2,3-Epoxy-2,3-dimethylcyclohexanone | 35502-46-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 2,3-Epoxy-2,3-dimethylcyclohexanone
• 英文别名: 1,6-Dimethyl-7-oxabicyclo<4.1.0>heptan-2-on；2,3-Dimethyl-2,3-epoxy-cyclohexanon-(1)；2,3-Epoxy-2,3-dimethylcyclohexanon；1,6-Dimethyl-7-oxabicyclo[4.1.0]heptan-2-one
• CAS: 35502-46-6
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: YOINCJZWDCOINW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-Epoxy-2,3-dimethylcyclohexanone 在 对甲苯磺酰肼 作用下， 以78.2%的产率得到6-octyn-2-one
  参考文献：
  名称：

  Mechanism of the intramolecular cyclization of acetylenic ketones

  摘要：

  Acid-catalyzed intramolecular cyclization of 5-cyclodecynone (1) under a variety of conditions gives bicyclo-[4,4,0]-1(6)-decen-2-one (6) as the only product. In a recent report, evidence for a reaction mechanism involving transannular triple-bond participation with a polarized carbonyl group followed by attack of the original carbonyl oxygen on the developing vinyl cation to give an unstable oxete intermediate (4) was presented. Subsequently, several workers have suggested a mechanism involving acid-catalyzed enolization of 1, followed by the transannular attack of the enol double bond at the acetylenic function, as the first two steps in an alternate process for explaining this rearrangement. When 6-octyn-2-one (9) was treated with either mineral or Lewis acids, a mixture of 1-acetyl-2-methyl-1-cyclopentene (12) and 2,3-dimethyl-2-cyclohexen-1-one (14) were produced. Experiments have shown that the oxygen atoms in the starting acetylenic ketone 9 are the same ones found in the cyclic products 12 and 14. A mechanism involving cyclization of enol intermediates cannot account for the formation of 14. On the other hand, formation and rearrangement of oxete intermediates demonstrates how both 12 and 14 are produced. The results from acid-catalyzed cyclization of 6-octyn-2-one (9) are also compared to those reported for the solvolysis of the tosylate of 6-octyn-2-ol (18).

  DOI：

  10.1021/jo00029a019
• 作为产物：
  描述：

  2,3-二甲基环己-2-烯-1-酮 在 sodium hydroxide 、 双氧水 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以64.8%的产率得到2,3-Epoxy-2,3-dimethylcyclohexanone
  参考文献：
  名称：

  Mechanism of the intramolecular cyclization of acetylenic ketones

  摘要：

  Acid-catalyzed intramolecular cyclization of 5-cyclodecynone (1) under a variety of conditions gives bicyclo-[4,4,0]-1(6)-decen-2-one (6) as the only product. In a recent report, evidence for a reaction mechanism involving transannular triple-bond participation with a polarized carbonyl group followed by attack of the original carbonyl oxygen on the developing vinyl cation to give an unstable oxete intermediate (4) was presented. Subsequently, several workers have suggested a mechanism involving acid-catalyzed enolization of 1, followed by the transannular attack of the enol double bond at the acetylenic function, as the first two steps in an alternate process for explaining this rearrangement. When 6-octyn-2-one (9) was treated with either mineral or Lewis acids, a mixture of 1-acetyl-2-methyl-1-cyclopentene (12) and 2,3-dimethyl-2-cyclohexen-1-one (14) were produced. Experiments have shown that the oxygen atoms in the starting acetylenic ketone 9 are the same ones found in the cyclic products 12 and 14. A mechanism involving cyclization of enol intermediates cannot account for the formation of 14. On the other hand, formation and rearrangement of oxete intermediates demonstrates how both 12 and 14 are produced. The results from acid-catalyzed cyclization of 6-octyn-2-one (9) are also compared to those reported for the solvolysis of the tosylate of 6-octyn-2-ol (18).

  DOI：

  10.1021/jo00029a019

文献信息

• Hanack,M. et al., Chemische Berichte, 1972, vol. 105, p. 421 - 433
  作者：Hanack,M. et al.

  DOI：——

  日期：——
• Hanack, Michael; Michel, Ulrich; Winter, Werner, Chemische Berichte, 1981, vol. 114, # 7, p. 2392 - 2398
  作者：Hanack, Michael、Michel, Ulrich、Winter, Werner

  DOI：——

  日期：——
• Mechanism of the intramolecular cyclization of acetylenic ketones
  作者：Charles E. Harding、Salane L. King

  DOI：10.1021/jo00029a019

  日期：1992.1

  Acid-catalyzed intramolecular cyclization of 5-cyclodecynone (1) under a variety of conditions gives bicyclo-[4,4,0]-1(6)-decen-2-one (6) as the only product. In a recent report, evidence for a reaction mechanism involving transannular triple-bond participation with a polarized carbonyl group followed by attack of the original carbonyl oxygen on the developing vinyl cation to give an unstable oxete intermediate (4) was presented. Subsequently, several workers have suggested a mechanism involving acid-catalyzed enolization of 1, followed by the transannular attack of the enol double bond at the acetylenic function, as the first two steps in an alternate process for explaining this rearrangement. When 6-octyn-2-one (9) was treated with either mineral or Lewis acids, a mixture of 1-acetyl-2-methyl-1-cyclopentene (12) and 2,3-dimethyl-2-cyclohexen-1-one (14) were produced. Experiments have shown that the oxygen atoms in the starting acetylenic ketone 9 are the same ones found in the cyclic products 12 and 14. A mechanism involving cyclization of enol intermediates cannot account for the formation of 14. On the other hand, formation and rearrangement of oxete intermediates demonstrates how both 12 and 14 are produced. The results from acid-catalyzed cyclization of 6-octyn-2-one (9) are also compared to those reported for the solvolysis of the tosylate of 6-octyn-2-ol (18).