ethyl 2-methyl-4-chloromethyl-5-tert-butylfuran-3-carboxylate | 502990-73-0

• 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 2-methyl-4-chloromethyl-5-tert-butylfuran-3-carboxylate
• 英文别名: Ethyl 5-t-butyl-4-(chloromethyl)-2-methylfuran-3-carboxylate；ethyl 5-tert-butyl-4-(chloromethyl)-2-methylfuran-3-carboxylate
• CAS: 502990-73-0
• 化学式: C₁₃H₁₉ClO₃
• 分子量: 258.745
• InChiKey: DEKXEQPDFCUAFR-UHFFFAOYSA-N

物化性质

• 沸点：
  327.8±42.0 °C(Predicted)
• 密度：
  1.090±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  5
• 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 2-methyl-4-chloromethyl-5-tert-butylfuran-3-carboxylate 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 sodium ethanolate 作用下， 以 四氯化碳 为溶剂， 反应 14.0h， 生成 ethyl 2-(bromomethyl)-5-tert-butyl-4-(phenoxymethyl)furan-3-carboxylate
  参考文献：
  名称：

  摘要：

  Ethyl 5-tert-butyl-4-(chloromethyl)-2-methylfuran-3-carboxylate was brominated with N-bromo-succinimide to obtain the corresponding 2-bromomethyl derivative. The latter is selectively phosphorylated with trimethyl and triethyl phosphites by the bromomethyl group. The resulting [4-(chloromethyl)furyl]methyl-phosphonates in the presence of secondary amines and sodium butanethiolate behave as alkylating agents, while sodium phenolate causes their decomposition. 4-Acetoxymethyl- and 4-phenoxymethyl derivatives of the starting product are also selectively brominated with N-bromosuccinimide by the 2-methyl group. The first of the 2-(bromomethyl)furans formed is smoothly phosphorylated with trimethyl phosphite, while the second one under the action of triethyl phosphite gives a mixture of phosphorylation and debromination products. In all the cases, an additional electron-acceptor group in position 4 of alkyl 2-(bromomethyl)-5-tert-butylfuran-3-carboxylate considerably accelerates the Arbuzov reaction.

  DOI：

  10.1023/a:1024962020862
• 作为产物：
  描述：

  聚合甲醛 、 2-methyl-5-(tert-butyl)furan-3-carboxylic acid ethyl ester 在 盐酸 、 zinc(II) chloride 作用下， 以 氯仿 为溶剂， 反应 3.0h， 以61%的产率得到ethyl 2-methyl-4-chloromethyl-5-tert-butylfuran-3-carboxylate
  参考文献：
  名称：

  摘要：

  3-Ethoxycarbonyl- and 3-acetyl-2-methyl-5-tert-butylfurans undergo chloromethylation under the unusually rigorous conditions (55-60degreesC, 3-3.5 h). The corresponding diethylamide and nitrite were prepared by standard modification of the carboxy group. In phosphorylation of the resulting chloromethylfurans under the conditions of the Michaelis-Becker reaction, in the case of the ester and diethylamide, the phosphonate yields were close to those obtained with compounds containing no tert-butoxy group, and in the case of acetylfuran the yield was even somewhat higher. On the contrary, the chloromethylated nitrite reacts considerably more slowly than all the other compounds under consideration and than the similar compound containing no tert-butyl substituent. Thus,,the effect of the tert-butyl group in the a-position of the furan ring is clearly pronounced in the electrophilic substitutions in the neighboring position of the heteroring. When the reaction center is located in the side chain (substitution of chlorine), the effect of the bulky substituent is manifested only in special cases and can be attributed to the presence of a conformation in which the chloromethyl group is shielded.

  DOI：

  10.1023/a:1020750715942

文献信息

• ——
  作者：L. M. Pevzner

  DOI：10.1023/a:1021605324604

  日期：——

  Reduction of 2- and 4-acetoxymethyl derivatives of 5-tert-butylfuran-3-carboxylic acid leads to the corresponding bis(hydroxymethyl)furans. Bis(chloromethyl)furans prepared from the latter were involved in reaction with sodium diethyl phosphite. In the presence of two equivalents of a phosphorus-containing nucleophile, bis(phosphonomethyl)furans are formed. One equivalent of sodium diethyl phosphite reacts with 3,4-bis(chloromethyl)furan to give a mixture of 3-and 4-phosphorylated products in a 4.5:1 ratio in a low yield. The revealed difference in reactivity between the 3- and 4-chloromethyl groups demonstrates the importance of shielding of the chloromethyl group by the neighboring tert-butyl substituent. Examination of the H-1 NMR spectra of 3,4-bis(hydroxymethyl)-, 3,4-bis(chloromethyl)-, 3,4-bis(diethoxyphosphorylmethyl)5-tert-butylfurans, and also specially prepared 5-tert-butyl-3-(diethoxyphosphorylmethyl)-4-(ethoxymethyl)-2-methylfuran established that the signal of the substituent neighboring to the tert-butyl group is always shifted downfield.