2,5,6-Trimethyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione | 141707-82-6

• 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: 2,5,6-Trimethyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione
• CAS: 141707-82-6
• 化学式: C₁₁H₁₅NO₂
• 分子量: 193.246
• InChiKey: KYDLJSYPTLTQOB-UHFFFAOYSA-N

物化性质

• 沸点：
  318.7±42.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• 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

• 作为产物：
  描述：

  N-甲基马来酰亚胺 、 2,3-二甲基-1,3-丁二烯 以 甲苯 为溶剂， 反应 5.0h， 以90%的产率得到2,5,6-Trimethyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione
  参考文献：
  名称：

  Synthesis and Diels-Alder reactions of N-methylthionomaleimide

  摘要：

  N-Methylthionomaleimide (6) has been synthesized. It is the first example of a thionomaleimide unsubstituted on the olefinic C atoms. Its dienophilic behavior at the olefinic center, with representative dienes (symmetrical and unsymmetrical), has been investigated. There is appreciable regioselectivity with terminally oxygenated unsymmetricaI dienes, the O-substituted carbon of the diene adding preferentially to the thiono-substituted end of the olefin.

  DOI：

  10.1021/jo00040a046

文献信息

• Synthesis and Diels-Alder reactions of N-methylthionomaleimide
  作者：Zhongying Hu、M. V. Lakshmikantham、Michael P. Cava、Jan Becher、Thomas Hansen、Tine Jorgensen

  DOI：10.1021/jo00040a046

  日期：1992.7

  N-Methylthionomaleimide (6) has been synthesized. It is the first example of a thionomaleimide unsubstituted on the olefinic C atoms. Its dienophilic behavior at the olefinic center, with representative dienes (symmetrical and unsymmetrical), has been investigated. There is appreciable regioselectivity with terminally oxygenated unsymmetricaI dienes, the O-substituted carbon of the diene adding preferentially to the thiono-substituted end of the olefin.
• 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.