2,7,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione | 87991-86-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,7,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione
• 英文别名: (4aRS,8aSR)-2,7,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione；1,4-Naphthalenedione, 4a,5,8,8a-tetrahydro-2,7,8a-trimethyl-, cis-；(4aR,8aS)-2,7,8a-trimethyl-5,8-dihydro-4aH-naphthalene-1,4-dione
• CAS: 87991-86-4
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: SVVHKKJAOLCHBY-GWCFXTLKSA-N

物化性质

• 沸点：
  312.1±42.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,6-二甲基-2,5-环己二烯-1,4-二酮 、 天然橡胶 在 iron(III) chloride 作用下， 以 neat (no solvent, solid phase) 为溶剂， 反应 96.0h， 生成 2,7,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione 、 2,6,8a-trimethyl-4a,5,8,8a-tetrahydronaphthalene-1,4-dione
  参考文献：
  名称：

  不含溶剂的狄尔斯-阿尔德反应通过催化的FeCl 3上的Aerosil ®二氧化硅

  摘要：

  为促进简单二烯和的狄尔斯-阿尔德反应的温和无溶剂协议p -benzoquinones，由铁（III），氯化的Aerosil上的混合物催化®报道二氧化硅。

  DOI：

  10.1016/j.tet.2014.02.017

文献信息

• Control of the Regio- and Stereoselectivity in Diels-Alder Reactions with Quinone Boronic Acids
  作者：María C. Redondo、Marcos Veguillas、María Ribagorda、M. Carmen Carreño

  DOI：10.1002/anie.200803428

  日期：2009.1.2

  The dienophilic reactivity of 2‐methyl‐substituted quinones has been substantially increased by the introduction of a boronic acid substituent, which makes them equivalent to a highly reactive quinone. The Diels–Alder reactions of these quinones are followed by spontaneous and stereoselective protodeboronation to give the trans‐fused adducts. The boron group is a temporal regiocontroller and leads to

  所有这些加起来：通过引入硼酸取代基，大大提高了2-甲基取代的醌的亲二烯反应性，使其等同于高反应性的醌。在这些醌的狄尔斯-阿尔德反应之后，进行自发和立体选择性的原去硼硼烷反应，得到反式融合的加合物。硼基团是暂时的区域调节子，并导致罕见的间 加合物。
• Control of regioselectivity in the Diels–Alder reactions of alkyl-substituted 1,4-benzoquinones by β-cyclodextrin and its derivatives
  作者：Wen-Sheng Chung、Ju-Ying Wang

  DOI：10.1039/c39950000971

  日期：——

  The Diels-Alder reactions of benzoquinones 1-3with penta-1, 3-diene 4 and isoprene 5 are studied in aqueous cyclodextrin solutions, where highly enhanced ortho(6, 8 and 10) and meta(13, 15) regioselectivities are achieved.

  在水相环糊精溶液中，研究了苯醌1-3与五烯-1,3-二烯4和异戊烯5的迪尔斯-阿尔德反应，其中实现了高度增强的邻位（6、8和10）和间位（13、15）区域选择性。
• Catalysis and regioselectivity of quinone Diels–Alder reactions
  作者：James B. Hendrickson、Vishwakarma Singh

  DOI：10.1039/c39830000837

  日期：——

  In a series of six different cycloadditions of unsymmetrical quinones and alkyl-substituted butadienes, TiCl4 afforded considerable catalysis (–78 °C) and gave regioselectivity identical with that of the thermal reaction (200 °C) and therefore complementary to that BF3 catalysis.

  在一系列六种不对称醌和烷基取代的丁二烯的不同环加成反应中，TiCl 4具有相当的催化作用（–78°C），并具有与热反应（200°C）相同的区域选择性，因此可与BF 3催化作用互补。
• Synthesis of Benzo- and Naphthoquinonyl Boronic Acids: Exploring the Diels-Alder Reactivity
  作者：Marcos Veguillas、Maria C. Redondo、Isabel García、María Ribagorda、M. Carmen Carreño

  DOI：10.1002/chem.200902796

  日期：2010.3.22

  dehydroboronation, depending on the substitution on both the quinone and diene partners. The boronic acid acts as a temporary controller, opening a direct access to trans‐fused meta‐regiosomeric adducts when 3‐methyl‐substituted 2‐quinonyl boronic acids react with dienes with a substituent at C‐1. A particularly valuable synthetic result was obtained in the reaction between 3,6‐dimethyl‐2‐quinonyl

  由1,4-二甲氧基芳族衍生物可通过两个步骤合成取代的2-喹啉基硼酸：区域控制的硼化和氧化脱甲基。对它们的双亲性行为的研究表明，硼取代基显着提高了反应性，并触发了有效的多米诺骨牌过程，在该过程中，狄尔斯-阿尔德反应后将进行原脱硼或脱氢硼化，具体取决于醌和二烯配体上的取代。硼酸充当临时控制器，打开到一个直接存取的反式稠合的元3-甲基取代的2-喹啉基硼酸与在C-1处具有取代基的二烯反应时，会形成区域-顺式加合物。在氧气气氛下，3,6-二甲基-2-喹啉基硼酸与间戊二烯之间的反应获得了特别有价值的合成结果。直接形成反式的8a-羟基-2,4a，8-三甲基四氢萘醌，收率高，非对映选择性高。
• Regio- and Stereoselectivity in the Reductions of Cyclic Enedione Systems
  作者：Chunjian Liu、D. Jean Burnell

  DOI：10.1021/jo962377m

  日期：1997.5.1

  Reductions of cyclic enedione substrates by NaBH4 and by LiAl(O-t-Bu)(3)H very predominantly gave monoreduction products with very high regio- and stereoselectivity. The reductions involved axial delivery of the hydride. The results indicated that electronic factors were dominated by steric considerations in the transition state of the reduction, even though the seemingly more encumbered carbonyl was reduced.