methyl (6E,8E)-5-hydroxy-7-methyl-3-methylidene-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-6,8-dienoate | 1149615-01-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (6E,8E)-5-hydroxy-7-methyl-3-methylidene-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-6,8-dienoate
• CAS: 1149615-01-9
• 化学式: C₂₁H₃₂O₃
• 分子量: 332.483
• InChiKey: LNRQLXFSBVZARW-MKQCFFQWSA-N

物化性质

• 沸点：
  449.1±45.0 °C(predicted)
• 密度：
  1.012±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  24.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl (6E,8E)-5-hydroxy-7-methyl-3-methylidene-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-6,8-dienoate 在 sodium carbonate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以76%的产率得到4-methyl-6-[(1E,3E)-2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)buta-1,3-dien-1-yl]-5,6-dihydro-2H-pyran-2-one
  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
• 作为产物：
  描述：

  (7E,9E)-beta-离子亚基乙醛 、 methyl 3-(bromomethyl)but-3-enoate 在 氯化铵 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 以75%的产率得到methyl (6E,8E)-5-hydroxy-7-methyl-3-methylidene-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-6,8-dienoate
  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