(1R,2S,6R,7S)-4-propyl-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione | 29633-42-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (1R,2S,6R,7S)-4-propyl-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione
• 英文别名: 2-propyl-(3ac,7ac)-3a,4,7,7a-tetrahydro-4r,7c-methano-isoindole-1,3-dione；2-Propyl-(3ac,7ac)-3a,4,7,7a-tetrahydro-4r,7c-methano-isoindol-1,3-dion；(1R,2S,6R,7S)-4-propyl-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• CAS: 29633-42-9
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: RQGOXSVAQXFULZ-YNFQOJQRSA-N

物化性质

• 熔点：
  213-214 °C
• 沸点：
  347.8±42.0 °C(Predicted)
• 密度：
  1.201±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S,6R,7S)-4-propyl-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione 在 甲酸 、 双氧水 作用下， 生成
  参考文献：
  名称：

  N-取代的降冰片烷环氧酰亚胺的乙醇分解：根据取代基的特性发现各种途径†

  摘要：

  结合实验和理论研究进行了调查的环氧酰亚胺的转变 降冰片烷变成杂环化合物。我们确定了芳基取代的环氧酰亚胺的相互作用降冰片烷 和 乙醇钠导致形成新的杂环化合物，具有制备上有用的产率，并且具有完全的区域选择性。在这种情况下，含有芳基电子给体取代基的环氧酰亚胺的反应导致形成内-9氨基甲酰基-exo -2-羟基-5- oxo-4-氧三环[4.2.1.0 3,7 ]壬烷环氧酰亚胺，exo -2-hydroxy-5-oxo-4-azatricyclo [4.2.1.0 3,7 ] nonan- endo -9-获得羧酸作为乙醇化反应的产物。出乎意料的是，烷基取代的环氧酰亚胺的乙醇化导致二羟基酰亚胺形成为主要产品。为了了解酰亚胺取代基的重要作用，在PCM / B3LYP / 6-31 + G（d）水平进行了系统的理论DFT研究。我们发现，基于溶剂效应和分子内电子相互作用，环氧酰亚胺氮原子上的取代基对乙醇化

  DOI：

  10.1039/b917850c
• 作为产物：
  描述：

  环戊二烯 以 甲苯 为溶剂， 反应 1.5h， 生成 (1R,2S,6R,7S)-4-propyl-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione
  参考文献：
  名称：

  7,9-二甲氧基-3-丙基-3,4-二氢-1H-苯并[g]异色烯-1,5,10-三酮的合成。合成天然产物木聚糖苷的潜在单体

  摘要：

  3-丙基取代的苯并[g]异色烯醌是天然产物木茚的潜在单体，它的新合成是从 2,4-二甲氧基苯甲醛分 9 个步骤完成的（总产率为 8.2%）。关键步骤包括使用交叉复分解反应，其中乙基-3-烯丙基-4（苄氧基）-1,6,8-三甲氧基-2-萘甲酸酯被转化为乙基-4-（苄氧基）-1,6， 8-三甲氧基-3-(4oxopent-2-enyl)-2-naphthoate (E) 和 (Z)-异构体的混合物。在氧杂-迈克尔加成反应后，所需产物的外消旋混合物 5-(苄氧基)-7,9,10-三甲氧基-3-(2-氧代丙基)-3,4dihydro-1H-benzo[g]isochromen-获得了 1-one，基本的 xylindein 内酯骨架。

  DOI：

  10.24820/ark.5550190.p011.313

文献信息

• Fly spray
  申请人：DU PONT

  公开号：US02462835A1

  公开（公告）日：1949-03-01
• Effects of the Hydrophobicity of the Reactants on Diels−Alder Reactions in Water
  作者：Ale Meijer、Sijbren Otto、Jan B. F. N. Engberts

  DOI：10.1021/jo981359x

  日期：1998.11.1

  To assess the importance of the hydrophobicity of different parts of diene and dienophile on the aqueous acceleration of Diels-Alder reactions, second-order rate constants have been determined for the reactions of cyclopentadiene (1), 2,3-dimethyl-1,3-butadiene(4), and 1,3-cyclohexadiene (6) with N-methyl-, N-ethyl-, N-propyl-, and N-butyhmaleimide (2a-d) in different solvents. All these reactions are accelerated in water relative to organic solvents as a result of enhanced hydrogen bonding and enforced hydrophobic interactions during the activation process. The beneficial influence of water as compared to l-propanol on the rate of the Diels-Alder reaction of 4 with 2a-d increases linearly with the length of the alkyl chain of 2. In contrast, for the reaction of both 1 and 6 with 2a-d, no such effect was observed. This difference can be explained by a hydrophobic interaction between the methyl groups of 4 and the N-alkyl group of 2 during the activation process. In the reactions of I and 6, lacking the methyl substituents, this interaction is not possible and elongation of the alkyl chain from ethyl onward does not result in an additional acceleration by water. The enhanced hydrophobicity near the reaction center of dienes 4 and 6 compared to I results in an increased aqueous acceleration of the Diels-Alder reactions of the former dienes with 2a. These data indicate that an increase in the hydrophobicity close to the reaction center in the diene has a much more pronounced effect on the rate acceleration in water than a comparable increase in hydrophobicity in the dienophile further away from the reaction center. The Gibbs energies of transfer of initial state and activated complex of the Diels-Alder reactions under study have been determined. As expected, for all reactions the initial state in water is destabilized compared to that in l-propanol. This destabilization becomes more pronounced when the nonpolar character of diene (close to the reaction center) or dienophile (distant from the reaction center) is increased. Likewise, an increase in the nonpolar character of 2 results in a destabilization of the activated complex. In contrast, addition of methyl or methylene units to the diene is not accompanied by a significant destabilization of the activated complex in water as compared to I-propanol. We conclude that hydrophobic groups near the reaction center seem to lose their hydrophobic character completely in the activated complex of the Diels-Alder reaction, whereas more distant groups retain their nonpolar character throughout the reaction.