diethyl 2-(benzo[b]thiophen-2-yl)malonate | 149682-27-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: diethyl 2-(benzo[b]thiophen-2-yl)malonate
• 英文别名: diethyl 2-(1-benzothiophen-2-yl)propanedioate
• CAS: 149682-27-9
• 化学式: C₁₅H₁₆O₄S
• 分子量: 292.356
• InChiKey: ZDWGAIIDQDQDPR-UHFFFAOYSA-N

物化性质

• 沸点：
  393.0±27.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  diethyl 2-(benzo[b]thiophen-2-yl)malonate 在 sodium ethanolate 作用下， 反应 22.5h， 生成 diethyl 3-allyl-2-benzothiophenemalonate
  参考文献：
  名称：

  Cope rearrangements in the benzo[b]thiophene series

  摘要：

  The inability to observe Cope rearrangement products at elevated temperatures for diethyl alpha-allyl-2-naphthalenemalonate (1) and diethyl alpha-allyl-9-phenanthrenemalonate (2) does not extend to the analogous systems resulting from replacement of the aromatic units by 2- and 3-benzo[b]thiophene nuclei. Thermal rearrangement of diethyl alpha-allyl-3-benzo[b]thiophenemalonate (5) at 215-255-degrees-C for 11 h produces the expected Cope rearrangement product diethyl 2-allyl-3-benzo[b]thiophenemalonate (10) (8%) accompanied by trans- and cis-ethyl 2,3-dihydro-1-(ethoxycarbonyl)-1H-benzo-[b]cyclopenta[d]thiophene-2-acetate (9a) (10%) and (9b) (5%), respectively. The structure elucidation of 10, 9a, and 9b was done by spectroscopy. The attempted structure verification of 10 by an independent route gave diethyl 2-(1-propenyl)-3-benzo[b]thiophenemalonate (12) which when heated at 230-240-degrees-C for 18 h gave 1-carbethoxy-2-hydroxy-3-methyldibenzothiophene (16) as a major product. Similar results were observed with 2-substituted analogues of 5, both diethyl 3-allyl-2-benzo[b]thiophenemalonate (24) and ethyl 1,2-dihydro-3-(ethoxycarbonyl)-3H-benzo[b]cyclopenta-[d]thiophene-2-acetate (25) being formed. In this case the structure of 24 was verified by synthesis. An extension of this involved a study of thermal rearrangement of analogous compound ethyl alpha-allyl-alpha-cyano-3-benzo[b]thiopheneacetate (30). Thermal rearrangement of 30 at 235-245-degrees-C for 8 h gave the expected Cope rearrangement product ethyl alpha-cyano-2-allyl-3-benzo[b]thiopheneacetate (32) (6%) along with an unexpected diastereomeric mixture of 1-cyano-1-(ethoxycarbonyl)-2-methyl-2,3-dihydro-1H-benzo[b]cyclopenta[d]thiophenes(33)(18%). Speculative mechanistic considerations are offered regarding the mode of transformation of 12 to 16 and 32 to 33.

  DOI：

  10.1021/jo00068a034
• 作为产物：
  描述：

  酮基丙二酸二乙酯 在 4-二甲氨基吡啶 、 三乙胺 、 sodium naphthalenide 作用下， 以 六甲基磷酰三胺 、 二氯甲烷 、 苯 为溶剂， 反应 48.0h， 生成 diethyl 2-(benzo[b]thiophen-2-yl)malonate
  参考文献：
  名称：

