trans-2,3-dimethyl-1,4,4a,9a-tetrahydroxanthone | 113272-08-5

• 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: trans-2,3-dimethyl-1,4,4a,9a-tetrahydroxanthone
• 英文别名: 9H-Xanthen-9-one, 1,4,4a,9a-tetrahydro-2,3-dimethyl-, trans-；1,4,4a,9,9a-Tetrahydro-2,3-dimethyl-9H-xanthen-9-one；cis-2,3-dimethyl-1,4,4a,9a-tetrahydroxanthone
• CAS: 113272-08-5；113272-09-6
• 化学式: C₁₅H₁₆O₂
• 分子量: 228.291
• InChiKey: QGJFDPOBQUREBP-GXTWGEPZSA-N

物化性质

• 沸点：
  358.0±42.0 °C(Predicted)
• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  色酮 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 trans-2,3-dimethyl-1,4,4a,9a-tetrahydroxanthone
  参考文献：
  名称：

  Tandem reactions in 4-siloxy-1-benzopyrylium salts: introduction of substituents and cyclohexene and cyclopentane annulation in chromones

  摘要：

  Reactions of 4-[(tert-butyldimethylsilyl)oxy]-1-benzopyrylium triflates (2a-c) with silyl enol ethers (3a-d) or allyl organometallic reagents (5a-c) afforded the corresponding 2-substituted 4-siloxy-2H-1-benzopyrans (4a-d and 6a-d) along with 2,3-dihydrobenzopyrone derivatives (7a-c). An unexpected cyclopentane annulation to give 8a,b was observed in the reaction of 2a,b with 3-(trimethylsilyl)-1-butene (5d). Treatment of the products (4a and 6a) with electrophiles (iminium salt, NBS, and NCS) converted them into the corresponding 2,3-disubstituted 2,3-dihydrobenzopyrone derivatives (9a-c). Reaction of benzopyrylium salts (2a,b) with alpha,beta-unsaturated ketones (10a-g) in the presence of tert-butyldimethylsilyl triflate and 2,6-lutidine gave cyclohexene annulation products (xanthone derivatives, 11a-j) in moderate to high yield. The reaction mechanisms are explained in terms of stereoelectronic and 1,3-allylic strain effects together with steric hindrance during the reaction.

  DOI：

  10.1021/jo00006a018

文献信息

• Cycloadditions of substituted benzopyran-4-ones to electron-rich dienes: a new route to xanthone derivatives
  作者：Peter J. Cremins、Suthiweth T. Saengchantara、Timothy W. Wallace

  DOI：10.1016/s0040-4020(01)86849-6

  日期：1987.1

  3-butadiene 12 to give the respective adducts 13,14, and 18 as mixtures of C-l stereoisomers. Heating the 3-arylsulphinylchromone 5 with the diene 12 afforded 3-hydroxyxanthone 23 in 50% yield, the presumed cycloaddition - elimination sequence constituting a new route to xanthone systems. Desilylation of 13,14, and 18 in acidic media provided 25,26, and 27 respectively.

  在氯化钛（IV）的存在下，苯并吡喃酮1和3与2,3-二甲基-1,3-丁二烯反应，得到相应的（4 + 2）环加合物8和11，前者进行了简单的甲酰基化，得到9和10。化合物1，3和4例行高效非催化环加成到1-甲氧基-3-（三甲基甲硅烷基）-1,3-丁二烯12，得到相应加合物13,14，和18例如Cl立体异构体的混合物。用二烯12加热3-芳基亚磺酰基色酮5以50％的收率得到3-羟基黄酮23，假定的环加成-消除顺序构成了通往黄酮系统的新途径。在酸性介质中进行13,14和18的脱甲硅烷基分别提供25,26和27。