3-methylindene-2-carboxylic acid methyl ester | 7316-64-5

• 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-methylindene-2-carboxylic acid methyl ester
• 英文别名: Methyl 3-methyl-1H-indene-2-carboxylate；methyl 3-methyl-1H-2-indenecarboxylate；2-methoxycarbonyl-3-methyl-1H-indene；3-methyl-indene-2-carboxylic acid methyl ester；3-Methyl-inden-2-carbonsaeure-methylester；1-Methyl-2-inden-(1)-carbonsaeure-methylester
• CAS: 7316-64-5
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: VAFIJZGHDGTWFN-UHFFFAOYSA-N

物化性质

• 熔点：
  64.0-64.3 °C(Solv: hexane (110-54-3))
• 沸点：
  287.6±19.0 °C(Predicted)
• 密度：
  1.137±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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-methylindene-2-carboxylic acid methyl ester 在 三氟甲磺酸 、 三氟乙酸 作用下， 生成 3-甲基茚-2-羧酸
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja908749u
• 作为产物：
  描述：

  2-苄基乙酰乙酸乙酯 在 硫酸 硫酸氢铵 、 硫酸 作用下， 以 水 为溶剂， 反应 26.0h， 生成 3-methylindene-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Rao, C. Someswara; Ramachandra, R.; Kshirsagar, S., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1983, vol. 22, # 3, p. 230 - 233

  摘要：

  DOI：

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，
• Indane modulators of glucocorticoid receptor, AP-1, and/or NF/kB activity and use thereof
  申请人：Duan Jingwu

  公开号：US20070185056A1

  公开（公告）日：2007-08-09

  Novel non-steroidal compounds are provided that are useful in treating diseases associated with modulation of the glucocorticoid receptor, AP-1, and/or NF-κB activity including obesity, diabetes, inflammatory and immune diseases having the structure of formula (I): or enantiomers, diastereomers, or a pharmaceutically-acceptable salt, or hydrate, thereof, where X is -A 1 QA 2 -; Q is a bond, —C(═O)—, —OC(O)—, —C(═O)NR 5 —, —SO p —, —SO p NR 5 —, —C(O)O—, —NR 5 C(O)—, —OC(O)NR 5 —, —NR 5 C(O)O—, —S(O) p NR 5 C(O)—, —C(O)NR 5 S(O) p — —NR 5 S(O) p —, or —NR 5 C(═O)NR 6 —. Y is selected from hydrogen, C 1-4 alkyl, OR 16 , substituted C 1-6 alkyl, cycloalkyl, aryl, heterocyclo and heteroaryl. A 1 and A 2 are independently selected from a bond, C 1-3 alkylene, or C 1-3 alkenylene, and R 1 -R 11 are defined herein. Also provided are pharmaceutical compositions, combinations, and methods of treating obesity, diabetes and inflammatory- or immune-associated diseases comprising said compounds.

  提供了一种新型的非甾体化合物，可用于治疗与糖皮质激素受体、AP-1和/或NF-κB活性调节相关的疾病，包括肥胖、糖尿病、炎症性和免疫性疾病，其具有以下结构的化学式（I）： 或其对映体、非对映体、药用可接受的盐或水合物，其中X为-A 1 QA 2 -；Q为键，—C(═O)—，—OC(O)—，—C(═O)NR 5 —，—SO p —，—SO p NR 5 —，—C(O)O—，—NR 5 C(O)—，—OC(O)NR 5 —，—NR 5 C(O)O—，—S(O) p NR 5 C(O)—，—C(O)NR 5 S(O) p —，—NR 5 S(O) p —，或—NR 5 C(═O)NR 6 —。Y从氢、C 1-4 烷基、OR 16 、取代的C 1-6 烷基、环烷基、芳基、杂环烷基和杂芳基中选择。A 1 和A 2 独立选择自键、C 1-3 烷基或C 1-3 烯基，R 1 -R 11 在此定义。还提供了包含所述化合物的药物组合物、组合物和治疗肥胖、糖尿病和炎症性或免疫相关疾病的方法。
• Cobalt-Catalyzed Regioselective Carbocyclization Reaction of <i>o</i>-Iodophenyl Ketones and Aldehydes with Alkynes, Acrylates, and Acrylonitrile:  A Facile Route to Indenols and Indenes
  作者：Kuo-Jui Chang、Dinesh Kumar Rayabarapu、Chien-Hong Cheng

