(+/-)-oxyrubroflavin

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚砜
• 英文名称: (+/-)-oxyrubroflavin
• 英文别名: [[2,6-bis(methylsulfinyl)-4-oxocyclohexa-2,5-dien-1-ylidene]amino]urea
• 化学式: C₉H₁₁N₃O₄S₂
• 分子量: 289.336
• InChiKey: YAVOTDRFBZKABB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  157
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  deoxyrubroflavin 在 ammonium cerium(IV) nitrate 作用下， 以53%的产率得到(+/-)-rubroflavin
  参考文献：
  名称：

  Pigments from the Puffball Calvatia rubro-flava − Isolation, Structural Elucidation and Synthesis

  摘要：

  The orange pigment rubroflavin (1) from the dried fruit bodies of Calvatia rubro-flava (Lycoperdaceae) owes its high optical rotation to a methanesulfinyl group directly attached to a 1,4-benzoquinone semicarbazone chromophore. Rubroflavin is present in fresh fungi in its leuco form 4, which is easily oxidized to 1. Thermal fragmentation of 1 yields (-)-3-methanesulfinyl-5-(methylthio)phenol (6), whose configuration was assigned as (S) by quantum mechanical calculations. This result is supported by CD comparison of 6 with (S)-4-(methanesulfinyl) toluene, and the synthesis of (S)-1 from esters of deoxyrubroflavin (8) by stereoselective sulfoxidation. In the same manner, optically active (S,S)-oxyrubroflavin (2) and (S)-craniformin (3) were obtained. NMR measurements in different solvents indicate that 1 and the related 1,4-benzoquinone semicarbazones are in equilibrium with their azophenol tautomers.

  DOI：

  10.1002/1099-0690(200108)2001:16<3097::aid-ejoc3097>3.0.co;2-v

文献信息

• Pigments from the Puffball Calvatia rubro-flava − Isolation, Structural Elucidation and Synthesis
  作者：Burkhard Fugmann、Siegbert Arnold、Wolfgang Steglich、Jörg Fleischhauer、Charlotte Repges、Axel Koslowski、Gerhard Raabe

  DOI：10.1002/1099-0690(200108)2001:16<3097::aid-ejoc3097>3.0.co;2-v

  日期：2001.8

  The orange pigment rubroflavin (1) from the dried fruit bodies of Calvatia rubro-flava (Lycoperdaceae) owes its high optical rotation to a methanesulfinyl group directly attached to a 1,4-benzoquinone semicarbazone chromophore. Rubroflavin is present in fresh fungi in its leuco form 4, which is easily oxidized to 1. Thermal fragmentation of 1 yields (-)-3-methanesulfinyl-5-(methylthio)phenol (6), whose configuration was assigned as (S) by quantum mechanical calculations. This result is supported by CD comparison of 6 with (S)-4-(methanesulfinyl) toluene, and the synthesis of (S)-1 from esters of deoxyrubroflavin (8) by stereoselective sulfoxidation. In the same manner, optically active (S,S)-oxyrubroflavin (2) and (S)-craniformin (3) were obtained. NMR measurements in different solvents indicate that 1 and the related 1,4-benzoquinone semicarbazones are in equilibrium with their azophenol tautomers.