4-ethenyl-2,3-diethoxy-4-hydroxy-2-cyclobutenone | 171195-41-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-ethenyl-2,3-diethoxy-4-hydroxy-2-cyclobutenone
• 英文别名: 4-Ethenyl-2,3-diethoxy-4-hydroxycyclobut-2-en-1-one
• CAS: 171195-41-8
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: UOOHOXUGHAUVAH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-ethenyl-2,3-diethoxy-4-hydroxy-2-cyclobutenone 在 三氟化硼乙醚 、 potassium carbonate 、 silver(l) oxide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 2-ethenyl-3,4-diethoxy-4-(2-propenyl)-2-cyclobutenone
  参考文献：
  名称：

  将方酸衍生为高度取代的环丁烯酮的新方法：路易斯酸催化环丁烯-1,2-二酮单缩醛及其乙烯基与不饱和有机硅烷的反应，以及随后的加合物环转化

  摘要：

  本文描述了一种区域控制合成在 4 位具有不饱和取代基的高度取代的环丁烯酮的新方法，起始于可商购的方酸。环丁烯-1,2-二酮单缩醛（4,4-二乙氧基环丁烯酮）及其乙烯基（2,4-二乙氧基环丁烯酮）很容易从方酸二乙酯中获得，在 Et2O·BF3 存在下与烯丙基硅烷反应得到 4-烯丙基-4-乙氧基环丁烯酮在 2 位区域选择性地具有各种取代基。这些产物通过在二甲苯中回流有效地转化为高度取代的双环[3.2.0]庚烯酮。该方法的合成效用在三环系统的构建中得到了证明。使用丙二烯基硅烷、甲硅烷基烯醇醚进一步扩展路易斯酸催化的单缩醛反应，和甲硅烷基乙烯酮缩醛也提供相应的 4-取代产物。与上述 4-烯丙基化产物相比，4-炔丙基化和 4-酰基甲基化的 p...

  DOI：

  10.1246/bcsj.69.1353
• 作为产物：
  描述：

  乙烯基溴化镁 、 方酸二乙酯 以 四氢呋喃 为溶剂， 以46%的产率得到4-ethenyl-2,3-diethoxy-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

• 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).
• 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.
• New Method for Derivatization of Squaric Acid to Highly Substituted Cyclobutenones: Lewis Acid-Catalyzed Reaction of Cyclobutene-1,2-dione Monoacetal and Its Vinylog with Unsaturated Organosilanes, and Subsequent Ring Transformation of the Adducts
  作者：Yoshihiko Yamamoto、Masatomi Ohno、Shoji Eguchi

  DOI：10.1246/bcsj.69.1353

  日期：1996.5

  Described herein is a novel method for regio-controlled synthesis of highly substituted cyclobutenones having an unsaturated substituent at 4-position, starting from commercially available squaric acid. Both cyclobutene-1,2-dione monoacetal (4,4-diethoxycyclobutenone) and its vinylog (2,4-diethoxycyclobutenone), which were easily obtained from diethyl squarate, reacted with allylsilanes in the presence

  本文描述了一种区域控制合成在 4 位具有不饱和取代基的高度取代的环丁烯酮的新方法，起始于可商购的方酸。环丁烯-1,2-二酮单缩醛（4,4-二乙氧基环丁烯酮）及其乙烯基（2,4-二乙氧基环丁烯酮）很容易从方酸二乙酯中获得，在 Et2O·BF3 存在下与烯丙基硅烷反应得到 4-烯丙基-4-乙氧基环丁烯酮在 2 位区域选择性地具有各种取代基。这些产物通过在二甲苯中回流有效地转化为高度取代的双环[3.2.0]庚烯酮。该方法的合成效用在三环系统的构建中得到了证明。使用丙二烯基硅烷、甲硅烷基烯醇醚进一步扩展路易斯酸催化的单缩醛反应，和甲硅烷基乙烯酮缩醛也提供相应的 4-取代产物。与上述 4-烯丙基化产物相比，4-炔丙基化和 4-酰基甲基化的 p...