甲基2,2-二乙氧基环戊烷羧酸酯 | 450408-27-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 甲基2,2-二乙氧基环戊烷羧酸酯
• 英文名称: methyl cyclopentanone-2-carboxylate diethylketal
• 英文别名: Methyl 2,2-diethoxycyclopentanecarboxylate；methyl 2,2-diethoxycyclopentane-1-carboxylate
• CAS: 450408-27-2
• 化学式: C₁₁H₂₀O₄
• 分子量: 216.277
• InChiKey: QLGMBIAFHZFLTL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲基2,2-二乙氧基环戊烷羧酸酯 在 吡啶 、 lithium aluminium tetrahydride 、 硫酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.67h， 生成 <1-(4,8-Dimethyl-3,7-nonadienyl)-2-oxocyclopentyl>methyl 2,5-Dibromopentanoate
  参考文献：
  名称：

  Daphniphyllum alkaloids. 15. Total syntheses of (.+-.)-methyl homodaphniphyllate and (.+-.)-daphnilactone A

  摘要：

  Biomimetic total syntheses of (+/-)-daphnilactone A (6) and (+/-)-methyl homodaphniphyllate (4) have been carried out. The syntheses began with the preparation of tricyclic lactone ether 18d, which was reduced to diol 19d with LiAlH4. Oxidation of 19d gave a sensitive dialdehyde (20d), which was treated sequentially with ammonia and warm acetic acid to obtain the hexacyclic amino ether 22d. The tetracyclization process leading from 19d to 22d proceeded in 47% yield and resulted in the formation of five new sigma-bonds and four new rings. After hydrogenation of the double bond, the saturated amino ether 7 was fragmented by treatment with diisobutylaluminum hydride in refluxing toluene. Unsaturated amino alcohol 23 was obtained in 71% yield, accompanied by a smaller amount of the simple elimination product 24. Compound 23 was converted into (+/-)-daphnilactone A (6) by oxidation to the unsaturated amino acid, which was cyclized by treatment with aqueous formaldehyde at pH 7. For the preparation of 4, compound 23 was oxidized and the resulting amino acid esterified to obtain 26. Treatment of this compound with phenyl isocyanate gave a urea derivative (27) that underwent smooth cyclization to (+/-)-methyl homodaphniphyllate (4) in refluxing formic acid. From homogeranyl iodide, the limiting starting material, compound 6 was obtained in 11 steps and 8% overall yield and compound 4 was obtained in 13 steps and 11% overall yield.

  DOI：

  10.1021/jo00035a012
• 作为产物：
  描述：

  2-甲氧羰基环戊酮 、 原甲酸三乙酯 在 乙醇 、 tetra-N-butylammonium tribromide 作用下， 反应 2.0h， 以89%的产率得到甲基2,2-二乙氧基环戊烷羧酸酯
  参考文献：
  名称：

  四丁基三溴化铵（TBATB）作为HBr的有效生成剂，是用于羰基化合物缩醛化的有效化学选择试剂。

  摘要：

  在原甲酸三烷基酯和催化量的三丁基溴化四丁基铵（TBATB）在无水醇中存在的条件下，在温和的反应条件下，以优异的收率获得了各种羰基化合物的无环和环状缩醛。在酮存在下对醛进行化学选择性乙缩醛化，不对称缩醛形成，较短的反应时间，温和的反应条件，酸敏感保护基团的稳定性，高效率，所需产物的容易分离以及试剂的催化性质本方法学是一种实用的选择。

  DOI：

  10.1021/jo025701o