3,4-dihydro-5,8-dimethoxy-3-methylisocoumarin | 108207-07-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 3,4-dihydro-5,8-dimethoxy-3-methylisocoumarin
• 英文别名: 5,8-dimethoxy-3-methylisochroman-1-one；5,8-dimethoxy-3-methylisocoumarin；3-Methyl-5,8-dimethoxy-3,4-dihydroisocoumarin；5,8-dimethoxy-3-methyl-3,4-dihydroisochromen-1-one
• CAS: 108207-07-4
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: GPDRPMRZJXRCJW-UHFFFAOYSA-N

物化性质

• 沸点：
  409.1±45.0 °C(Predicted)
• 密度：
  1.158±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-dihydro-5,8-dimethoxy-3-methylisocoumarin 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 、 potassium tert-butylate 作用下， 以 四氯化碳 、 乙醚 、 甲苯 、 乙腈 为溶剂， 反应 56.0h， 生成 (E)-(3-(3,6-dimethoxy-2-(methoxycarbonyl)phenyl)allyl)triphenylphosphonium bromide
  参考文献：
  名称：

  Harwood, Laurence M., Journal of the Chemical Society. Perkin transactions I, 1984, # 11, p. 2577 - 2582

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4-dihydro-5,8-dimethoxy-3-methyl-1H-benzopyran 在 iron(II) triflate 、 2-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)-6-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)pyridine 、 氧气 作用下， 60.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 以5%的产率得到3,4-dihydro-5,8-dimethoxy-3-methylisocoumarin
  参考文献：
  名称：

  Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst

  摘要：

  Selective alpha-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective alpha-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O-2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H-2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O-2 into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H-2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts.

  DOI：

  10.1021/ja502167h

文献信息

• Synthesis of Azabenzisochromanequinone Antibiotics, II: 9(6)-Hydroxy-6(9)-Azabenzisochromanequinones via Aminoisochromanes and Meldrum's Acid
  作者：Carsten Tödter、Helmut Lackner

  DOI：10.1055/s-1997-1222

  日期：1997.5

  The synthesis of 6(7)-amino-5,8-dimethosyisochromanes 7,8, precursors of the B-C ring system of benzisochromanequinone antibiotics 1, is described. Subsequent N-alkylation using Meldrum's acid/trimethyl orthoformate followed by a high temperature cyclization and oxidative demethylation yields 9(6)-0-demethyl-6(9)-azaeleutherins 13 and 6(9)-azaepinanaomycin A methyl esters 14. The novel aza-analogues allowed further studies on the structure-activity relations in the field of (aza)benzisochromanequinone antibiotics.

  本文描述了苯并异色醌抗生素 1 的 B-C 环系统的前体 6(7)-氨基-5,8-二甲氧基异色醌 7,8 的合成过程。随后使用 Meldrum 酸/原甲酸三甲酯进行 N-烷基化，再经过高温环化和氧化去甲基化，得到 9(6)-0-demethyl-6(9)-azaeleutherins 13 和 6(9)-azaepinanaomycin A 甲酯 14。这些新型氮杂类似物有助于进一步研究（氮杂）苯并异色醌类抗生素的结构-活性关系。
• The synthesis of isochroman-4-ols and isochroman-3-ols: models for naturally occurring benzo[g]isochromanols
  作者：Charles B de Koning、Ivan R Green、Joseph P Michael、José R Oliveira

  DOI：10.1016/s0040-4020(01)00963-2

  日期：2001.11

  The synthesis of isochromanes containing hydroxy substituents at the 4- and 3-positions has been achieved. The key step for the synthesis of the isochroman-4-ols entailed an oxidative mercury mediated ring closure of 2-(prop-1-enyl)phenylmethanol derivatives, while in the synthesis of the isochroman-3-ols the key step involved ozonolysis of 2-(prop-2-enyl)phenylmethanol derivatives. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Toedter, Carsten; Lackner, Helmut, Liebigs Annalen, 1996, # 9, p. 1385 - 1394
  作者：Toedter, Carsten、Lackner, Helmut

  DOI：——

  日期：——
• Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst
  作者：Angela Gonzalez-de-Castro、Craig M. Robertson、Jianliang Xiao

  DOI：10.1021/ja502167h

  日期：2014.6.11

  Selective alpha-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective alpha-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O-2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H-2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O-2 into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H-2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts.
• Harwood, Laurence M., Journal of the Chemical Society. Perkin transactions I, 1984, # 11, p. 2577 - 2582
  作者：Harwood, Laurence M.

  DOI：——

  日期：——