2-chloro-5,8-dihydroxy-[1,4]naphthoquinone | 14918-68-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-chloro-5,8-dihydroxy-[1,4]naphthoquinone
• 英文别名: 5,8-dihydroxy-2-chloro-1,4-naphthoquinone；2-chloro-5,8-dihydroxy-1,4-naphthoquinone；2-Chlor-5,8-dihydroxy-[1,4]naphthochinon；2-chloro-5,8-dihydroxynaphthalene-1,4-dione
• CAS: 14918-68-4
• 化学式: C₁₀H₅ClO₄
• 分子量: 224.6
• InChiKey: FTPNIWQGVWICKY-UHFFFAOYSA-N

物化性质

• 熔点：
  178-179 °C
• 沸点：
  491.4±45.0 °C(Predicted)
• 密度：
  1.73±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-chloro-5,8-dihydroxy-[1,4]naphthoquinone 在 lead(IV) acetate 、 盐酸 作用下， 以 溶剂黄146 为溶剂， 反应 0.75h， 生成 2,6-dichloronaphthazarin
  参考文献：
  名称：

  Echavarren, Antonio; Prados, Pilar; Farina, Francisco, Journal of Chemical Research, Miniprint, 1986, # 10, p. 3162 - 3188

  摘要：

  DOI：
• 作为产物：
  描述：

  5,8-dihydroxy-2-[(trifluoromethanesulfonyl)oxy]-1,4-naphthoquinone 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 三丁基苯基锡 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 以85%的产率得到2-chloro-5,8-dihydroxy-[1,4]naphthoquinone
  参考文献：
  名称：

  Palladium-Catalyzed Coupling of Naphthoquinone Triflates with Stannanes. Unprecedented Nucleophilic Aromatic Substitution on a Hydroxynaphthoquinone Triflate

  摘要：

  DOI：

  10.1021/jo9621027
• 作为试剂：
  描述：

  3-羟基-2-吡喃酮 、 6-chloronaphthazarin 在 2-chloro-5,8-dihydroxy-[1,4]naphthoquinone 、 lead dioxide 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以13%的产率得到1,4-diacetoxy-5-hydroxy-9,10-anthraquinone
  参考文献：
  名称：

  Polycyclic hydroxyquinones. 13. A novel synthesis of islandicin and digitopurpone

  摘要：

  DOI：

  10.1021/jo00174a047

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。
• Spinochrome synthesis
  作者：I. Singh、R.E. Moore、C.W.J. Chang、R.T. Ogata、P.J. Scheuer

  DOI：10.1016/s0040-4020(01)98704-6

  日期：1968.1

  widely distributed structural pigments of the sea urchins (echinoids) one (spinochrome B) is a derivative of juglone, while four (spinochromes A, C, D, and E) are derivatives of naphthazarin. In addition to the two peri OH groups of naphthazarin these compounds bear one or more β-hydroxyls and/or an acetyl side chain. The synthesis of these four naphthazarin derivatives is described. The naphthalene skeleton

  在海胆的五种广泛分布的结构性颜料（类神经碱）中，一种（螺闪体色素B）是朱古龙的衍生物，而四种（螺闪体色素A，C，D和E）是萘甲萘林的衍生物。除了这两个围萘他沙林的OH基团带有一个或多个β-羟基和/或乙酰基侧链。描述了这四种萘他林衍生物的合成。萘骨架是通过将1,2-二羟基-3,4-二甲氧基苯与氯-或二氯马来酸酐在铝-氯化钠熔体中缩合而构建的。通过用甲醇盐离子的亲核取代氯或通过Thiele方法引入了更多的氧官能团。通过制备无色乙酸酯并将其用乙酸酐-三氟化硼处理，将乙酰基侧链连接至聚羟基萘醌。在加工过程中水解和氧化后，萘扎林体系得以再生。
• Reactions of Keten Acetals. Part I. A Simple Synthesis of Some Naturally Occurring Anthraquinones
  作者：Jacques Banville、Jean-Louis Grandmaison、Gérard Lang、Paul Brassard

  DOI：10.1139/v74-011

  日期：1974.1.1

  A study of the condensation of keten acetals with some halonaphthoquinones has led to the simple and regiospecific synthesis of some naturally occurring anthraquinones: catenarin, helminthosporin, emodin, and chrysophanol. The results show unambiguously that a previously proposed mechanism is erroneous. The reaction of these acetals with chloromaleic anhydride also provided a one-step preparation of

