-5-isobutyl-2-methylfuran-3-carboxylate 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 2.5h， 以4.5 g的产率得到ethyl 4-(chloromethyl)-2-(bromomethyl)-5-isobutylfuran-3-carboxylate
  参考文献：
  名称：

  摘要：

  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.

  DOI：

  10.1023/a:1024700307233