3-methyl-1H-indene-2-carboxylic acid ethyl ester | 118215-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 3-methyl-1H-indene-2-carboxylic acid ethyl ester
• 英文别名: ethyl 1-methyl-1-indene-2-carboxylate；ethyl 3-methyl-1H-indene-2-carboxylate；3-methyl-indene-2-carboxylic acid ethyl ester；3-Methyl-inden-2-carbonsaeure-aethylester
• CAS: 118215-65-9
• 化学式: C₁₃H₁₄O₂
• 分子量: 202.253
• InChiKey: MEWOLIKGIWNCSW-UHFFFAOYSA-N

物化性质

• 沸点：
  303.4±21.0 °C(Predicted)
• 密度：
  1.111±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-1H-indene-2-carboxylic acid ethyl ester 、 potassium ethoxide 、 草酸二乙酯 生成 (2-ethoxycarbonyl-3-methyl-inden-1-yl)-glyoxylic acid ethyl ester
  参考文献：
  名称：

  Wislicenus; Hentrich, Justus Liebigs Annalen der Chemie, 1924, vol. 436, p. 20

  摘要：

  DOI：
• 作为产物：
  描述：

  苯基丙酮 在 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.17h， 生成 3-methyl-1H-indene-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  α-重氮-β-羟基酯与三氟化硼醚的反应：不稳定乙烯基阳离子的生成和重排。详细的实验和理论研究

  摘要：

  通过用 LDA 处理重氮乙酸乙酯，然后与一系列环酮反应来制备环状 2-重氮-3-羟基羧酸乙酯。在各种溶剂中用三氟化硼醚合物进一步处理这些 α-重氮-β-羟基酯，可得到一系列不寻常的产品。发现产品类型和比例很大程度上取决于环大小和所用溶剂。该反应通过重氮羟基酯的醇官能团与 BF3 醚合物的路易斯酸络合进行，然后重氮部分的相邻基团参与生成亚环烷基重氮盐。氮的损失会产生高反应性、不稳定的线性乙烯基阳离子。通过 1,2-亚甲基位移的扩环导致形成更稳定的弯曲环烯基乙烯基阳离子。随后的 1, 2-亚甲基位移导致环收缩，最终形成稳定的烯丙基阳离子。该阳离子要么被溶剂捕获，要么与相邻的离子发生环化...

  DOI：

  10.1021/ja950971s

文献信息

• Reactions and Mechanistic Studies of Rhenium-Catalyzed Insertion of α,β-Unsaturated Carbonyl Compounds into a C–H Bond
  作者：Yoichiro Kuninobu、Yuta Nishina、Kayo Okaguchi、Makoto Shouho、Kazuhiko Takai

  DOI：10.1246/bcsj.81.1393

  日期：2008.11.15

  A rhenium complex, [ReBr(CO) 3 (thf)] 2 , catalyzes the insertion of α,β-unsaturated carbonyl compounds into a C-H bond of aromatic compounds having nitrogen-containing directing groups. In this reaction, Re 2 (CO) 10 can also be used as a catalyst. When imines are employed as the aromatic substrates, sequential cyclization proceeds and indene derivatives are obtained in good to excellent yields. This

  铼络合物[ReBr(CO) 3 (thf)] 2 催化α,β-不饱和羰基化合物插入具有含氮导向基团的芳族化合物的CH键中。在该反应中，Re 2 (CO) 10 也可用作催化剂。当使用亚胺作为芳族底物时，顺序环化进行，并以良好至极好的产率获得茚衍生物。这种反应性与钌和铑配合物的反应性相反，钌和铑配合物通常用作不饱和分子插入 CH 键的催化剂。对反应机理的研究表明，铼催化剂促进了芳香族化合物的 CH 键活化，α,β-不饱和羰基化合物插入 Re-C 键，
• Preparation of Conformationally Constrained α2 Antagonists:The Bicyclo[3.1.0]hexane Approach
  作者：Bernard Bonnaud、Philippe Funes、Nathalie Jubault、Bernard Vacher

  DOI：10.1002/ejoc.200500143

  日期：2005.8

  The aim of this research was to discover α2-receptor antagonist subtypes that are more selective than known compounds. We focused on rigid molecules possessing a benzo-fused bicyclo[3.2.0]heptane skeleton. The synthetic route used relied upon the intramolecular [2+2] cycloaddition of styrylketene precursors. The cycloaddition was remarkably efficient and delivered multigram quantities of the cycloadduct

  本研究的目的是发现比已知化合物更具选择性的 α2 受体拮抗剂亚型。我们专注于具有苯并稠合双环[3.2.0]庚烷骨架的刚性分子。所使用的合成路线依赖于苯乙烯基乙烯酮前体的分子内 [2+2] 环加成。环加成非常有效，并产生了数克数量的环加合物 2。对 2 中酮基去除的研究表明四元环的打开很容易。在热消除 TCI-13-endo（TCI = 硫代羰基咪唑）和 TCI-13-exo 后，根据前体的 OH 功能的立体化学获得不同的产物。提出了不同的机制来解释观察到的不同结果。彻底研究了甲基环丁烯或亚甲基环丁烷异构体的双键还原，以优化 C-1 位置的立体控制。内部 π 键的氢化产生具有高非对映选择性的内型 1-甲基环丁烷衍生物，而外型 1-甲基异构体最好通过酸 37 的色谱分离来分离。最后，原型咪唑烷 1，未取代并带有甲基C-1 组，合成用于生物学评估。 (© Wiley-VCH Verlag GmbH
• Co^III–Carbene Radical Approach to Substituted 1<i>H</i>-Indenes
  作者：Braja Gopal Das、Andrei Chirila、Moniek Tromp、Joost N. H. Reek、Bas de Bruin

