1,2-二(3,4-二甲氧基苯基)乙烷-1,2-二酮 | 554-34-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 1,2-二(3,4-二甲氧基苯基)乙烷-1,2-二酮
• 英文名称: 1,2-bis(3,4-dimethoxyphenyl)ethane-1,2-dione
• 英文别名: 3,3',4,4'-tetramethoxybenzil；Veratril
• CAS: 554-34-7
• 化学式: C₁₈H₁₈O₆
• mdl: MFCD00808342
• 分子量: 330.337
• InChiKey: GMPWPTYBCCEVKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-二(3,4-二甲氧基苯基)乙烷-1,2-二酮 在 tin 、 乙醇 、 copper(II) sulfate 作用下， 生成 1,2-bis(3,4-dimethoxyphenyl)ethanone
  参考文献：
  名称：

  PAPAVERINE: AN ATTEMPTED RÜGHEIMER SYNTHESIS

  摘要：

  DOI：

  10.1021/ja01364a044
• 作为产物：
  描述：

  (3,4-二甲氧基苯基)乙酰氯 在 selenium(IV) oxide 、 aluminum (III) chloride 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 18.0h， 生成 1,2-二(3,4-二甲氧基苯基)乙烷-1,2-二酮
  参考文献：
  名称：

  Hexaphenylbenzene-based polymers of intrinsic microporosity

  摘要：

  由1,2-和1,4-位异构体的二(3′,4′-二羟基苯基)四苯基苯衍生的微孔聚合物具有非常不同的特性，前者主要由环状低聚物组成，而后者具有高相对分子质量，适合形成高气体渗透性且坚固的溶剂铸造薄膜。

  DOI：

  10.1039/c1cc11717c

文献信息

• Facile synthesis of triphenylenes and triphenylene/phenanthrene fused heteroaromatics
  作者：Vijay Gupta、Satish K. Pandey、Ravi P. Singh

  DOI：10.1039/c8ob01930d

  日期：——

  and comparatively less toxic methods in organic synthesis has received great attention. We report a simple and facile method for the synthesis of substituted triphenylenes and their heteroaryl analogues using ceric ammonium nitrate (CAN) via oxidative biaryl coupling. We describe the structural and photophysical properties of these unique heteroaryl fused triphenylenes.

  近年来，在有机合成中开发更温和，安全和相对较少毒性的方法受到了广泛的关注。我们报告了一种简单而简便的方法，用于通过硝酸联芳基氧化偶合硝酸铈铵（CAN）来合成取代的联苯及其杂芳基类似物。我们描述了这些独特的杂芳基稠合苯并菲的结构和光物理性质。
• Substituted 5- and 6-quinoxalinecarboxylic acids and their tuberculostatic activity
  作者：František Roubínek、Viktor Bydžovský、Zdeněk Buděšínský

  DOI：10.1135/cccc19840285

  日期：——

  Condensation of aliphatic and aliphatic-aromatic α-diketones, and of substituted benzils with 2,3- and 3,4-diaminobenzoic acids and with 4,5-diamino-2-hydroxybenzoic acid gave 74 5- and 6-quinoxalinecarboxylic acids, with the same or different alkyls and aryls as substituents at position 2 and 3. The compounds with different substituents at positions 2 and 3 were resolved into positional isomers. Their structures were determined by means of the dipole moments. The compounds were tested for tuberculostatic activity. Some exhibited it in vitro (LI, LVII), but failed in vivo.

  脂肪族和脂肪族-芳香族α-二酮与2,3-和3,4-二氨基苯甲酸以及4,5-二氨基-2-羟基苯甲酸的缩合反应产生了74种5-和6-喹啉羧酸，位置2和3上的取代基可以是相同的或不同的烷基和芳基。在位置2和3有不同取代基的化合物被分解成位置异构体。它们的结构是通过偶极矩确定的。这些化合物被检测其抗结核活性。一些化合物在体外（LI，LVII）表现出该活性，但在体内失败。
• Toward the oxidative deconstruction of lignin: oxidation of β-1 and β-5 linkages
  作者：Zhen Fang、Mark S. Meier

