N-ethyl 4-azatricyclo[5.2.1.02,6]dec-8-en-3,5-dione | 100898-11-1

• 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: N-ethyl 4-azatricyclo[5.2.1.02,6]dec-8-en-3,5-dione
• 英文别名: (1α,2α,6α,7α)-4-ethyl-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione；N-ethyl cis-5-norbornene-endo-2,3-dicarboximide；2-ethyl-(3ac,7ac)-3a,4,7,7a-tetrahydro-4r,7c-methano-isoindole-1,3-dione；2-Aethyl-(3ac,7ac)-3a,4,7,7a-tetrahydro-4r,7c-methano-isoindol-1,3-dion；(1R,2S,6R,7S)-4-ethyl-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• CAS: 100898-11-1
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: HDNAENGLYCLHFK-SPJNRGJMSA-N

物化性质

• 熔点：
  78.0-78.7 °C
• 沸点：
  335.9±42.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  N-ethyl 4-azatricyclo[5.2.1.02,6]dec-8-en-3,5-dione 在 RuH₂(CO)(PPh₃)₃ 、 苯硫酚 、 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.37h， 生成 dimethyl 6-ethyl-14, 15-di(4-fluorophenylthiouredioethylcarboxamide)6-aza-19-oxaheptacyclo[9.6.1.13,8.113,16.02,10.04,8.012,17]icosane-3,7-dione-1,11-dicarboxylate
  参考文献：
  名称：

  框架的影响：使用熔融[n]聚降冰片烷的阴离子结合研究

  摘要：

  一系列双-硫脲-官能化[的Ñ ]降冰片烯主机（1 - 6）与尺寸的增加，合成，并通过使用他们的阴离子结合特性进行了评价1 1 H NMR光谱和滴定工作的图分析。较大的双硫脲-[ 3 ]聚降冰片烷支架4和5以1：1（合作）排列结合乙酸盐，而相应的较小的降冰片烷宿主2，在预组织方面相同，以1：2（独立）排列结合乙酸盐。相反，框架的大小对磷酸二氢的结合没有影响。这些结果清楚地表明了框架本身可能对主机与访客之间的交互产生微妙的影响。

  DOI：

  10.1002/asia.201301677
• 作为产物：
  描述：

  3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 以 四氢呋喃 、 甲苯 为溶剂， 生成 N-ethyl 4-azatricyclo[5.2.1.02,6]dec-8-en-3,5-dione
  参考文献：
  名称：

  通过整体开环复分解聚合和NCA聚合合成杂化嵌段共聚物。

  摘要：

  通过开环易位聚合（ROMP），然后进行氨基酸N-羧基酐的开环聚合，合成了具有良好控制的分子量和窄的多分散性的线性杂化嵌段共聚物。

  DOI：

  10.1039/c1cc13531g

文献信息

• Synthesis of hybrid block copolymers via integrated ring-opening metathesis polymerization and polymerization of NCA
  作者：Yugang Bai、Hua Lu、Ettigounder Ponnusamy、Jianjun Cheng

  DOI：10.1039/c1cc13531g

  日期：——

  Linear hybrid block copolymers with well controlled molecular weights and narrow polydispersities were synthesized via ring-opening metathesis polymerization (ROMP) followed by ring-opening polymerization of amino acid N-carboxyanhydrides.

  通过开环易位聚合（ROMP），然后进行氨基酸N-羧基酐的开环聚合，合成了具有良好控制的分子量和窄的多分散性的线性杂化嵌段共聚物。
• Micellar Catalysis of Diels−Alder Reactions:  Substrate Positioning in the Micelle
  作者：Theo Rispens、Jan B. F. N. Engberts

  DOI：10.1021/jo0260802

  日期：2002.10.1

  be enhanced up to a factor of about 4.5. The low micellar rate constants can be attributed to the relatively apolar (water-poor) region of the micelle, in which the reactions take place. NMR experiments indicate that the reactants usually reside near the alpha- or beta-CH2 groups of the surfactant molecules in the micelle. Comparison of the micellar rate constants with rate constants in water/1-propanol

  我们研究了在胶束介质中环戊二烯，山梨醇和山梨基三甲基溴化铵与一系列N-取代的马来酰亚胺的Diels-Alder反应动力学。已经确定了胶束速率常数，发现其比各自的含水速率常数低20-40倍。然而，发现添加十二烷基硫酸钠后，观察到的速率常数可以提高到约4.5倍。低胶束速率常数可归因于发生反应的胶束的相对非极性（贫水）区域。NMR实验表明，反应物通常位于胶束中表面活性剂分子的α-或β-CH2基团附近。
• Mechanochemical <i>N</i>-alkylation of imides
  作者：Anamarija Briš、Mateja Đud、Davor Margetić

  DOI：10.3762/bjoc.13.169

  日期：——

  The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their

  研究了酰亚胺衍生物的机械化学N-烷基化。在球磨机中在无溶剂条件下进行反应可获得良好的收率，可以代替传统的溶液条件。该方法是通用的，可以应用于各种酰亚胺和烷基卤。在球磨条件下制备的邻苯二甲酰亚胺通过与1，2-二氨基乙烷反应而用于胺的机械化学加百利合成中。
• 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.
• Preparation of maleimide and n-sub-stituted derivatives
  申请人：US RUBBER CO

  公开号：US02524145A1

  公开（公告）日：1950-10-03