  DOI：10.1021/jacs.6b05434

  日期：2016.7.20

  successfully applied to a broad range of substrates, producing 1H-indenes in good to excellent yields. The metallo-radical catalyzed indene synthesis in this paper represents a unique example of a net (formal) intramolecular carbene insertion reaction into a vinylic C(sp(2))-H bond, made possible by a controlled radical ring-closure process of the carbene radical intermediate involved. The mechanism was investigated

  提出了一种通过邻肉桂基 N-甲苯磺酰腙的金属基活化催化合成取代 1H-茚的新策略，利用 Co(III) 卡宾自由基中间体的固有反应性。该反应使用容易获得的起始材料并且操作简单，因此代表了构建官能化1H-茚衍生物的实用方法。廉价且易于制备的低自旋钴 (II) 配合物 [Co(II)(MeTAA)]（MeTAA = 四甲基四氮杂 [14] 环烯）被证明是所研究的催化剂中最活跃的催化剂，它证明了催化卡宾自由基反应性非卟啉钴 (II) 络合物，以及 [Co(II)(MeTAA)] 的首次催化活性。该方法已成功应用于广泛的基材，以良好到极好的收率生产 1H-茚。本文中金属自由基催化的茚合成代表了一个独特的例子，即净（正式）分子内卡宾插入反应成乙烯基 C(sp(2))-H 键，通过受控自由基闭环过程使之成为可能。卡宾自由基中间体参与其中。通过计算研究了该机制，并通过一系列支持实验反应证实了结果。密度泛
• Sequential Ruthenium-Catalyzed Hydroamination and Rhenium-Catalyzed C−H Bond Activation Leading to Indene Derivatives
  作者：Yoichiro Kuninobu、Yuta Nishina、Kazuhiko Takai

  DOI：10.1021/ol0611292

  日期：2006.6.1

  [reaction: see text] Formal [3 + 2] annulation of arylacetylenes and alpha,beta-unsaturated carbonyl compounds is achieved in a one-pot reaction by successive treatment of the acetylenes with aniline and a catalytic amount of Ru(3)(CO)(12) and NH(4)PF(6) and C-H bond activation catalyzed by [ReBr(CO)(3)(thf)](2). The result suggests that the second rhenium-catalyzed indene formation is not disturbed

  [反应：参见正文]通过依次用苯胺和催化量的Ru（3）（CO）连续处理乙炔，可以在一锅反应中实现芳基乙炔和α，β-不饱和羰基化合物的正式[3 + 2]环化反应）（12）以及由[ReBr（CO）（3）（thf）]（2）催化的NH（4）PF（6）和CH键活化。结果表明第二rh催化的茚形成不受第一催化剂体系的干扰。
• Cyclization of Arylacetoacetates to Indene and Dihydronaphthalene Derivatives in Strong Acids. Evidence for Involvement of Further Protonation of O,O-Diprotonated β-Ketoester, Leading to Enhancement of Cyclization
  作者：Hiroaki Kurouchi、Hiromichi Sugimoto、Yuko Otani、Tomohiko Ohwada

  DOI：10.1021/ja908749u

  日期：2010.1.20

  The chemical features, such as substrate stability, product distribution, and substrate generality, and the reaction mechanism of Bronsted superacid-catalyzed cyclization reactions of aromatic ring-containing acetoacetates (beta-ketoesters) were examined in detail. While two types of carbonyl cyclization are possible, i.e., keto cyclization and ester cyclization, the former was found to take place exclusively. The reaction constitutes an efficient method to synthesize indene and 3,4-dihydronapthalene derivatives. Acid-base titration monitored with C-13 NMR spectroscopy showed that the acetoacetates are fully O-1,O-3-diprotonated at H-0 = -11. While the five-membered ring cyclization of the arylacetoacetates proceeded slowly at H-0 = -11, a linear increase in the rate of the cyclization was found with increasing acidity in the high acidity region of H-0 = -11.8 to -13.3. Therefore, the O-1,O-3-diprotonated acetoacetates exhibited some cyclizing reactivity, but they are not the reactive intermediates responsible for the acceleration of the cyclization in the high acidity region. The reactive cationic species might be formed by further protonation (or protosolvation) of the O-1,O-3-diprotonated acetoacetates; i.e., they may be tricationic species. Thermochemical data on the acid-catalyzed cyclization of the arylacetoacetates showed that the activation energy is decreased significantly as compared with that of the related acid-catalyzed cyclization reaction of a compound bearing a single functional group, such as a ketone. These findings indicate that intervention of the trication contributes to the activation of the cyclization of arylacetoacetates in strong acid, and the electron-withdrawing nature of the O-protonated ester functionality significantly increases the electrophilicity of the ketone moiety.