2-acetyl-11-hydroxy-7-methoxy-5,12-naphthacenedione | 130858-21-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 并四苯
• 英文名称: 2-acetyl-11-hydroxy-7-methoxy-5,12-naphthacenedione
• 英文别名: 2-acetyl-11-hydroxy-7-methoxytetracene-5,12-dione
• CAS: 130858-21-8
• 化学式: C₂₁H₁₄O₅
• 分子量: 346.339
• InChiKey: VLIFUKMZWSKCED-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  80.67
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  5-deoxydaunorubicin 在 氢溴酸 、 溶剂黄146 作用下， 反应 0.5h， 以35%的产率得到2-acetyl-11-hydroxy-7-methoxy-5,12-naphthacenedione
  参考文献：
  名称：

  柔红霉素氢醌七乙酸酯厌氧皂化的糖苷裂解

  摘要：

  早先报道，在氩气脱气的四氢呋喃 (THF)/水介质中，用 7 当量氢氧化锂将柔红霉素氢醌 (6) 的七乙酸酯皂化为 N-乙酰柔红霉素氢醌 (7)，不会产生糖苷裂解，生成 7-脱氧柔红霉素(5) (J. Am. Chem. Soc. 1991, 113, 1373)。暴露于空气后表征的唯一产品是 N-乙酰道诺霉素 (8)。该结果被解释为反对在氢醌氧化还原状态下柔红霉素糖苷裂解的可能证据。我们现在报告，在真空中在冻融脱气的 THF/水中进行皂化产生 10% (5), 17% 8, 28% N-乙酰-5-脱氧道诺霉素 (12), 7% 7-表道诺霉素 (13) , 2% 道诺霉素 (14), 9% 2-乙酰-11-羟基-7-甲氧基-5,12-萘二酮 (15), 14% 分布在三种不明产品中

  DOI：

  10.1021/ja00066a013

文献信息

• An entry to the ring B:ring C bishydroquinone leucodaunomycin series containing an intact carbohydrate
  作者：Gary A. Sulikowski、Edward Turos、Samuel J. Danishefsky、Gayle M. Shulte

  DOI：10.1021/ja00004a045

  日期：1991.2

  It has been found that diacetylation of the phenolic hydroxyl groups at C-6 and C-11 of daunomycin provides a product that undergoes reduction of the ring C quinone to a hydroquinone without loss of the glycosyloxy function at C-7. Access to a stable heptaacetate incorporating the nuclear bishydroquinone ensemble is thus provided. Basic hydrolysis of this compound accompanied by oxidation restores

  已经发现，道诺霉素的 C-6 和 C-11 处的酚羟基的二乙酰化提供了一种产物，该产物在不丧失 C-7 处的糖基氧基官能团的情况下将环 C 醌还原为氢醌。因此提供了获得包含核双氢醌系综的稳定七乙酸酯的途径。该化合物的碱性水解伴随氧化还原 N-乙酰道诺霉素。该反应的成功揭示了通过这种无色中间体形成醌甲基化物的惊人抗性
• 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.
• SULIKOWSKI, GARY A.;TUROS, EDWARD;DANISHEFSKY, SAMUEL J.;SHULTE, GAYLE M., J. AMER. CHEM. SOC., 113,(1991) N, C. 1373-1377
  作者：SULIKOWSKI, GARY A.、TUROS, EDWARD、DANISHEFSKY, SAMUEL J.、SHULTE, GAYLE M.

  DOI：——

  日期：——