(+/-)-cycloshikonin | 77386-93-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+/-)-cycloshikonin
• 英文别名: 2-(5,5-Dimethyloxolan-2-yl)-5,8-dihydroxynaphthalene-1,4-dione
• CAS: 77386-93-7
• 化学式: C₁₆H₁₆O₅
• 分子量: 288.3
• InChiKey: ALRXDRQNAJOPCP-UHFFFAOYSA-N

物化性质

• 熔点：
  79-80 °C
• 沸点：
  530.3±50.0 °C(Predicted)
• 密度：
  1.377±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  83.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-cycloshikonin 在 吡啶 、 对甲苯磺酸 作用下， 反应 2.5h， 生成 5,8-diacetoxy-2-(1,4-diacetoxy-4-methylpentyl)-1,4-naphthoquinone
  参考文献：
  名称：

  Synthesis of naphthoquinone derivatives. 3. Cycloshikonin and its derivatives. A synthetic route to shikonin

  摘要：

  DOI：

  10.1021/jo00384a011
• 作为产物：
  描述：

  紫草素 在 三氯化铝 作用下， 以 硝基苯 为溶剂， 反应 1.5h， 以34 mg的产率得到(+/-)-cycloshikonin
  参考文献：
  名称：

  Two quinones from callus cultures of Echium lycopsis

  摘要：

  DOI：

  10.1016/s0031-9422(00)98558-3

文献信息

• A Novel Synthesis of Naphthazarin and Juglone Derivatives by Reaction of Naphthazarin and Juglone with Cyclic Enol Ethers
  作者：Yasuhiro Tanoue、Akira Terada、Hiroshige Taniguchi、Tadashi Okuma、Hiroshi Kaai、Mihoko Anan、Yasuyuki Kakara、Mika Doi、Shin-ichi Morishita

  DOI：10.1246/bcsj.66.3712

  日期：1993.12

  presence of BF3·OEt2 gave naphthazarin derivatives such as cycloshikonin, having a cyclic ether substituent, in one step. Cyclic enol ethers did not attack the quinone ring of naphthazarin but the benzene ring, and the corresponding naphthazarin derivatives were produced after tautomerization. This reaction was applicable to juglone to give juglone derivatives bearing a cyclic ether substituent.

  在BF3·OEt2的存在下，萘甲素与环烯醇醚在乙酸中的反应一步得到萘甲素衍生物，例如具有环醚取代基的环紫草素。环状烯醇醚不攻击萘并芴的醌环，而是攻击苯环，互变异构化后生成相应的萘并衍生物。该反应适用于胡桃酮，得到带有环醚取代基的胡桃酮衍生物。
• Synthesis of Shikalkin (±Shikonin) and Related Compounds
  作者：Akira Terada、Yasuhiro Tanoue、Akira Hatada、Hiroshi Sakamoto

  DOI：10.1246/bcsj.60.205

  日期：1987.1

  2-formyl-1,4,5,8-tetramethoxynaphthalene, was prepared through 1,4,5,8-tetramethoxynaphthalene, which was obtained from 1,5-naphthalenediol via three steps or from naphthazarin via one step. A total synthesis of shikalkin and dihydroshikalkin have been accomplished with this aldehyde via a side-chain introductions with Grignard reactions and the following demethylations.

  关键中间体2-甲酰基-1,4,5,8-四甲氧基萘是以1,4,5,8-四甲氧基萘为原料，由1,5-萘二醇三步法或萘甲素一步法制得。shikalkin 和二氢shikalkin 的全合成已经用这种醛通过侧链引入与格氏反应和以下去甲基化完成。
• Successive Michael Reaction-Sigmatropic Rearrangement of Naphthodiquinone with O-Silylated Ketene Acetals Leading to Synthesis of Cycloshikonin and Structure-Reactivity Relationship for Side Chain of Naphthazarins.
  作者：Mariko ASO、Ken KANEMATSU

  DOI：10.1248/cpb.41.1549

  日期：——

  Synthesis of cycloshikonin via successive Michael reaction-sigmatropic rearrangement of naphthodiquinone with O-silylated ketene acetals is described. The structure dependence of the reactivity of the side chain of intermediary naphthazarin derivatives has also been investigated.

  该研究描述了通过萘醌与 O-硅烷化酮乙缩醛的连续迈克尔反应-对位重排合成环紫草素的过程。此外，还研究了中间萘甲萘醌衍生物侧链反应活性的结构依赖性。
• Process for preparing derivatives of naphthazarin
  申请人：NIPPON OIL CO. LTD.

  公开号：EP0200219A2

  公开（公告）日：1986-11-05

  A process is provided for preparing a derivative of naphthazarin represented by the general formula (I) of: wherein R is an atom or a group selected from the group consisting of hydroxyl, oxyhydrocarbon, siloxy and acyloxy groups and halogen atoms. wherein X1, X2 and X3 each stands for an atom or a group consisting of hydrogen, a hydroxyl group, organic residues and halogens, and R1 to R6 each stands for an atom or a group selected from the group consisting of hydrogen and hydrocarbon groups. The derivative of naphthazarin is prepared by the step of reacting, in the presence of an acid catalyst, the following compounds represented by the general formulae (II) and (III):

  提供了一种制备由通式(I)代表的萘甲萘灵衍生物的工艺： 其中R是原子或选自羟基、氧烃基、硅氧基、酰氧基和卤素原子组成的基团。 其中X1、X2和X3各自代表原子或选自氢、羟基、有机残基和卤素组成的基团，R1至R6各自代表原子或选自氢和烃基组成的基团。 该萘甲萘灵衍生物的制备步骤是：在酸催化剂存在下，使通式(II)和(III)代表的下列化合物反应：
• Synthesis of shikalkin and certain related compounds
  作者：V. L. Novikov、N. N. Balaneva、A. M. Moiseenkov、G. B. Elyakov

  DOI：10.1007/bf00864352

  日期：1992.8

  A successful total synthesis of a biologically active pigment from plants of the Boraginaceae family was carried out with naphthazarine as the starting material, and using the 1,4,5,8-tetramethoxynaphthalene, the corresponding 2-vinyl derivative and its epoxide or a cyclopropane adduct with diazoacetic ester at the key stages. In the course of developing the scheme of the synthesis of shikalkin, its three analogs were obtained, differing in the nature of the monoterpenoid side chain.