4-n-butyl-2,3-diethoxy-4-hydroxy-2-cyclobuten-1-one | 113976-67-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-n-butyl-2,3-diethoxy-4-hydroxy-2-cyclobuten-1-one
• 英文别名: 4-butyl-2,3-diethoxy-4-hydroxy-cyclobut-2-enone；4-Butyl-2,3-diethoxy-4-hydroxycyclobut-2-en-1-one
• CAS: 113976-67-3
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: BRXALYIGNUSUFT-UHFFFAOYSA-N

物化性质

• 沸点：
  392.8±42.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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-n-butyl-2,3-diethoxy-4-hydroxy-2-cyclobuten-1-one 在 吡啶 、 三氟乙酸酐 作用下， 以 乙醚 为溶剂， 反应 0.25h， 以81%的产率得到3-ethoxy-4-n-butyl-3-cyclobutene-1,2-dione
  参考文献：
  名称：

  Synthesis of 4-substituted-3-alkoxy-3-cyclobutene-1,2-diones

  摘要：

  DOI：

  10.1021/jo00246a016
• 作为产物：
  描述：

  正丁基锂 、 方酸二乙酯 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成 4-n-butyl-2,3-diethoxy-4-hydroxy-2-cyclobuten-1-one
  参考文献：
  名称：

  Water-Driven Chemoselective Reaction of Squarate Derivatives with Amino Acids and Peptides

  摘要：

  Here, we report a new class of highly chemoselective reactions between squarate derivatives and the amino acid cysteine or unprotected peptides with a N-terminus cysteine that proceed most efficiently in entirely aqueous solution at neutral pH. Kinetic and structural studies reveal that the presence of hydrogen bonding in water is primarily responsible for both the high yield and fast rate of the reaction.

  DOI：

  10.1021/ol702275q

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).
• REED, MICHAEL W.;POLLART, DANIEL J.;PERRI, STEVEN T.;FOLAND, LAFAYETTE D.+, J. ORG. CHEM., 53,(1988) N 11, C. 2477-2482
  作者：REED, MICHAEL W.、POLLART, DANIEL J.、PERRI, STEVEN T.、FOLAND, LAFAYETTE D.+

  DOI：——

  日期：——