(+/-)-phyllodulcin 3'-benzyl-8-methyl ether | 82780-52-7

• 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: (+/-)-phyllodulcin 3'-benzyl-8-methyl ether
• 英文别名: (+/-)-phyllodulcin benzyl methyl ether；Phyllodulcin benzyl methyl ether；8-Methoxy-3-(4-methoxy-3-phenylmethoxyphenyl)-3,4-dihydroisochromen-1-one
• CAS: 82780-52-7
• 化学式: C₂₄H₂₂O₅
• 分子量: 390.436
• InChiKey: XORDDEORUZSJCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-phyllodulcin 3'-benzyl-8-methyl ether 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 以51%的产率得到phyllodulcin
  参考文献：
  名称：

  叔苯甲酰胺的定向金属化：苯酚和叶绿素的短合成

  摘要：

  描述了通过邻位锂化的苯甲酰胺中间体简短合成异香豆素天然产物hydrangenol（）和phyllodulcin（）。

  DOI：

  10.1016/s0040-4039(00)87180-4
• 作为产物：
  描述：

  3-苄氧基-4-甲氧基苯甲醛 在 sodium hydroxide 、 氢气 、 lithium diisopropyl amide 作用下， 反应 8.0h， 生成 (+/-)-phyllodulcin 3'-benzyl-8-methyl ether
  参考文献：
  名称：

  叔苯甲酰胺的定向金属化：苯酚和叶绿素的短合成

  摘要：

  描述了通过邻位锂化的苯甲酰胺中间体简短合成异香豆素天然产物hydrangenol（）和phyllodulcin（）。

  DOI：

  10.1016/s0040-4039(00)87180-4

文献信息

• Ortho-lithiated tertiary benzamides. Chain extension via o-toluamide anion and general synthesis of isocoumarins including hydrangenol and phyllodulcin
  作者：Mitsuaki Watanabe、Masanori Sahara、Masaki Kubo、Sunao Furukawa、R. J. Billedeau、V. Snieckus

  DOI：10.1021/jo00179a002

  日期：1984.3
• Facile generation and trapping of .alpha.-oxo-o-quinodimethanes: synthesis of 3-aryl-3,4-dihydroisocoumarins and protoberberines
  作者：Satinder V. Kessar、Paramjit Singh、Rahul Vohra、Nachhattar Pal Kaur、D. Venugopal

  DOI：10.1021/jo00051a009

  日期：1992.12

  Fluorodesilylation of o-((trimethylsilyl)methyl)benzoyl derivatives 5 in the presence of aromatic aldehydes and alkyl fumarates gives 3-aryl-3,4-dihydroisocoumarins 6 and alpha-tetralones 10, respectively. Reaction of 5 with 3,4-dihydroisoquinolinium salts 19 leads to 8-oxoberbines 21. Using this procedure, racemic hydrangenol, phyllodulcin, tetrahydropalmatine (22a), and canadine (22b) have been synthesized.
• Kessar, S V; Gupta, Y P; Singh, Surat, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1993, vol. 32, # 6, p. 668 - 669
  作者：Kessar, S V、Gupta, Y P、Singh, Surat

  DOI：——

  日期：——
• Arnoldi, Anna; Bassoli, Angela; Merlini, Lucio, Gazzetta Chimica Italiana, 1992, vol. 122, # 10, p. 403 - 407
  作者：Arnoldi, Anna、Bassoli, Angela、Merlini, Lucio、Ragg, Enzio

  DOI：——

  日期：——
• Reaction of Benzocyclobutene Oxides with Aldehydes: Synthesis of Peshawarine and Other 3,4-Dihydroisocoumarins
  作者：John J. Fitzgerald、Alex R. Pagano、Vianne M. Sakoda、R. A. Olofson

  DOI：10.1021/jo00094a022

  日期：1994.7

  Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.