2,3-diethoxy-4-hydroxy-4-methyl-2-cyclobutenone | 158599-27-0

• 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-hydroxy-4-methyl-2-cyclobutenone
• 英文别名: 2,3-Diethoxy-4-hydroxy-4-methylcyclobut-2-en-1-one
• CAS: 158599-27-0
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: ZCCCLYIBVQKNII-UHFFFAOYSA-N

物化性质

• 沸点：
  360.5±42.0 °C(predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  2,3-diethoxy-4-hydroxy-4-methyl-2-cyclobutenone 在 三氟化硼乙醚 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 xylene 为溶剂， 反应 4.0h， 生成 2,3-diethoxy-1,5-dimethylbicyclo<3.2.0>hept-2-en-7-one
  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：

  甲基锂 、 方酸二乙酯 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.5h， 生成 2,3-diethoxy-4-hydroxy-4-methyl-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

文献信息

• 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.
• 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).
• Squarate desymmetrisation–ozonolysis as an approach to β-substituted-α-ketosuccinates and squalestatin synthesis
  作者：Herman O. Sintim、Anne Valade、David C. Harling、David M. Hodgson

  DOI：10.1016/j.tet.2019.130747

  日期：2019.12

  Silylated tertiary alcohols from 1,2-addition of alkyllithiums to dialkyl squarates undergo alkene ozonolysis to give beta-substituted-alpha-keto-beta-(silyloxy)succinates. With 3-(triethylsilyloxy)butyllithium the methodology was applied to the 2,8-dioxabicyclo[3.2.1]octane core of the squalestatins. Enantioselective 1,2-addition to di-tert-butyl squarate using butyllithium or diethylzinc/Ti(iPrO)(4) in the presence of chiral ligands (such as bisoxazolines or camphorsulfonamides, respectively) gave the corresponding tertiary alcohols in up to 67.5:32.5 er. (C) 2019 Elsevier Ltd. All rights reserved.
• 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...