methyl 3-[3-(benzyloxy)-2-hydroxypropyl]but-3-enoate | 1149615-04-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 3-[3-(benzyloxy)-2-hydroxypropyl]but-3-enoate
• 英文别名: Methyl 3-[3-(benzyloxy)-2-hydroxypropyl]but-3-enoate；methyl 5-hydroxy-3-methylidene-6-phenylmethoxyhexanoate
• CAS: 1149615-04-2
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: QBCXNSNVXPIDMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  methyl 3-(bromomethyl)but-3-enoate 、 苄氧基乙醛 在 氯化铵 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 以73%的产率得到methyl 3-[3-(benzyloxy)-2-hydroxypropyl]but-3-enoate
  参考文献：
  名称：

  Synthesis of methyl 3-bromomethylbut-3-enoate and its reactions with aldehydes and tributylchlorostannane in the presence of zinc

  摘要：

  Methyl 3-bromomethylbut-3-enoate smoothly reacted with prenal, beta-ionylideneacetaldehyde, benzyloxyacetaldehyde, and tributylchlorostannane in the presence of zinc and aqueous ammonium chloride in tetrahydrofuran to give the corresponding delta-hydroxy-beta-methylidenecarboxylic acid esters. In the absence of ammonium chloride, satisfactory yields of the products were obtained only in the reactions with prenal and benzyloxyacetaldehyde; these reactions involved lactonization of intermediate delta-hydroxy-beta-methylidenecarboxylic acid esters, and the double carbon-carbon bond migrated to the conjugated position with the lactone carbonyl group. The condensation of beta-ionylideneacetaldehyde with methyl 3-bromomethylbut-3-enoate was successfully used to obtain isotretinoin. Initial methyl 3-bromomethylbut-3-enoate was synthesized in a good yield from readily accessible ethyl 3,3-diethoxypropionate via cyclopropanation with ethylmagnesium bromide in the presence of titanium tetra(isopropoxide), oxidation of the acetal moiety to ester, and cleavage of the cyclopropane ring in intermediate methyl (1-methylsulfonyloxycyclopropyl)acetate.

  DOI：

  10.1134/s1070428008090029

文献信息

• Synthesis of methyl 3-bromomethylbut-3-enoate and its reactions with aldehydes and tributylchlorostannane in the presence of zinc
  作者：I. V. Mineeva、O. G. Kulinkovich

  DOI：10.1134/s1070428008090029

  日期：2008.9

  Methyl 3-bromomethylbut-3-enoate smoothly reacted with prenal, beta-ionylideneacetaldehyde, benzyloxyacetaldehyde, and tributylchlorostannane in the presence of zinc and aqueous ammonium chloride in tetrahydrofuran to give the corresponding delta-hydroxy-beta-methylidenecarboxylic acid esters. In the absence of ammonium chloride, satisfactory yields of the products were obtained only in the reactions with prenal and benzyloxyacetaldehyde; these reactions involved lactonization of intermediate delta-hydroxy-beta-methylidenecarboxylic acid esters, and the double carbon-carbon bond migrated to the conjugated position with the lactone carbonyl group. The condensation of beta-ionylideneacetaldehyde with methyl 3-bromomethylbut-3-enoate was successfully used to obtain isotretinoin. Initial methyl 3-bromomethylbut-3-enoate was synthesized in a good yield from readily accessible ethyl 3,3-diethoxypropionate via cyclopropanation with ethylmagnesium bromide in the presence of titanium tetra(isopropoxide), oxidation of the acetal moiety to ester, and cleavage of the cyclopropane ring in intermediate methyl (1-methylsulfonyloxycyclopropyl)acetate.