  Cope rearrangements in the benzo[b]thiophene series

  摘要：

  The inability to observe Cope rearrangement products at elevated temperatures for diethyl alpha-allyl-2-naphthalenemalonate (1) and diethyl alpha-allyl-9-phenanthrenemalonate (2) does not extend to the analogous systems resulting from replacement of the aromatic units by 2- and 3-benzo[b]thiophene nuclei. Thermal rearrangement of diethyl alpha-allyl-3-benzo[b]thiophenemalonate (5) at 215-255-degrees-C for 11 h produces the expected Cope rearrangement product diethyl 2-allyl-3-benzo[b]thiophenemalonate (10) (8%) accompanied by trans- and cis-ethyl 2,3-dihydro-1-(ethoxycarbonyl)-1H-benzo-[b]cyclopenta[d]thiophene-2-acetate (9a) (10%) and (9b) (5%), respectively. The structure elucidation of 10, 9a, and 9b was done by spectroscopy. The attempted structure verification of 10 by an independent route gave diethyl 2-(1-propenyl)-3-benzo[b]thiophenemalonate (12) which when heated at 230-240-degrees-C for 18 h gave 1-carbethoxy-2-hydroxy-3-methyldibenzothiophene (16) as a major product. Similar results were observed with 2-substituted analogues of 5, both diethyl 3-allyl-2-benzo[b]thiophenemalonate (24) and ethyl 1,2-dihydro-3-(ethoxycarbonyl)-3H-benzo[b]cyclopenta-[d]thiophene-2-acetate (25) being formed. In this case the structure of 24 was verified by synthesis. An extension of this involved a study of thermal rearrangement of analogous compound ethyl alpha-allyl-alpha-cyano-3-benzo[b]thiopheneacetate (30). Thermal rearrangement of 30 at 235-245-degrees-C for 8 h gave the expected Cope rearrangement product ethyl alpha-cyano-2-allyl-3-benzo[b]thiopheneacetate (32) (6%) along with an unexpected diastereomeric mixture of 1-cyano-1-(ethoxycarbonyl)-2-methyl-2,3-dihydro-1H-benzo[b]cyclopenta[d]thiophenes(33)(18%). Speculative mechanistic considerations are offered regarding the mode of transformation of 12 to 16 and 32 to 33.

  DOI：

  10.1021/jo00068a034

文献信息

• Visible-Light Photocatalytic Double C–H Functionalization of Indoles: A Synergistic Experimental and Computational Study
  作者：Jørn Hansen、Uranbaatar Erdenebileg、Taye Demissie

  DOI：10.1055/s-0036-1588719

  日期：——

  C–H functionalization of indoles. The reaction affords 2,3-difunctionalized indoles in up to 84% yield, but the reaction rate depends strongly on electronic substituent effects. Mechanistic DFT studies and control experiments suggest that the secondary functionalization occurs through an independent photocatalytic oxidation of bromide ions formed during the reaction to generate molecular bromine capable

  本文公开了一种新型的吲哚的可见光光催化双 C-H 功能化。该反应以高达 84% 的产率提供 2,3-双官能化吲哚，但反应速率很大程度上取决于电子取代基的影响。机械 DFT 研究和控制实验表明，二次官能化是通过对反应过程中形成的溴离子进行独立的光催化氧化而发生的，以生成能够亲电 C-3 溴化的分子溴。
• A simple approach to C3-ethoxycarbonylmethylation of thiophenes/furans with diethyl bromomalonate
  作者：Mengmeng Huang、Jingzhou Tang、Jung Keun Kim、Ming Gong、Jianye Zhang、Yabo Li、Yangjie Wu

  DOI：10.1039/d2ob00835a

  日期：——

  thiophenes/furans and diethyl bromomalonate as the starting materials. Various 2-substituted (benzo)thiophenes/furans were suitable for the C3-ethoxycarbonylmethylation. The free radical mechanism was proposed based on the results of control experiments, cyclic voltammetry experiments and luminescence quenching experiments. We suggested that the heteroleptic halogen-bridged iridium(III) dimers might play

  以2-取代噻吩/呋喃和溴丙二酸二乙酯为起始原料，开发了一种温和高效的可见光诱导自由基方法制备C3-丙二酸五元杂环化合物。各种2-取代的(苯并)噻吩/呋喃适用于C3-乙氧基羰基甲基化。根据对照实验、循环伏安实验和发光猝灭实验的结果，提出了自由基机理。我们认为杂配卤素桥接的铱（III）二聚体可能在该系统中发挥重要作用。