ethyl 3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate | 420782-22-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: ethyl 3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate
• 英文别名: Ethyl 3-methyl-4,7-dioxo-1-benzothiophene-2-carboxylate
• CAS: 420782-22-5
• 化学式: C₁₂H₁₀O₄S
• 分子量: 250.275
• InChiKey: GCFASPBFGHJPRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  88.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate 在 sodium sulfate 、 silver(l) oxide 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 48.0h， 生成 ethyl 5-benzoyl-3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate
  参考文献：
  名称：

  苯并[1,2-b:5,4-b']二噻吩-4,8-​​二酮衍生物的合成

  摘要：

  4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (1) 在辐照下与一系列醛在 5 位发生区域选择性酰化反应，得到相应的 5-acyl-4,7-dihydroxybenzo [b]噻吩-2-羧酸盐(2)，然后用Ag 2 O氧化得到5-酰基-4,7-二氧代-4,7-二氢苯并[b]噻吩-2-羧酸盐(3)。这些酰化苯并噻吩醌衍生物在一锅中通过巯基乙酸盐处理转化为 4,8-二氧代-4,8-​​二氢苯并[1,2-b:5,4-b']二噻吩-2,6-二羧酸盐 (5) ，然后是 1-三甲基甲硅烷基咪唑介导的环化和硝酸铈 (IV) 铵 (CAN) 氧化。

  DOI：

  10.3987/com-03-9790
• 作为产物：
  描述：

  (2-Acetyl-3,6-dihydroxy-phenylsulfanyl)-acetic acid ethyl ester 在 盐酸 、 ammonium cerium(IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 3.58h， 生成 ethyl 3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate
  参考文献：
  名称：

  An Improved Method for the Preparation of 4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates from 2-Acyl-1,4-benzoquinones and Mercaptoacetates

  摘要：

  4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (4) have been synthesized in a one-pot procedure from 2-acyl-1,4-benzoquinones (1) and mercaptoacetates (2) by using 1-trimethylsilylimidazole as a protective reagent as well as a base. Thus, reaction of 1 with 2 in THF at room temperature was followed by treatment with excess of 1-trimethylsilylimidazole at 80 degreesC. Then the cooled mixture was hydrolyzed with hydrochloric acid and oxidized with cerium(IV) ammonium nitrate (CAN) to give the expected thiophenequinone derivatives (4). 4,9-Dioxo-4,9-dihydronaphtho[2,3-b]thiophene-2-carboxylates (7) were similarly prepared from 2-acyl-1,4-naphthoquinones (5) and mercaptoacetates, in general, by omitting the CAN oxidation procedure.

  DOI：

  10.3987/com-01-9358

文献信息

• Synthesis of Thienobenzofuranquinone Derivatives by Photoinduced and CAN-mediated 3+2-Type Cycloaddition Reactions
  作者：Kazuhiro Kobayashi、Keiichi Yoneda、Kazutaka Hayashi、Osamu Morikawa、Hisatoshi Konishi

  DOI：10.3987/com-05-10359

  日期：——

  8-tetrahydrothieno[2,3-f]benzofuran-6-carboxylates (2). Cerium(IV) ammonium nitrate (CAN)-mediated cycloaddition of ethyl 5-hydroxy-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (1) to alkenes or phenylacetylene, giving ethyl 4,8-dioxo-4,8-dihydrothieno[2,3-f]benzofuran-6-carboxylate (2 or 4) and ethyl 4,5-dioxo-4,5-dihydrothieno[3,2-g]benzofuran-7-carboxylate derivatives (3 or 5), is also reported.

  5-hydroxy-3-methyl-4,7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylate (la) 和烯烃之间的光诱导环加成反应生成 7-methyl-4,8-​​dioxo 乙酯-2,3,4,8-四氢噻吩并[2,3-f]苯并呋喃-6-羧酸盐 (2)。铈 (IV) 硝酸铵 (CAN) 介导 5-羟基-4,7-二氧代-4,7-二氢苯并[b]噻吩-2-羧酸乙酯 (1) 与烯烃或苯乙炔的环加成反应，得到 4,8 乙酯-dioxo-4,8-​​dihydrothieno[2,3-f]benzofuran-6-carboxylate（2 或 4）和 4,5-dioxo-4,5-dihydrothieno[3,2-g]benzofuran-7-carboxylate还报告了衍生物（3 或 5）。
• An Improved Method for the Preparation of 4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates from 2-Acyl-1,4-benzoquinones and Mercaptoacetates
  作者：Kazuhiro Kobayashi、Keiichi Yoneda、Masaharu Uchida、Hideki Matsuoka、Osamu Morikawa、Hisatoshi Konishi

  DOI：10.3987/com-01-9358

  日期：——

  4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (4) have been synthesized in a one-pot procedure from 2-acyl-1,4-benzoquinones (1) and mercaptoacetates (2) by using 1-trimethylsilylimidazole as a protective reagent as well as a base. Thus, reaction of 1 with 2 in THF at room temperature was followed by treatment with excess of 1-trimethylsilylimidazole at 80 degreesC. Then the cooled mixture was hydrolyzed with hydrochloric acid and oxidized with cerium(IV) ammonium nitrate (CAN) to give the expected thiophenequinone derivatives (4). 4,9-Dioxo-4,9-dihydronaphtho[2,3-b]thiophene-2-carboxylates (7) were similarly prepared from 2-acyl-1,4-naphthoquinones (5) and mercaptoacetates, in general, by omitting the CAN oxidation procedure.
• Synthesis of Benzo[1,2-b:5,4-b']dithiophene-4,8-dione Derivatives
  作者：Kazuhiro Kobayashi、Toshikazu Ogata、Kazuna Miyamoto、Osamu Morikawa、Hisatoshi Konishi

  DOI：10.3987/com-03-9790

  日期：——

  7-dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (3 ). These acylated benzothiophenquinone derivatives were transformed in one-pot to 4,8-dioxo-4,8-dihydrobenzo[1,2-b:5,4-b']dithiophene-2,6-dicarboxylates (5) by treatment with mercaptoacetates, followed by 1-trimethylsilylimidazole-mediated cyclization and cerium(IV) ammonium nitrate (CAN) oxidation.

  4,7-Dioxo-4,7-dihydrobenzo[b]thiophene-2-carboxylates (1) 在辐照下与一系列醛在 5 位发生区域选择性酰化反应，得到相应的 5-acyl-4,7-dihydroxybenzo [b]噻吩-2-羧酸盐(2)，然后用Ag 2 O氧化得到5-酰基-4,7-二氧代-4,7-二氢苯并[b]噻吩-2-羧酸盐(3)。这些酰化苯并噻吩醌衍生物在一锅中通过巯基乙酸盐处理转化为 4,8-二氧代-4,8-​​二氢苯并[1,2-b:5,4-b']二噻吩-2,6-二羧酸盐 (5) ，然后是 1-三甲基甲硅烷基咪唑介导的环化和硝酸铈 (IV) 铵 (CAN) 氧化。