1-methyl-2,6-dioxabicyclo[5.3.0]decan-8-one | 188407-08-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧环庚烷
• 英文名称: 1-methyl-2,6-dioxabicyclo[5.3.0]decan-8-one
• 英文别名: 5a-Methyl-2,3,4,6,7,8a-hexahydrocyclopenta[b][1,4]dioxepin-8-one
• CAS: 188407-08-1
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: VNFFJYAVXKBFJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-methyl-2,6-dioxabicyclo[5.3.0]decan-8-one 在 silica gel 作用下， 以 溶剂黄146 为溶剂， 生成 2-(3-Hydroxypropoxy)-3-methylcyclopent-2-en-1-one
  参考文献：
  名称：

  Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides

  摘要：

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

  DOI：

  10.1021/jo961844x
• 作为产物：
  描述：

  乙酰丙酸乙酯 在 盐酸 、 dirhodium tetraacetate 、 sodium hydroxide 、 对甲苯磺酸 、 溶剂黄146 、 三乙胺 、 氯甲酸甲酯 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 1-methyl-2,6-dioxabicyclo[5.3.0]decan-8-one
  参考文献：
  名称：

  Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides

  摘要：

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

  DOI：

  10.1021/jo961844x

文献信息

• Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides
  作者：Akira Oku、Nobuhito Murai、Julia Baird

  DOI：10.1021/jo961844x

  日期：1997.4.1

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.