2,3-Dihydro-5-(4(E))-3-hydroxy-[4-methyl-6-(2,6,6-trimethylcyclohexenyl)-4-hexen-1-ynyl]-5-methyl-1,4-dioxepin | 1027025-10-0

• 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: 2,3-Dihydro-5-(4(E))-3-hydroxy-[4-methyl-6-(2,6,6-trimethylcyclohexenyl)-4-hexen-1-ynyl]-5-methyl-1,4-dioxepin
• 英文别名: (E)-4-methyl-1-(5-methyl-2,3-dihydro-1,4-dioxepin-5-yl)-6-(2,6,6-trimethylcyclohexen-1-yl)hex-4-en-1-yn-3-ol
• CAS: 1027025-10-0
• 化学式: C₂₂H₃₂O₃
• 分子量: 344.494
• InChiKey: VPXQWWCWFOYTAT-QGMBQPNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,3-Dihydro-5-(4(E))-3-hydroxy-[4-methyl-6-(2,6,6-trimethylcyclohexenyl)-4-hexen-1-ynyl]-5-methyl-1,4-dioxepin 在 盐酸 、 methoxycarbonylsulfamoyl-triethylammmonium hydroxide 、 水 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 22.0h， 生成
  参考文献：
  名称：

  A Novel Aldol Condensation Alternative:α,β-Unsaturated Aldehydes from 3-Hydroxy-1-alkynes via Dihydrodioxepins

  摘要：

  The controlled aldol condensation between an aliphatic ketone and an acetaldehyde equivalent remains a challenge. One solution to this evergreen problem consists of the nucleophilic addition of acetylene to the ketone and the subsequent isomerization of the resulting 3-hydroxy-1-alkyne to the corresponding 2-alkenal. So far, however, the latter step could only be executed with acid-insensitive substrates. We now present a milder, three-step method which extends the scope of the procedure considerably. In the first step, the 3-hydroxy-1-alkynes are converted into 2-propynyl ethylene glycol monoethers; these then undergo base-catalyzed cyclization to give the dihydro-1,4-dioxepins, which are hydrolyzed in acidic medium in the third and final step.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1738::aid-chem1738>3.0.co;2-p
• 作为产物：
  描述：

  3-methyl-1,4-pentadiyne-3-ol 在 氢氧化钾 、 正丁基锂 、 水 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 2,3-Dihydro-5-(4(E))-3-hydroxy-[4-methyl-6-(2,6,6-trimethylcyclohexenyl)-4-hexen-1-ynyl]-5-methyl-1,4-dioxepin
  参考文献：
  名称：

  A Novel Aldol Condensation Alternative:α,β-Unsaturated Aldehydes from 3-Hydroxy-1-alkynes via Dihydrodioxepins

  摘要：

  The controlled aldol condensation between an aliphatic ketone and an acetaldehyde equivalent remains a challenge. One solution to this evergreen problem consists of the nucleophilic addition of acetylene to the ketone and the subsequent isomerization of the resulting 3-hydroxy-1-alkyne to the corresponding 2-alkenal. So far, however, the latter step could only be executed with acid-insensitive substrates. We now present a milder, three-step method which extends the scope of the procedure considerably. In the first step, the 3-hydroxy-1-alkynes are converted into 2-propynyl ethylene glycol monoethers; these then undergo base-catalyzed cyclization to give the dihydro-1,4-dioxepins, which are hydrolyzed in acidic medium in the third and final step.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1738::aid-chem1738>3.0.co;2-p

文献信息

• A Novel Aldol Condensation Alternative:α,β-Unsaturated Aldehydes from 3-Hydroxy-1-alkynes via Dihydrodioxepins
  作者：Heng-xu Wei、Manfred Schlosser

  DOI：10.1002/(sici)1521-3765(19980904)4:9<1738::aid-chem1738>3.0.co;2-p

  日期：1998.9.4

  The controlled aldol condensation between an aliphatic ketone and an acetaldehyde equivalent remains a challenge. One solution to this evergreen problem consists of the nucleophilic addition of acetylene to the ketone and the subsequent isomerization of the resulting 3-hydroxy-1-alkyne to the corresponding 2-alkenal. So far, however, the latter step could only be executed with acid-insensitive substrates. We now present a milder, three-step method which extends the scope of the procedure considerably. In the first step, the 3-hydroxy-1-alkynes are converted into 2-propynyl ethylene glycol monoethers; these then undergo base-catalyzed cyclization to give the dihydro-1,4-dioxepins, which are hydrolyzed in acidic medium in the third and final step.