  对烯酮缩醛与一些卤代萘醌缩合的研究导致了一些天然蒽醌的简单和区域特异性合成：连环素、蠕孢菌素、大黄素和大黄酚。结果明确表明，先前提出的机制是错误的。这些缩醛与氯代马来酸酐的反应也提供了一些取代邻苯二甲酸酐的一步制备。
• Reactions of ketene acetals-14 The use of simple mixed vinylketene acetals in the annulation of quinones
  作者：Jacques Savard、Paul Brassard

  DOI：10.1016/s0040-4020(01)91496-6

  日期：1984.1

  α,β- β, γ-unsaturated esters can be converted by strong base and chlorotrimethylsilane to the corresponding mixed vinylketene acetals which are shown to be particularly useful and generally applicable reagents for the regiospecific annulation of halogenoquinones. The reaction proceeds readily with a variety of substrates including benzoquinones.

  α，β-β，γ-不饱和酯可通过强碱和三甲基氯硅烷转化为相应的混合乙烯酮缩醛，这对于卤代醌的区域特异性环合而言是特别有用和普遍适用的试剂。该反应在包括苯醌在内的多种底物下容易进行。
• Synthesis of carminic acid, the colourant principle of cochineal
  作者：Pietro Allevi、Mario Anastasia、Steve Bingham、Pierangela Ciuffreda、Alberto Fiecchi、Giuliana Cighetti、Max Muir、Antonio Scala、John Tyman

  DOI：10.1039/a705145j

  日期：——

  The first synthesis of carminic acid (7β-D-glucopyranosyl-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid) is described. Selective C-glycosylation at the 7-position of ethyl and benzyl 3,5,8,9,10-pentamethoxy-1-methylanthracene-2-carboxylates with 2,3,4,6-tetra-O-benzyl-1-trifluoroacetyl-α-D-glucopyranose afforded intermediates which were oxidised to ethyl and benzyl 3,5,8-trimethoxy-1-methyl-9,10-dioxo-7-(2′,3′,4′,6′-tetra-O-benzyl-β-D-glucopyranosyl)-9,10-dihydroanthracene-2-carboxylate respectively. The benzyl compound was hydrogenolysed and the ethyl analogue hydrogenolysed and hydrolysed to give the same product, which was tetraacetylated and demethylated to afford 6-deoxycarminic acid tetraacetate, 3,5,8-trihydroxy-1-methyl-9,10-dioxo-7-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyl)-9,10-dihydroanthracene-2-carboxylic acid. The pentamethoxy intermediates were obtained from 2-chloronaphthazarin by Diels–Alder addition to 3-alkoxycarbonyl-2,4-bis(trimethylsiloxy)penta-2,4-dienes to give alkyl 6-deoxykermesates. Methylation afforded the corresponding trimethyl ethers, which by reductive methylation gave the required pentamethoxy compounds. By known steps 6-deoxycarminic acid tetraacetate was converted into the 5,8,9,10-bisquinone, acetoxylation of which gave carminic acid octaacetate. Acidic hydrolysis afforded carminic acid.

  首次合成了胭脂酸（7β-D-葡萄糖吡喃糖基-3,5,6,8-四羟基-1-甲基-9,10-二氧基-9,10-二氢蒽-2-羧酸）。选择性地在乙基和苄基3,5,8,9,10-五甲氧基-1-甲基蒽-2-羧酸酯的7位进行C-糖苷化，与2,3,4,6-四-O-苄基-1-三氟乙酰-α-D-葡萄糖吡喃糖反应得到了中间体，随后氧化得到乙基和苄基3,5,8-三甲氧基-1-甲基-9,10-二氧基-7-(2′,3′,4′,6′-四-O-苄基-β-D-葡萄糖吡喃糖)-9,10-二氢蒽-2-羧酸酯。苄基化合物经过氢解，乙基类似物经过氢解和水解，得到了相同的产物，然后进行四乙酰化和脱甲基反应，得到6-脱氧胭脂酸四乙酸酯，即3,5,8-三羟基-1-甲基-9,10-二氧基-7-(2′,3′,4′,6′-四-O-乙酰-β-D-葡萄糖吡喃糖)-9,10-二氢蒽-2-羧酸。五甲氧基中间体是通过将2-氯萘扎林与3-烷氧基羧基-2,4-双(trimethylsiloxy)戊-2,4-二烯进行Diels-Alder反应获得的，以得到烷基6-脱氧克尔梅酸酯。甲基化反应产生相应的三甲基醚，经过还原甲基化得到所需的五甲氧基化合物。通过已知步骤，6-脱氧胭脂酸四乙酸酯被转化为5,8,9,10-双醌，进一步的醋酸化反应得到胭脂酸八乙酸酯。酸性水解反应得到胭脂酸。