6-methyl-3,4-benzotropolone

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 环庚三烯酮
• 英文名称: 6-methyl-3,4-benzotropolone
• 英文别名: 6-hydroxy-8-methyl-5H-benzo[7]annulen-5-one；5-Hydroxy-8-methylbenzo[7]annulen-6-one
• 化学式: C₁₂H₁₀O₂
• 分子量: 186.21
• InChiKey: XLQQRQNEGJTPGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  乙基1-氧亚基-2,3-二氢-1H-茚-2-甲酸基酯 在 samarium diiodide 、 ammonium cerium(IV) nitrate 、 氢溴酸 、 sodium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 0.83h， 生成 6-methyl-3,4-benzotropolone
  参考文献：
  名称：

  Novel transformation of 2-substituted alkyl 1-indanone-2-acetates to 6-substituted 3,4-benzotropolones through sequential reduction and oxidation processes using Sm(II) and Ce(IV) salts

  摘要：

  When 2-substituted alkyl 1-indanone-2-acetates 1 were treated with samarium diiodide, 3-substituted 2-hydroxy-2,3-methano-1-oxo-1,2,3,4-tetrahydronaphthalenes 4 were obtained. The reaction is proposed to proceed through a rearrangement initiated by intramolecular ketone-ester coupling. Oxidation of these products 4 or their silyl ethers 13 by ceric(IV) ammonium nitrate involving regioselective bond cleavage of their bicyclo[4.1.0]-rings produced the corresponding benzotropolone derivatives 10. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.10.083

文献信息

• In situ generated tris(p-bromophenyl)amine radical cation promoted electron transfer reaction of cyclopropyl silyl ethers
  作者：Eietsu Hasegawa、Koji Kakinuma、Tomoyo Yanaki、Shota Komata

  DOI：10.1016/j.tet.2009.09.108

  日期：2009.12

  utilized to promote the oxidative ring-opening reaction of cyclopropyl silyl ethers giving ring-expanded ketones. Exploration of salt quantity effect on the reaction allowed us to hypothesize that amine radical cation is regenerated through the oxidation of neutral amine by hexachloroantimonate anion. Based on this hypothesis, amine radical cation was initially generated by the treatment of parent amine

  利用三（对-溴苯基）六氯锑酸铵和高氯酸根来促进环丙基甲硅烷基醚的氧化开环反应，得到扩环的酮。探索盐对反应的影响使我们可以假设胺自由基阳离子是通过六氯锑酸根阴离子将中性胺氧化而再生的。基于该假设，首先通过用五氯化锑或高氯酸银和分子碘的混合物处理母体胺来生成胺自由基阳离子，然后与相同的底物反应。发现原位产生的胺自由基阳离子促进了反应，并且与使用相应的盐试剂相比，以更好的产率获得了预期的产物。
• Syntheses of 7‐, 8‐ and 9‐Bromobenzotropolone, Cross‐Couplings of Their Methyl Ethers, and Deprotection to 7‐, 8‐ or 9‐Substituted Benzotropolones
  作者：Philip Koblischek、Reinhard Brückner

  DOI：10.1002/ejoc.202200686

  日期：2022.10.7

  While unprotected benzotropolone is brominated at C-7 we found that O-acetylbenzotropolone is brominated at C-8 and O-methylbenzotropolone at C-9. 7-, 8-, and 9-bromo-O-methylbenzotropolone underwent Suzuki-Miyaura, Sonogashira, Negishi, and Mizoroki-Heck couplings. O-Demethylation provided 31 new and 3 already known benzotropolones.

  虽然未受保护的苯并托酚酮在 C-7 处溴化，但我们发现O-乙酰苯并托酚酮在 C-8 处溴化，而O-甲基苯并托酚酮在 C-9 处溴化。7-、8-和 9-溴-O-甲基苯并托酚酮经历了 Suzuki-Miyaura、Sonogashira、Negishi 和 Mizoroki-Heck 偶联。O-去甲基化提供了 31 种新的和 3 种已知的苯并托品酮。
• Novel transformation of 2-substituted alkyl 1-indanone-2-acetates to 6-substituted 3,4-benzotropolones through sequential reduction and oxidation processes using Sm(II) and Ce(IV) salts
  作者：Kazuki Iwaya、Mutsuko Tamura、Momoe Nakamura、Eietsu Hasegawa

  DOI：10.1016/j.tetlet.2003.10.083

  日期：2003.12

  When 2-substituted alkyl 1-indanone-2-acetates 1 were treated with samarium diiodide, 3-substituted 2-hydroxy-2,3-methano-1-oxo-1,2,3,4-tetrahydronaphthalenes 4 were obtained. The reaction is proposed to proceed through a rearrangement initiated by intramolecular ketone-ester coupling. Oxidation of these products 4 or their silyl ethers 13 by ceric(IV) ammonium nitrate involving regioselective bond cleavage of their bicyclo[4.1.0]-rings produced the corresponding benzotropolone derivatives 10. (C) 2003 Elsevier Ltd. All rights reserved.