2-(4,4-dimethyl-2,6-dioxocyclohexyl)-1,4-diphenylbutane-1,4-dione | 287736-73-6

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 2-(4,4-dimethyl-2,6-dioxocyclohexyl)-1,4-diphenylbutane-1,4-dione
• 英文别名: 2-(2-Hydroxy-4,4-dimethyl-6-oxocyclohexen-1-yl)-1,4-diphenylbutane-1,4-dione
• CAS: 287736-73-6
• 化学式: C₂₄H₂₄O₄
• 分子量: 376.452
• InChiKey: VUJGCMMQVISUQG-UHFFFAOYSA-N

物化性质

• 沸点：
  582.4±50.0 °C(Predicted)
• 密度：
  1.194±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  71.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(4,4-dimethyl-2,6-dioxocyclohexyl)-1,4-diphenylbutane-1,4-dione 在 一水合肼 作用下， 以 乙醇 为溶剂， 反应 0.17h， 以97%的产率得到3,6-二苯基哒嗪
  参考文献：
  名称：

  Adduct of dimedone and 1,2-dibenzoylethene in reactions with nitrogen binucleophiles

  摘要：

  Dimedone adduct with 1,2-dibenzoylethene in reaction with p-phenylenediamine formed a bispyrrole derivative, and with benzidine and ethylenediamine afforded the corresponding monopyrroles. The reaction of the initial adduct with tryptamine results in a product containing a pyrrole and an indole fragments. Both versions of N-heterocyclization proceed in the reaction with urea yielding derivatives of tetrahydroindole and pyrrole. In the reaction with hydrazine hydrate a substituted pyridazine was obtained as a result of a dimedone molecule elimination from the intermediate cyclization product.

  DOI：

  10.1134/s1070428012050090
• 作为产物：
  描述：

  苯 生成 2-(4,4-dimethyl-2,6-dioxocyclohexyl)-1,4-diphenylbutane-1,4-dione
  参考文献：
  名称：

  Synthesis of dioxapropellanes using Mn(III)-based oxidative tandem cyclization of tetracarbonyl compounds with diarylethenes

  摘要：

  摘要 基于锰（III）的四羰基化合物与 1,1-二叔丁烯的氧化反应生成了二氧丙环。使用亚甲基双（3-羟基环己-2-烯-1-酮）作为四羰基化合物，可以生产出 3,4,5,6,7,9-六氢-8H-4a,9a-(环氧乙烷)氧杂蒽-1,8(2H)-二酮，收率很高。虽然该反应与自环化反应竞争生成 3,5,6,7-四氢-4H-螺[苯并呋喃-2,1′-环己烷]-2′,4,6′-三酮，但在室温下加入辅助溶剂甲酸可以控制反应。烷基和芳基取代的亚甲基双（3-羟基环己-2-烯-1-酮）反应生成相应的非对映混合物二氧丙环。形成非对映异构体的原因是串联环化过程中中间碳位的立体阻碍。使用 2-(2-羟基-4,4-二甲基-6-氧代环己-1-烯-1-基)丁烷-1,4-二酮和 2,2′-亚甲基双(3-羟基环戊-2-烯-1-酮)的反应也产生了相应的二氧杂环丙烷。本文讨论了生成物的结构测定和二氧杂环戊烷的生成反应途径。

  DOI：

  10.1093/bulcsj/uoae011

文献信息

• Nitrogen-containing heterocycles derived from tetracarbonyl compounds and their analogs. Synthesis of 2-(4,4-dimethyl-2,6-dioxocyclohexyl)-1,4-diphenylbutane-1,4-dione and its reaction with N-nucleophiles
  作者：A. N. Andin、V. A. Kaminskii、S. V. Dubovitskii

  DOI：10.1007/bf02251998

  日期：1999.11
• Adduct of dimedone and 1,2-dibenzoylethene in reactions with nitrogen binucleophiles
  作者：V. A. Vertkova、A. N. Andin

  DOI：10.1134/s1070428012050090

  日期：2012.5

  Dimedone adduct with 1,2-dibenzoylethene in reaction with p-phenylenediamine formed a bispyrrole derivative, and with benzidine and ethylenediamine afforded the corresponding monopyrroles. The reaction of the initial adduct with tryptamine results in a product containing a pyrrole and an indole fragments. Both versions of N-heterocyclization proceed in the reaction with urea yielding derivatives of tetrahydroindole and pyrrole. In the reaction with hydrazine hydrate a substituted pyridazine was obtained as a result of a dimedone molecule elimination from the intermediate cyclization product.
• Synthesis of dioxapropellanes using Mn(III)-based oxidative tandem cyclization of tetracarbonyl compounds with diarylethenes
  作者：Keisuke Shibuya、Ayaka Chikamatsu、Kazuki Hisano、Hiroshi Nishino

  DOI：10.1093/bulcsj/uoae011

  日期：2024.3.1

  The Mn(III)-based oxidation of tetracarbonyl compounds with 1,1-diarylethenes formed dioxapropellanes. The use of methylenebis(3-hydroxycyclohex-2-en-1-one)s as a tetracarbonyl compound led to the production of 3,4,5,6,7,9-hexahydro-8H-4a,9a-(epoxyethano)xanthene-1,8(2H)-diones in good yields. Although the reaction competed with self-cyclization to form 3,5,6,7-tetrahydro-4H-spiro[benzofuran-2,1′-cyclohexane]-2′,4,6′-triones, it could be controlled by adding the co-solvent formic acid at room temperature. The reactions of alkyl- and aryl-substituted methylenebis(3-hydroxycyclohex-2-en-1-one)s resulted in the corresponding dioxapropellanes as a diastereomixture. The formation of diastereomers is explained by the steric hindrance of the intermediate carbocations during tandem cyclization. The reactions using 2-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)butane-1,4-diones and 2,2′-methylenebis(3-hydroxycyclopent-2-en-1-one)s also produced the corresponding dioxapropellanes. The structure determination of the products and the reaction pathway for the formation of dioxapropellanes are discussed.

  摘要 基于锰（III）的四羰基化合物与 1,1-二叔丁烯的氧化反应生成了二氧丙环。使用亚甲基双（3-羟基环己-2-烯-1-酮）作为四羰基化合物，可以生产出 3,4,5,6,7,9-六氢-8H-4a,9a-(环氧乙烷)氧杂蒽-1,8(2H)-二酮，收率很高。虽然该反应与自环化反应竞争生成 3,5,6,7-四氢-4H-螺[苯并呋喃-2,1′-环己烷]-2′,4,6′-三酮，但在室温下加入辅助溶剂甲酸可以控制反应。烷基和芳基取代的亚甲基双（3-羟基环己-2-烯-1-酮）反应生成相应的非对映混合物二氧丙环。形成非对映异构体的原因是串联环化过程中中间碳位的立体阻碍。使用 2-(2-羟基-4,4-二甲基-6-氧代环己-1-烯-1-基)丁烷-1,4-二酮和 2,2′-亚甲基双(3-羟基环戊-2-烯-1-酮)的反应也产生了相应的二氧杂环丙烷。本文讨论了生成物的结构测定和二氧杂环戊烷的生成反应途径。