2,3-diethoxy-4-(2-furyl)-4-hydroxy-2-cyclobutenone | 138225-12-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-diethoxy-4-(2-furyl)-4-hydroxy-2-cyclobutenone
• 英文别名: 2,3-Diethoxy-4-(furan-2-yl)-4-hydroxycyclobut-2-en-1-one
• CAS: 138225-12-4
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: SEWHFCYRMIKXPM-UHFFFAOYSA-N

物化性质

• 沸点：
  420.0±45.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  68.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3-diethoxy-4-(2-furyl)-4-hydroxy-2-cyclobutenone 在 potassium carbonate 、 iron(III) chloride 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 乙醚 、 乙醇 为溶剂， 反应 3.0h， 以10.5 g的产率得到5,6-diethoxybenzofuran-4,7-dione
  参考文献：
  名称：

  REARRANGEMENT OF 4-ARYL-4-HYDROXY-2,3-DIALKOXYCYCLOBUTENONES TO ANNULATED HYDROQUINONES AND QUINONES: 5,6-DIETHOXYBENZOFURAN-4,7-DIONE

  摘要：

  DOI：

  10.15227/orgsyn.069.0220
• 作为产物：
  描述：

  呋喃-2-基-锂 、 方酸二乙酯 以 四氢呋喃 为溶剂， 以79%的产率得到2,3-diethoxy-4-(2-furyl)-4-hydroxy-2-cyclobutenone
  参考文献：
  名称：

  Radical-mediated ring enlargement of cyclobutenones: new synthetic potential of squaric acid.

  摘要：

  4-Hydroxy-2-cyclobutenones, which are readily obtainable from diethyl squarate, reacted with lead tetraacetate to give 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones via oxy-radical-triggered ring opening (beta-scission) and subsequent 5-endo reclosure. This method was extended to saturated four-membered alpha-ketol and applied to the synthesis of a natural product (Z-isomer of multicolanate). A carbon-centered radical-triggered reaction was also performed in which photolysis of a mixed anhydride of thiohydroxamic acid and (4-oxo-2-cyclobutenyl)acetic acid afforded a 4-cyclopentene-1,3-dione rather than the furanone as a rearranged product. The similarity of these rearrangements is discussed using a PM3 calculation in terms of pentadienoyl radical to cyclopentenone radical cyclization and its oxa version.

  DOI：

  10.1021/ja00143a006

文献信息

• Oxidative Rearrangement of 4-Hydroxy-2-cyclobutenone. A New Route to Highly Substituted Furanones from Squaric Acid
  作者：Yoshihiko Yamamoto、Masatomi Ohno、Shoji Eguchi

  DOI：10.1021/jo00096a001

  日期：1994.8

  4-Hydroxy-2-cyclobutenones, which were obtained by the reaction of diethyl squarate with an organolithium, reacted with lead tetraacetate (to generate an oxy radical) affording 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones. This type of rearrangement was realized in a simple four-membered cyclic alpha-ketol but not in the corresponding five-membered ring.
• PhI(OAc)₂-Promoted Rearrangement of the Hydroxyl Group:  Ring Expansion of 4-Hydroxy-2-cyclobutenone to 2(5<i>H</i>)-Furanone in Comparison with Ring Cleavage of the α-Hydroxycycloalkanone to the ω-Formyl Ester
  作者：Masatomi Ohno、Isamu Oguri、Shoji Eguchi

  DOI：10.1021/jo990704v

  日期：1999.12.1

  Reaction of 4-hydroxy-2-cyclobutenones with PhI(OAc)(2) in 1,2-dichloroethane at reflux temperature gave rise to 5-acetoxy-2(5H)-furanones as a rearranged product, formation of which is explained by ring cleavage of the once formed hypervalent iodine intermediate and following recyclization of the resulting acyl cation with a carbonyl oxygen. Likewise, 5-methoxy-2(5H)-furanones were obtained in better yields by using methanol as both a solvent and a nucleophile. Extension of this reaction to simple 2-hydroxycycloalkanones resulted in ring cleavage to methyl omega-formylalkanoates under milder conditions. In this case, the mechanism is explained by known glycol cleavage with PhI(OAc)(2).
• REARRANGEMENT OF 4-ARYL-4-HYDROXY-2,3-DIALKOXYCYCLOBUTENONES TO ANNULATED HYDROQUINONES AND QUINONES: 5,6-DIETHOXYBENZOFURAN-4,7-DIONE
  作者：Perri、Rice、Moore

  DOI：10.15227/orgsyn.069.0220

  日期：——
• Radical-mediated ring enlargement of cyclobutenones: new synthetic potential of squaric acid.
  作者：Yoshihiko Yamamoto、Masatomi Ohno、Shoji Eguchi

  DOI：10.1021/ja00143a006

  日期：1995.9

  4-Hydroxy-2-cyclobutenones, which are readily obtainable from diethyl squarate, reacted with lead tetraacetate to give 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones via oxy-radical-triggered ring opening (beta-scission) and subsequent 5-endo reclosure. This method was extended to saturated four-membered alpha-ketol and applied to the synthesis of a natural product (Z-isomer of multicolanate). A carbon-centered radical-triggered reaction was also performed in which photolysis of a mixed anhydride of thiohydroxamic acid and (4-oxo-2-cyclobutenyl)acetic acid afforded a 4-cyclopentene-1,3-dione rather than the furanone as a rearranged product. The similarity of these rearrangements is discussed using a PM3 calculation in terms of pentadienoyl radical to cyclopentenone radical cyclization and its oxa version.