(+/-)-3-(3-benzyloxy-4-methoxyphenyl)-3,4-dihydro-8-hydroxy-1H-2-benzopyran-1-one | 66380-87-8

• 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-(3-benzyloxy-4-methoxyphenyl)-3,4-dihydro-8-hydroxy-1H-2-benzopyran-1-one
• 英文别名: 3'-O-benzylphyllodulcin；3-(3'-benzyloxy-4'-methoxyphenyl)-8-hydroxy-3,4-dihydrobenzopyran-1-one；3-(3-benzyloxy-4-methoxyphenyl)-3,4-dihydro-8-hydroxyisocoumarin；8-Hydroxy-3-(4-methoxy-3-phenylmethoxyphenyl)-3,4-dihydroisochromen-1-one
• CAS: 66380-87-8
• 化学式: C₂₃H₂₀O₅
• 分子量: 376.409
• InChiKey: RYDPHYUWUYGMSX-UHFFFAOYSA-N

物化性质

• 熔点：
  141-143 °C
• 沸点：
  590.9±50.0 °C(Predicted)
• 密度：
  1.275±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-3-(3-benzyloxy-4-methoxyphenyl)-3,4-dihydro-8-hydroxy-1H-2-benzopyran-1-one 在 palladium on activated charcoal 吡啶 、 氢气 、 sodium ethanolate 作用下， 以 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 7.55h， 生成 (-)-phyllodulcin
  参考文献：
  名称：

  Enantiodifferentiation in Taste Perception of the phyllodulcins

  摘要：

  Both enantiomers of phyllodulcin 1 have been prepared. Ester 2 was synthesized in a Wittig reaction from O-benzyl isovanillin. The corresponding stilbene carboxylic acid 3 could be cyclized with CF3CO2H to produce the 3'-benzyl ether 4 of (+/-)-phyllodulcin. Acylation with (1R,4S)-camphanoyl chloride gave first 5 and after hydrogenolysis of the benzyl ether group in 5 the diastereomeric esters 6. The diastereomerically pure 8-(1R,4S)-camphanoate (+)-6 of (R)-phyllodulcin could be isolated by repeated recrystallization. With (1S,4R)-camphanoyl chloride the enantiomeric 8-(1S,4R)-camphanoate (-)-6 of O-phyllodulcin could be prepared via ent-5 from a mixture of the diastereomeric esters ent-6. Ethanolysis of (+)-6 gave (R)-phyllodulcin [(+)-1] with 99% ee. The enantiomeric (S)-(-)-1 with 98% ee could be obtained from (-)-6. While (+)-1, the enantiomer occuring in fermented leaves of amacha, has an intense sweet taste, the enantiomer (-)-1 is completely tasteless.

  DOI：

  10.1016/0957-4166(95)00367-x
• 作为产物：
  描述：

  (3-acetyloxy-2-ethoxycarbonylbenzyl)-triphenylphosphonium bromide 在 氢氧化钾 、 sodium ethanolate 、 三氟乙酸 作用下， 以 乙醇 、 水 、 1,2-二氯乙烷 为溶剂， 反应 51.0h， 生成 (+/-)-3-(3-benzyloxy-4-methoxyphenyl)-3,4-dihydro-8-hydroxy-1H-2-benzopyran-1-one
  参考文献：
  名称：

  Efficient syntheses of (±)-hydrangenol, (±)-phyllodulcin and (±)-macrophyllol

  摘要：

  In this paper we report on a efficient and flexible synthetic route towards the total syntheses of the dihydrocoumarine derivatives hydrangenol (1), phyllodulcin (1a) and macrophyllol (6b). The syntheses started with a readily available phosphonium salt 2 and suitable modified benzaldehydes 3/3a/3b resulting in 46 to 61% overall yields in three to four-steps sequences. The racemic products could be separated by chiral HPLC. The evidence of the(R)-enantiomer for sweetness could be demonstrated for la. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.09.046

文献信息

• Takeuchi, Naoki; Ochi, Kazue; Murase, Masayuki, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 12, p. 4360 - 4363
  作者：Takeuchi, Naoki、Ochi, Kazue、Murase, Masayuki、Tobinaga, Seisho

  DOI：——

  日期：——
• Takeuchi, Naoki; Murase, Masayuki; Ochi, Kazue, Chemical and pharmaceutical bulletin, 1980, vol. 28, # 10, p. 3013 - 3019
  作者：Takeuchi, Naoki、Murase, Masayuki、Ochi, Kazue、Tobinaga, Seisho

  DOI：——

  日期：——
• Enantiodifferentiation in Taste Perception of the phyllodulcins
  作者：Reinhard Zehnter、Hans Gerlach

  DOI：10.1016/0957-4166(95)00367-x

  日期：1995.11

  Both enantiomers of phyllodulcin 1 have been prepared. Ester 2 was synthesized in a Wittig reaction from O-benzyl isovanillin. The corresponding stilbene carboxylic acid 3 could be cyclized with CF3CO2H to produce the 3'-benzyl ether 4 of (+/-)-phyllodulcin. Acylation with (1R,4S)-camphanoyl chloride gave first 5 and after hydrogenolysis of the benzyl ether group in 5 the diastereomeric esters 6. The diastereomerically pure 8-(1R,4S)-camphanoate (+)-6 of (R)-phyllodulcin could be isolated by repeated recrystallization. With (1S,4R)-camphanoyl chloride the enantiomeric 8-(1S,4R)-camphanoate (-)-6 of O-phyllodulcin could be prepared via ent-5 from a mixture of the diastereomeric esters ent-6. Ethanolysis of (+)-6 gave (R)-phyllodulcin [(+)-1] with 99% ee. The enantiomeric (S)-(-)-1 with 98% ee could be obtained from (-)-6. While (+)-1, the enantiomer occuring in fermented leaves of amacha, has an intense sweet taste, the enantiomer (-)-1 is completely tasteless.
• Efficient syntheses of (±)-hydrangenol, (±)-phyllodulcin and (±)-macrophyllol
  作者：Mehmet Günes、Andreas Speicher

  DOI：10.1016/j.tet.2003.09.046

  日期：2003.10

  In this paper we report on a efficient and flexible synthetic route towards the total syntheses of the dihydrocoumarine derivatives hydrangenol (1), phyllodulcin (1a) and macrophyllol (6b). The syntheses started with a readily available phosphonium salt 2 and suitable modified benzaldehydes 3/3a/3b resulting in 46 to 61% overall yields in three to four-steps sequences. The racemic products could be separated by chiral HPLC. The evidence of the(R)-enantiomer for sweetness could be demonstrated for la. (C) 2003 Elsevier Ltd. All rights reserved.