  DOI：10.1021/jo049506g

  日期：2004.7.1

  efficient cobalt-catalyzed carbocylization for the synthesis of indenols and indenes and a new method for reductive decyanation are described. 2-Iodophenyl ketones and aldehydes 1a−g undergo carbocyclization with various disubstituted alkynes 2a−k in the presence of Co(dppe)I2 and zinc powder in acetonitrile at 80 °C for 3 h to afford the corresponding indenol derivatives 3a−s and 4a−m in good to excellent

  描述了一种高效的钴催化的羰基化反应，用于合成茚满和茚满，以及一种新的还原性脱氰方法。2-碘苯基酮和醛1a - g在Co（dppe）I 2和锌粉存在下于80°C在乙腈中与各种二取代炔烃2a - k进行碳环化3小时，得到相应的茚满醇衍生物3a - s和图4a -米产量高到极好。对于某些不对称炔烃，碳环化反应具有显着的区域选择性，可提供一个单一的区域异构体。钴催化的碳环化反应已成功地扩展到茚衍生物的合成。因此，在存在Co（dppe）Cl 2 / dppe的情况下，2-碘苯基酮和醛（1）与丙烯酸酯H 2 C CHCO 2 R（7a - d）和丙烯腈H 2 C CHCN（7e）的反应顺利进行。和在乙腈中于80℃下24小时锌粉末，得到相应的茚8A - ķ和9A -c以中等至良好的产量。有趣的是，当使用7e进行碳环化时，还发生了还原性脱氰反应，得到了没有氰基官能度的茚衍生物。还提出了这种钴催化的碳环化反应的可能机理。
• Synthesis of 2-(2,3-dihydro-2-oxo-1,3,4-oxadiazol-5-yl) benzo heterocycles. A novel series of orally active antiallergic agents
  作者：John H. Musser、Richard E. Brown、Bernard Loev、Kevin Bailey、Howard Jones、Robert Kahen、Fuchih Huang、Atul Khandwala、Mitchell Leibowitz

  DOI：10.1021/jm00368a004

  日期：1984.2

  A series of new 2-(2,3-dihydro-2-oxo-1,3,4-oxadiazol-5-yl) benzo heterocycles has been prepared. These compounds were tested as inhibitors of antigen-induced release of histamine (AIR) in vitro from rat peritoneal mast cells (RMC) and as inhibitors of IgE-mediated rat passive cutaneous anaphylaxis in the rat (PCA). Most of this new class of antiallergic agents showed good activity in the RMC assay

  制备了一系列新的2-（2,3-二氢-2-氧代-1,3,4-恶二唑-5-基）苯并杂环。测试了这些化合物作为体外从大鼠腹膜肥大细胞（RMC）中抗原诱导的组胺（AIR）释放的抑制剂，以及作为IgE介导的大鼠大鼠被动皮肤过敏反应（PCA）的抑制剂。大多数这类新的抗过敏剂在RMC分析中显示出良好的活性。最有效的化合物3-氯-2-（2,3-二氢-2-氧代-1,3,4-恶二唑-5-基）苯并[b]噻吩（6t），I50值为0.2在RMC分析中，microM的效能比色甘酸二钠（DSCG）强15倍。在PCA测试中，许多化合物具有口服活性，当以这种方式给予时，这些化合物中的几种显示出比通过腹膜内给予时DSCG所显示的更高的效力。
• Rapid Synthesis of Functionalized Indenes, Triazoles, and Glucocorticoid Receptor Modulators by Sequential Multicatalysis Cascade Reactions
  作者：Dhevalapally B. Ramachary、Rumpa Mondal、Chintalapudi Venkaiah

  DOI：10.1002/ejoc.201000220

  日期：2010.6

  general process for the synthesis of substituted indenes and 1,2,3-triazoles was achieved for the first time through a multicatalysis cascade reaction of 2-ethynylbenzaldehydes, CH acids, organic hydrides, and azides in the presence of a catalytic amount of L-proline/CuI/DIPEA. In this communication, we discovered the utilization of a single copper catalyst for two different reactions and shown synthetic

  通过2-乙炔基苯甲醛、CH酸、有机氢化物和叠氮化物在催化量的L存在下的多催化级联反应，首次实现了合成取代茚和1,2,3-三唑的通用方法-脯氨酸/CuI/DIPEA。在本次交流中，我们发现了一种铜催化剂可用于两种不同的反应，并展示了其在糖皮质激素受体调节剂的高产合成中的合成应用。