3-chloro-2,5,6,8-tetrahydroxy-1,4-naphthoquinone | 367922-79-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3-chloro-2,5,6,8-tetrahydroxy-1,4-naphthoquinone
• CAS: 367922-79-0
• 化学式: C₁₀H₅ClO₆
• 分子量: 256.599
• InChiKey: YPOXQUDCHQWVFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.19
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  115.06
• 氢给体数：
  4.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 3-chloro-2,5,6,8-tetrahydroxy-1,4-naphthoquinone 以 乙醚 为溶剂， 以78%的产率得到3-chloro-5,8-dihydroxy-2,6-dimethoxy-1,4-naphthoquinone
  参考文献：
  名称：

  Synthesis of Echinamines A and B, the First Aminated Hydroxynaphthazarins Produced by the Sea Urchin Scaphechinus mirabilis and Its Analogues

  摘要：

  The first total synthesis of two marine aminated hydroxynaphthazarins, echinamines A (3-amino-7-ethyl- 2,5,6,8-tetrahydroxy-1,4- naphthoquinone) and B (2-amino-7-ethyl- 3,5,6,8-tetrahydroxy-1,4- naphthoquinone), produced by the sea urchin Scaphechinus mirabilis is described. This was achieved from 1,2,4-triacetoxybenzene (13) through a sequence involving double Fries rearrangement of 13, reduction of 3,5-diacetyl-1,2,4-trihydroxybenzene (14), methylation of 3,5-diethyl-1,2,4- trihydroxybenzene (15), simultaneous double acylation of 3,5-diethyl-1,2,4- trimethoxybenzene ( 16) with a dichloromaleic anhydride-ethyl radical elimination process, methylation of 6,7-dichloro-3-ethyl-2-hydroxynaphthazarin (17), nucleophilic substitution of a chlorine atom by the methoxy group in 6,7-dichloro-3-ethyl-2-methoxynaphthazarin (18), introduction of an amino group via direct substitution of a chlorine atom in 7-chloro-3-ethyl-2,6- dimethoxy- (11) and 7-chloro-2-ethyl-3,6-dimethoxynaphthazarins (12) by an azido group, and functional group deprotection. The synthesis of amino analogues of spinazarin and spinochrome D is also described.

  DOI：

  10.1021/np0502185
• 作为产物：
  描述：

  2,3-dichloro-5,8-dihydroxy-[1,4]naphthoquinone 在 硫酸 、 硼酸 作用下， 反应 0.33h， 以69%的产率得到3-chloro-2,5,6,8-tetrahydroxy-1,4-naphthoquinone
  参考文献：
  名称：

  Synthesis of Echinamines A and B, the First Aminated Hydroxynaphthazarins Produced by the Sea Urchin Scaphechinus mirabilis and Its Analogues

  摘要：

  The first total synthesis of two marine aminated hydroxynaphthazarins, echinamines A (3-amino-7-ethyl- 2,5,6,8-tetrahydroxy-1,4- naphthoquinone) and B (2-amino-7-ethyl- 3,5,6,8-tetrahydroxy-1,4- naphthoquinone), produced by the sea urchin Scaphechinus mirabilis is described. This was achieved from 1,2,4-triacetoxybenzene (13) through a sequence involving double Fries rearrangement of 13, reduction of 3,5-diacetyl-1,2,4-trihydroxybenzene (14), methylation of 3,5-diethyl-1,2,4- trihydroxybenzene (15), simultaneous double acylation of 3,5-diethyl-1,2,4- trimethoxybenzene ( 16) with a dichloromaleic anhydride-ethyl radical elimination process, methylation of 6,7-dichloro-3-ethyl-2-hydroxynaphthazarin (17), nucleophilic substitution of a chlorine atom by the methoxy group in 6,7-dichloro-3-ethyl-2-methoxynaphthazarin (18), introduction of an amino group via direct substitution of a chlorine atom in 7-chloro-3-ethyl-2,6- dimethoxy- (11) and 7-chloro-2-ethyl-3,6-dimethoxynaphthazarins (12) by an azido group, and functional group deprotection. The synthesis of amino analogues of spinazarin and spinochrome D is also described.

  DOI：

  10.1021/np0502185

文献信息

• ——
  作者：V. P. Glazunov、A. Ya. Tchizhova、O. P. Shestak、G. I. Sopel"nyak、V. Ph. Anufriev

  DOI：10.1023/a:1009533403588

  日期：——

  A set of substituted 2-hydroxy-6(7)-methoxynaphthazarins and 7(8)-hydroxypyranonaphthazarins were synthesized. The IR spectra of 2-hydroxy-6-methoxynaphthazarins and 7-hydroxypyranonaphthazarins, on the one hand, and of 2-hydroxy-7-methoxynaphthazarins and 8-hydroxypyranonaphthazarins, on the other hand, have the characteristic nonoverlapping intervals of stretching vibration frequencies of the beta -hydroxy groups. These regularities confirm the structures of cristazarin and 6-methylcristazarin, which are metabolites of lichen Cladonia cristatella.
• First direct observation of tautomerism of monohydroxynaphthazarins by IR-spectroscopy
  作者：Valery P. Glazunov、Alla Ya. Tchizhova、Nataly D. Pokhilo、Victor Ph. Anufriev、George B. Elyakov

  DOI：10.1016/s0040-4020(02)00060-1

  日期：2002.2

  Some substituted monohydroxylated naphthazarins (5,8-dihydroxy-1,4-naphthoquinones) were synthesized and studied by IR-spectroscopy in aprotic organic solvents at ambient temperature. Two narrow stretching mode bands in the high frequency range 3540-3410 cm(-1) due to a beta-hydroxy group were observed; it was established that this effect was caused by tautomerism. This allowed the creation of a convenient and accurate method for the measurement of a small amount of tautomer engaged in rapid exchange with the principal tautomer. Solvent and substituent effects were estimated. (C) 2002 Elsevier Science Ltd. All rights reserved.