3-methylene-1-phenylpentane-1,4-dione | 909014-39-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methylene-1-phenylpentane-1,4-dione
• 英文别名: 3-Methylidene-1-phenylpentane-1,4-dione；3-methylidene-1-phenylpentane-1,4-dione
• CAS: 909014-39-7
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: JTMIAYQBHOCAFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methylene-1-phenylpentane-1,4-dione 、 甲醇 在 对甲苯磺酸 作用下， 反应 1.0h， 以53%的产率得到3-Methoxymethyl-2-methyl-5-phenyl-furan
  参考文献：
  名称：

  Ring-opening of tertiary cyclopropanols derived from β-diketones

  摘要：

  The ring-opening reaction of 1,2-di substituted cyclopropanols, prepared from beta-diketones, mediated by Cu(NO3)(2), p-TsOH, and NaOH is reported. The Cu(II)-mediated ring-opening of cyclopropanols gave alpha-methylene-gamma-diketones in good yields. The reaction took place at the less substituted carbon of the cyclopropanols, involving mild conditions and a simple procedure. The reaction induced by p-TsOH in CH2O2 afforded alpha-methyl-gamma-diketones as the major product with minor amounts of 8-diketones. The 2,3,5-tri substituted furans were obtained in high yields when the ring-opening reaction was mediated by p-TsOH in methanol under reflux conditions. In the presence of sodium hydroxide the reaction proceeded smoothly in preference to the formation of beta-diketones, particularly for substrates with an aromatic group on the cyclopropane. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.05.064
• 作为产物：
  描述：

  2-(2-hydroxy-2-methylcyclopropyl)-1-phenylethan-1-one 在 copper(II) nitrate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以90%的产率得到3-methylene-1-phenylpentane-1,4-dione
  参考文献：
  名称：

  Ring-opening of tertiary cyclopropanols derived from β-diketones

  摘要：

  The ring-opening reaction of 1,2-di substituted cyclopropanols, prepared from beta-diketones, mediated by Cu(NO3)(2), p-TsOH, and NaOH is reported. The Cu(II)-mediated ring-opening of cyclopropanols gave alpha-methylene-gamma-diketones in good yields. The reaction took place at the less substituted carbon of the cyclopropanols, involving mild conditions and a simple procedure. The reaction induced by p-TsOH in CH2O2 afforded alpha-methyl-gamma-diketones as the major product with minor amounts of 8-diketones. The 2,3,5-tri substituted furans were obtained in high yields when the ring-opening reaction was mediated by p-TsOH in methanol under reflux conditions. In the presence of sodium hydroxide the reaction proceeded smoothly in preference to the formation of beta-diketones, particularly for substrates with an aromatic group on the cyclopropane. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.05.064

文献信息

• Synthesis of Heterocyclic Systems by Transition-Metal-Catalyzed Cyclization-Migration Reactions – A Diversity-Oriented Strategy for the Construction of Spirocyclic 3(2H)-Furanones and 3-Pyrrolones
  作者：Jörg T. Binder、Benedikt Crone、Stefan F. Kirsch、Clémence Liébert、Helge Menz

  DOI：10.1002/ejoc.200601060

  日期：2007.4

  proceed through an oxonium ion intermediate B, which triggers a stereospecific 1,2-shift analogous to an α-ketol rearrangement. When exploited in a different manner, the 2-alkynyl-2-hydroxy carbonyl compounds 1 afford 3-pyrrolones 3 in 33–81 % yield. For this purpose, the starting compounds 1 are treated with primary amines in the presence of 5 mol-% of PtCl2 at 100 °C in a convenient one-pot process. These

  描述了提供五元杂环产品的两个铂 (II) 催化的杂环化迁移反应。使用 5 mol% PtCl2 作为催化剂，2-炔基-2-羟基羰基化合物 1 在 80 °C 下以中等至极好的产率在非常温和的反应条件下转化为 3(2H)-呋喃酮 2。建议该反应通过氧鎓离子中间体 B 进行，这会触发类似于 α-酮醇重排的立体定向 1,2-位移。当以不同的方式开发时，2-炔基-2-羟基羰基化合物 1 以 33-81% 的产率提供 3-吡咯酮 3。为此，起始化合物 1 在 5 mol% PtCl 2 的存在下，在 100 °C 下以方便的一锅法处理。这些环化-迁移反应为获得 2-位带有芳基或烷基取代基的 3(2H)-呋喃酮和 3-吡咯酮提供了新的途径。合成上具有挑战性的螺环化合物可以通过环收缩以这种方式制备。还描述了定义杂环系统环化-迁移合成的范围和局限性的研究。(© Wiley-VCH Verlag GmbH &
• Ring-opening of tertiary cyclopropanols derived from β-diketones
  作者：Le-Zhen Li、Bin Xiao、Qing-Xiang Guo、Song Xue

  DOI：10.1016/j.tet.2006.05.064

  日期：2006.8

  The ring-opening reaction of 1,2-di substituted cyclopropanols, prepared from beta-diketones, mediated by Cu(NO3)(2), p-TsOH, and NaOH is reported. The Cu(II)-mediated ring-opening of cyclopropanols gave alpha-methylene-gamma-diketones in good yields. The reaction took place at the less substituted carbon of the cyclopropanols, involving mild conditions and a simple procedure. The reaction induced by p-TsOH in CH2O2 afforded alpha-methyl-gamma-diketones as the major product with minor amounts of 8-diketones. The 2,3,5-tri substituted furans were obtained in high yields when the ring-opening reaction was mediated by p-TsOH in methanol under reflux conditions. In the presence of sodium hydroxide the reaction proceeded smoothly in preference to the formation of beta-diketones, particularly for substrates with an aromatic group on the cyclopropane. (c) 2006 Elsevier Ltd. All rights reserved.