methyl 6-deoxykermesate | 141111-38-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: methyl 6-deoxykermesate
• 英文别名: methyl 3,5,8-trihydroxy-1-methyl-9,10-anthroquinone-2-carboxylate；Methyl 3,5,8-trihydroxy-1-methyl-9,10-dioxoanthracene-2-carboxylate
• CAS: 141111-38-8
• 化学式: C₁₇H₁₂O₇
• 分子量: 328.278
• InChiKey: OGWJUPLGVRHQIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  121
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 6-deoxykermesate 在 sodium hydroxide 、 sodium dithionite 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.92h， 生成 7-[(4-Bromo-phenyl)-hydroxy-methyl]-3,9,10-trihydroxy-1-methyl-5,8-dioxo-5,8,9,10-tetrahydro-anthracene-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Bingham, Steve J.; Tyman, John H. P.; Malik, K. M. A., Journal of Chemical Research, Miniprint, 1998, # 9, p. 2465 - 2496

  摘要：

  DOI：
• 作为产物：
  描述：

  萘茜 以 溶剂黄146 为溶剂， 生成 methyl 6-deoxykermesate
  参考文献：
  名称：

  Synthesis of carminic acid and principal intermediates

  摘要：

  本发明涉及基于2-卤代萘酞与双三甲基硅基-二烯的反应合成6-去氧红树酸酯，6-去氧红树酸和胭脂酸的方法。

  公开号：

  US05424421A1

文献信息

• 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。
• The synthesis of kermesic acid and isokermesic acid derivatives and of related dihydroxyanthraquinones
  作者：Stephen J. Bingham、John H. P. Tyman

  DOI：10.1039/a704317a

  日期：——

  bis(quinone), Thiele acetoxylation of which gives after hydrolysis and permethylation, a mixture of derivatives of kermesic and isokermesic acids in equal proportions. The Diels–Alder addition of 3-chlorojuglone and 3-alkoxycarbonyl-2,4-bis(trimethylsilyloxy)penta-1,3-dienes has led to an improved synthesis of aloesaponarin-I (3,8-dihydroxy-2-methoxycarbonyl-1-methylanthra-9,10-quinone), while juglone itself affords

  Cochinellic酐甲基，乙基和苄基酯（4-甲氧基-4-乙氧基和4-苄氧基-羰基-5-羟基-3-甲基邻苯二甲酸酐）是通过2-溴马来酸酐与2-溴马来酸酐的单阶段狄尔斯-阿尔德反应制备的3-烷氧基羰基-2,4-双（三甲基甲硅烷氧基）戊-1,3-二烯。通过类似的加成反应，但与3-乙氧基羰基-2-甲氧基-4-三甲基甲硅烷基氧基戊-1,3-二烯一起获得了相应的5-甲基醚乙酯。在三氟化硼-二乙醚与椰油酰胺酐甲酯的存在下，通过1,4-二甲氧基苯的酰化反应合成6-脱氧kermes甲酯是不成功的。首选途径是通过Diels-Alder将3-烷氧基羰基-2,4-双（三甲基甲硅烷基氧基）戊-1,3-二烯添加到萘他林（或2-氯萘他林）中。六-脱氧kermes的四乙酸铅氧化得到双（醌），其Thiele乙酰氧基化在水解和过甲基化后产生等比例的kermes酸和isokermes酸的衍生物的混合物。Diels–Alde
• Synthesis of tetracenomycins
  作者：Donald W. Cameron、Pauline J. de Bruyn

  DOI：10.1016/s0040-4039(00)61155-3

  日期：1992.9

  Tetracenomycins D, A2, B1 and B2 (2)-(5) have been synthesised for the first time, by an efficient, regioselective sequence based on cycloaddition methodology; the ambiguity that existed for tetracenomycins B1 and B2 has thereby been resolved in favour of structures (4a) and (5b) respectively.
• SYNTHESIS OF CARMINIC ACID AND PRINCIPAL INTERMEDIATES
  申请人：EUROPEAN COLOUR PLC

  公开号：EP0602027A1

  公开（公告）日：1994-06-22
• US5424421A
  申请人：——

  公开号：US5424421A

  公开（公告）日：1995-06-13