5-iminodaunorubicin | 72983-78-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-iminodaunorubicin
• 英文别名: (8S,10S)-8-acetyl-10-[(2R,4S,5S,6S)-4-amino-5-hydroxy-6-methyloxan-2-yl]oxy-6,8,11-trihydroxy-12-imino-1-methoxy-9,10-dihydro-7H-tetracen-5-one
• CAS: 72983-78-9
• 化学式: C₂₇H₃₀N₂O₉
• 分子量: 526.543
• InChiKey: BLLIIPIJZPKUEG-HPTNQIKVSA-N

物化性质

• 沸点：
  747.6±60.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  193
• 氢给体数：
  6
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  5-iminodaunorubicin 在 盐酸 、 sodium dithionite 、 氧气 作用下， 以 甲醇 为溶剂， 以3.0 mg的产率得到5-deoxydaunorubicin
  参考文献：
  名称：

  Synthesis and redox chemistry of 5-deoxydaunomycin. A long-lived hydroquinone tautomer

  摘要：

  Reduction of 5-iminodaunomycin with dithionite in anaerobic methanol followed by lowering the pH to 3 and saturating with air led to deamination without glycosidic cleavage to yield 89% 5-deoxydaunomycin. An intermediate observed during the reaction is proposed to be the hydroquinone tautomer, 8-acetyl-12-amino-10-[(3-amino-2,3,6-trideoxy-alpha-lyxo-hexopyranosyl)oxy]-1-methoxy-7,9,10,12-tetrahydro-6,8,11-trihydroxy-5(8H)-naphthacenone hydrochloride (1), which loses ammonia with a half-life of 49 min. Anaerobic reduction of 5-deoxydaunomycin with bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) (TM-3 dimer) in methanol buffered to an apparent pH of 8 yielded 26% recovered 5-deoxydaunomycin, 56% 5,7-dideoxydaunomycinone, and 18% 2-acetyl-11-hydroxy-7-methoxy-5,12-naphthacenedione (5) after 42 h and subsequent exposure to molecular oxygen. The reduction leads to relatively rapid formation of a long-lived transient proposed to be, 8-acetyl-10-[(3-amino-2,3,6-trideoxy-a-lyxo-hexopyranosyl)oxy]-l-methoxy-7,9,10,12-tetrahydro-6,8,11-trihydroxy-5(8H)-naphthacenone (4). Exposure of 4 at its maximum concentration to molecular oxygen yielded 88% recovered 5-deoxydaunomycin and 12% 5. Tetrahydronaphthacenone 4 disappeared with a half-life of 2283 min in the absence of oxygen and 16 min in air-saturated methanol. Mechanistic pathways to the products are proposed in Scheme II. Analysis of the apparent rate constants for disappearance of 4 indicates that 5-deoxydaunomycin undergoes glycosidic cleavage to its 7-deoxyaglycon 8000 times slower than daunomycin upon reduction to the hydroquinone state.

  DOI：

  10.1021/ja00066a012

文献信息

• Tresselt; Ihn; Horn, Pharmazie, 1984, vol. 39, # 6, p. 417 - 419
  作者：Tresselt、Ihn、Horn、Berg

  DOI：——

  日期：——
• Cu(II)-5-iminodaunorubicin complex. A circular dichroism study
  作者：Abderrahmane Moustatih、Arlette Garnier-Suillerot

  DOI：10.1016/s0020-1693(00)81291-8

  日期：1987.3
• Synthesis and redox chemistry of 5-deoxydaunomycin. A long-lived hydroquinone tautomer
  作者：Barbara Ann Schweitzer、Tad H. Koch

  DOI：10.1021/ja00066a012

  日期：1993.6

  Reduction of 5-iminodaunomycin with dithionite in anaerobic methanol followed by lowering the pH to 3 and saturating with air led to deamination without glycosidic cleavage to yield 89% 5-deoxydaunomycin. An intermediate observed during the reaction is proposed to be the hydroquinone tautomer, 8-acetyl-12-amino-10-[(3-amino-2,3,6-trideoxy-alpha-lyxo-hexopyranosyl)oxy]-1-methoxy-7,9,10,12-tetrahydro-6,8,11-trihydroxy-5(8H)-naphthacenone hydrochloride (1), which loses ammonia with a half-life of 49 min. Anaerobic reduction of 5-deoxydaunomycin with bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) (TM-3 dimer) in methanol buffered to an apparent pH of 8 yielded 26% recovered 5-deoxydaunomycin, 56% 5,7-dideoxydaunomycinone, and 18% 2-acetyl-11-hydroxy-7-methoxy-5,12-naphthacenedione (5) after 42 h and subsequent exposure to molecular oxygen. The reduction leads to relatively rapid formation of a long-lived transient proposed to be, 8-acetyl-10-[(3-amino-2,3,6-trideoxy-a-lyxo-hexopyranosyl)oxy]-l-methoxy-7,9,10,12-tetrahydro-6,8,11-trihydroxy-5(8H)-naphthacenone (4). Exposure of 4 at its maximum concentration to molecular oxygen yielded 88% recovered 5-deoxydaunomycin and 12% 5. Tetrahydronaphthacenone 4 disappeared with a half-life of 2283 min in the absence of oxygen and 16 min in air-saturated methanol. Mechanistic pathways to the products are proposed in Scheme II. Analysis of the apparent rate constants for disappearance of 4 indicates that 5-deoxydaunomycin undergoes glycosidic cleavage to its 7-deoxyaglycon 8000 times slower than daunomycin upon reduction to the hydroquinone state.