3,5,8-Trimethoxy-1-methyl-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester | 137410-33-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 3,5,8-Trimethoxy-1-methyl-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester
• 英文别名: Ethyl 3,5,8-trimethoxy-1-methyl-9,10-dioxoanthracene-2-carboxylate；ethyl 3,5,8-trimethoxy-1-methyl-9,10-dioxoanthracene-2-carboxylate
• CAS: 137410-33-4
• 化学式: C₂₁H₂₀O₇
• 分子量: 384.386
• InChiKey: YIVXMGBYBAYGDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,5,8-Trimethoxy-1-methyl-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester 在 palladium on activated charcoal chromium(VI) oxide 、 sodium hydroxide 、 sodium dithionite 、 硫酸 、 三氟化硼乙醚 、 氢气 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 生成 3,5,8-Trimethoxy-1-methyl-9,10-dioxo-7-((2S,3R,4R,5S,6R)-3,4,5-trihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yl)-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  The first total synthesis of carminic acid

  摘要：

  胭脂红酸（7β-D-吡喃葡萄糖基-1-甲基-3,5,6,8-四羟基-9,10-蒽醌-2-羧酸）的首次合成是通过乙基3的直接C-葡萄糖基化完成的，此处合成的5,8,9,10-五甲氧基-1-甲基蒽-2-甲酸酯，其提供乙基7-(2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基)-3，通过掩蔽官能团的再生得到5,8,9,10-五甲氧基-1-甲基蒽-2-羧酸酯和胭脂红酸。

  DOI：

  10.1039/c39910001319
• 作为产物：
  描述：

  3,5,8-Trihydroxy-1-methyl-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester 、 硫酸二甲酯 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 以85%的产率得到3,5,8-Trimethoxy-1-methyl-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  The first total synthesis of carminic acid

  摘要：

  胭脂红酸（7β-D-吡喃葡萄糖基-1-甲基-3,5,6,8-四羟基-9,10-蒽醌-2-羧酸）的首次合成是通过乙基3的直接C-葡萄糖基化完成的，此处合成的5,8,9,10-五甲氧基-1-甲基蒽-2-甲酸酯，其提供乙基7-(2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基)-3，通过掩蔽官能团的再生得到5,8,9,10-五甲氧基-1-甲基蒽-2-羧酸酯和胭脂红酸。

  DOI：

  10.1039/c39910001319

文献信息

• The first total synthesis of carminic acid
  作者：Pietro Allevi、Mario Anastasia、Pierangela Ciuffreda、Alberto Fiecchi、Antonio Scala、Steve Bingham、Max Muir、John Tyman

  DOI：10.1039/c39910001319

  日期：——

  The first synthesis of carminic acid (7β-D-glucopyranosyl-1-methyl-3,5,6,8-tetrahydroxy-9,10-anthraquinone-2-carboxylic acid), was accomplished by direct C-glucosylation of ethyl 3,5,8,9,10-pentamethoxy-1-methylanthracene-2-carboxylate, here synthesized, which affords ethyl 7-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-3,5,8,9,10-pentamethoxy-1-methylanthracene-2-carboxylate and carminic acid by regeneration of the masked functionalities.

  胭脂红酸（7β-D-吡喃葡萄糖基-1-甲基-3,5,6,8-四羟基-9,10-蒽醌-2-羧酸）的首次合成是通过乙基3的直接C-葡萄糖基化完成的，此处合成的5,8,9,10-五甲氧基-1-甲基蒽-2-甲酸酯，其提供乙基7-(2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖基)-3，通过掩蔽官能团的再生得到5,8,9,10-五甲氧基-1-甲基蒽-2-羧酸酯和胭脂红酸。
• 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。