3'-methylenespiro-4'-one | 126255-70-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3'-methylenespiro-4'-one
• 英文别名: 3'-methylenespiro(adamantane-2,2'-oxetan)-4'-one；Spiro[tricyclo[3.3.1.1(3,7)]decane-2,2'-oxetan]-4'-one, 3'-methylene-；3'-methylidenespiro[adamantane-2,4'-oxetane]-2'-one
• CAS: 126255-70-7
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: FVRCIKRURSRHOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3'-methylenespiro-4'-one 400.0 ℃ 、13.33 Pa 条件下， 以91%的产率得到亚乙烯基三环[3.3.1.13,7]癸烷
  参考文献：
  名称：

  .alpha.-Methylene .beta.-lactones as masked allenes and allene equivalents: some selected chemical transformations

  摘要：

  Selective chemical transformations have been performed on a number of alpha-methylene beta-lactones to illustrate that these highly functionalized heterocycles serve as useful building blocks in organic synthesis. Thus, thermal decarboxylation of these ''masked allenes'' provides a useful regioselective preparation of allenes with a predetermined substitution pattern. Nucleophilic addition takes place at the carbonyl group with ring opening, but free-radical addition, e.g., thiophenol, and electrophilic addition, e.g., bromine, proceed at the exomethylene group with preservation of the beta-lactone ring. [4 + 2] Cycloaddition with cyclopentadiene affords the expected beta-lactones, which on thermal decarboxylation lead to 2-alkylidenenorbornenes. This regio- and stereoselective transformation establishes the alpha-methylene beta-lactones as valuable allene equivalents. The alpha-methylene beta-lactones serve also as dipolarophiles by undergoing readily 1,3-dipolar cycloaddition with diazoalkanes. Reaction with Lawesson's reagent affords a hitherto unknown alpha-methylene beta-(S)-lactone.

  DOI：

  10.1021/jo00020a017
• 作为产物：
  描述：

  2-(2-adamantylidene)propionic acid 在 硫酸 、 氧气 、 tetraphenylporphyrin 、 三苯基膦 作用下， 以 四氯化碳 、 氯仿 为溶剂， 反应 66.0h， 生成 3'-methylenespiro-4'-one
  参考文献：
  名称：

  Adam, Waldemar; Hasemann, Ludwig, Chemische Berichte, 1990, vol. 123, # 6, p. 1449 - 1451

  摘要：

  DOI：

文献信息

• .alpha.-Methylene .beta.-lactones as masked allenes and allene equivalents: some selected chemical transformations
  作者：Waldemar Adam、Rainer Albert、Ludwig Hasemann、Victor O. Nava Salgado、Bernd Nestler、Eva Maria Peters、Karl Peters、Frank Prechtl、Hans Georg Von Schnering

  DOI：10.1021/jo00020a017

  日期：1991.9

  Selective chemical transformations have been performed on a number of alpha-methylene beta-lactones to illustrate that these highly functionalized heterocycles serve as useful building blocks in organic synthesis. Thus, thermal decarboxylation of these ''masked allenes'' provides a useful regioselective preparation of allenes with a predetermined substitution pattern. Nucleophilic addition takes place at the carbonyl group with ring opening, but free-radical addition, e.g., thiophenol, and electrophilic addition, e.g., bromine, proceed at the exomethylene group with preservation of the beta-lactone ring. [4 + 2] Cycloaddition with cyclopentadiene affords the expected beta-lactones, which on thermal decarboxylation lead to 2-alkylidenenorbornenes. This regio- and stereoselective transformation establishes the alpha-methylene beta-lactones as valuable allene equivalents. The alpha-methylene beta-lactones serve also as dipolarophiles by undergoing readily 1,3-dipolar cycloaddition with diazoalkanes. Reaction with Lawesson's reagent affords a hitherto unknown alpha-methylene beta-(S)-lactone.
• Adam, Waldemar; Hasemann, Ludwig, Chemische Berichte, 1990, vol. 123, # 6, p. 1449 - 1451
  作者：Adam, Waldemar、Hasemann, Ludwig

  DOI：——

  日期：——