methyl 4,5-dioxo-4,5-dihydrobenzindole-2-carboxylate | 139975-66-9

• 分子结构分类: 有机化合物
• 英文名称: methyl 4,5-dioxo-4,5-dihydrobenzindole-2-carboxylate
• 英文别名: methyl 4,5-dihydro-4,5-dioxobenzindole-2-carboxylate；methyl 4,5-dioxo-1H-benzo[g]indole-2-carboxylate
• CAS: 139975-66-9
• 化学式: C₁₄H₉NO₄
• 分子量: 255.23
• InChiKey: ZZOBIVPFJSORGB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  76.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4,5-dioxo-4,5-dihydrobenzindole-2-carboxylate 、 丙酮 在 三乙胺 作用下， 反应 20.0h， 以79%的产率得到methyl 4-oxo-5-acetonyl-5-hydroxy-4,5-dihydro-benzindole-2-carboxylate
  参考文献：
  名称：

  Synthesis and characterization of the 6-deaza derivative of coenzyme PQQ, methyl 4,5-dihydro-4,5-dioxobenz[g]indole-2-carboxylate

  摘要：

  The synthesis of the 6-deaza derivative of coenzyme PQQ, methyl 4,5-dihydro-4,5-dioxobenz[g]indole-2-carboxylate (4), is described, and its physical and chemical properties are compared to those of the trimethyl ester of PQQ (2) and the methyl ester of 7,9-didecarboxy PQQ (3). The synthesis of 4 was achieved by starting with 1-aminonaphthalene and constructing 2-carbomethoxybenz[g]indole (7) by a Japp-Klingemann reaction with methyl alpha-methylacetoacetate and a subsequent Fischer indolization reaction. The quinone function was introduced by a Fremy's salt oxidation of 5-aminoindole 9 which was prepared from 7 by regioselective nitration and catalytic hydrogenation. From the physical properties, it can be recognized that the peri pyridine nitrogen and the ester groups at the 7- and 9-positions considerably affect the electronic nature of the molecules. This is reflected on the reactivities of the quinones in the acetone-adduct formation, the reaction with phenylhydrazine, and the aerobic autorecycling oxidation of benzylamine. The significant roles of the pyridine nitrogen and the ester groups in these reactions are discussed.

  DOI：

  10.1021/jo00036a007
• 作为产物：
  描述：

  1H-苯并[g]吲哚-2-羧酸,5-氨基-,甲基酯 在 potassium dihydrogenphosphate 、 potassium nitrososulfonate 作用下， 以 丙酮 为溶剂， 反应 7.0h， 以44%的产率得到methyl 4,5-dioxo-4,5-dihydrobenzindole-2-carboxylate
  参考文献：
  名称：

  Synthesis and characterization of the 6-deaza derivative of coenzyme PQQ, methyl 4,5-dihydro-4,5-dioxobenz[g]indole-2-carboxylate

  摘要：

  The synthesis of the 6-deaza derivative of coenzyme PQQ, methyl 4,5-dihydro-4,5-dioxobenz[g]indole-2-carboxylate (4), is described, and its physical and chemical properties are compared to those of the trimethyl ester of PQQ (2) and the methyl ester of 7,9-didecarboxy PQQ (3). The synthesis of 4 was achieved by starting with 1-aminonaphthalene and constructing 2-carbomethoxybenz[g]indole (7) by a Japp-Klingemann reaction with methyl alpha-methylacetoacetate and a subsequent Fischer indolization reaction. The quinone function was introduced by a Fremy's salt oxidation of 5-aminoindole 9 which was prepared from 7 by regioselective nitration and catalytic hydrogenation. From the physical properties, it can be recognized that the peri pyridine nitrogen and the ester groups at the 7- and 9-positions considerably affect the electronic nature of the molecules. This is reflected on the reactivities of the quinones in the acetone-adduct formation, the reaction with phenylhydrazine, and the aerobic autorecycling oxidation of benzylamine. The significant roles of the pyridine nitrogen and the ester groups in these reactions are discussed.

  DOI：

  10.1021/jo00036a007

文献信息

• C-4 and C-5 adducts of cofactor PQQ (pyrroloquinolinequinone). Model studies directed toward the action of quinoprotein methanol dehydrogenase
  作者：Shinobu Itoh、Masaki Ogino、Yoshifumi Fukui、Hiroshi Murao、Mitsuo Komatsu、Yoshiki Ohshiro、Tsuyoshi Inoue、Yasushi Kai、Nobutami Kasai

  DOI：10.1021/ja00075a012

  日期：1993.11

  Methanol addition to the trimethyl ester of cofactor PQQ (PQQTME) was investigated in detail to obtain information on the action of quinoprotein methanol dehydrogenase. The hemiacetal-type adduct was easily isolated from a methanol solution of PQQTME. The crystal structure of the adduct was determined by X-ray diffraction for the first time, showing that methanol addition occurred at the S-position

  对辅因子 PQQ (PQQTME) 的三甲酯中添加甲醇进行了详细研究，以获得有关喹蛋白甲醇脱氢酶作用的信息。半缩醛型加合物很容易从 PQQTME 的甲醇溶液中分离出来。加合物的晶体结构首次通过 X 射线衍射确定，表明与丙酮加合物形成的情况一样，甲醇加成发生在醌的 S 位 (CS)。另一方面，在酸性条件下在甲醇中处理 PQQTME 得到二甲基缩醛衍生物作为主要产物，通过 X 射线晶体学分析确定甲醇的加成位置为 C-4