  DOI：10.1039/c8ob00409a

  日期：——

  reports on methods for the oxidative cleavage of β-O-4 linkages in lignin model compounds, but relatively few reports of how those methods affect other linkages that are present in lignin. We have investigated the effect of several of these oxidation methods on the β-1 and the β-5 lignin linkages, using four β-1 and β-5 model compounds. We observed that direct oxidative cleavage of C–C bonds occurs in

  关于木质素模型化合物中β-O-4键的氧化裂解方法的报道很多，但是关于那些方法如何影响木质素中其他键的报道相对较少。我们使用四种β-1和β-5模型化合物研究了其中几种氧化方法对β-1和β-5木质素键的影响。我们观察到C–C键的直接氧化裂解发生在金属催化的TEMPO氧化系统和铁卟啉氧化中，而我们都没有在β-O-4模型中观察到类似的氧化。事实证明，β-5键对所有这些氧化系统都具有较强的抗性，但是当用KMnO 4处理时，β-5模型3中的二氢呋喃环被打开。在高温下。最有前途的是用DDQ氧化2，就像在与β-O-4模型的反应中一样，它以高收率（84％）生成苄基酮。该反应显示出对苄基位置的选择性以及与苯酚的相容性，这是两步，苄基氧化/木质素裂解的Baeyer-Villiger路线非常需要的特性。
• A new general method for the synthesis of 4-hydroxylated 3-aryltetrahydroisoquinolines
  作者：Raúl SanMartín、Roberto Olivera、Eduardo Martínez de Marigorta、Esther Domínguez

  DOI：10.1016/0040-4020(95)00197-g

  日期：1995.5

  3-Aryl-4-hydroxytetrahydroisoquinolines have been prepared from deoxybenzoins. The nitrosation of the latter derivatives has been improved and the catalytic reduction of the obtained oximinoketones has been carried out with the help of ultrasounds. Heterocyclization to the isoquinoline moiety occurred on the unprotected 1,2-aminoalcohol to give stereoselectively the corresponding hydroxylated heterocycle

  3-芳基-4-羟基四氢异喹啉已由脱氧苯偶姻制备。后一种衍生物的亚硝化得到了改善，并且所获得的肟基酮的催化还原已经借助超声波进行了。在未保护的1,2-氨基醇上发生杂环化成异喹啉部分，从而以良好的产率立体选择性地给出了相应的羟基化杂环。
• STUDIES IN THE POLYOXYPHENOL SERIES: IX. THE SYNTHESIS OF PAPAVERINE AND PAPAVERALDINE BY THE POMERANZ-FRITSCH METHOD
  作者：Donald A. Guthrie、Arlen W. Frank、C. B. Purves

  DOI：10.1139/v55-090

  日期：1955.5.1

  Fritsch's cyclization of N-(α-veratrylveratrylidene)-aminoacetal in sulphuric acid was shown to give 1.1% of papaverine and 23% of an isomer, m.p. 164.5–165.5 °C.; hydrochloride, m.p. 212 °C. decomp., which was supposed to be 4,5-bis(3,4-dimethoxyphenyl)-2H-pyrrolenine, produced by an internal condensation of the acetal or the corresponding aldehyde with the reactive methylene group. A similar structure was proposed for another unidentified isomer prepared by Schlittler and Müller. Hydrogenation of Fritsch's acetal gave N-(α-veratryl-veratryl)-aminoacetal, m.p. 69.5–70 °C., which was cyclized to a base, m.p. 155.5–156 °C.; N-acetyl derivative, m.p. 203.5–204 °C., formulated as 2,3-bis(3,4-dimethoxyphenyl)-3-pyrroline. Substances presumed to be the intermediate aldehyde and aldol were isolated as colorless oils. Condensation of the diketone veratril with aminoacetal, followed by cyclization of the crude product, constituted a new two-step synthesis of papaveraldine in 8% yield, and the reduction of the latter to papaverine was known.Other crystalline compounds prepared incidentally and thought to be new were veratril monoanil, m.p. 172–173 °C.; α,α′-biveratrylideneaminoacetal, m.p. 101–102 °C.; a compound formulated as 2,3-bis(3,4-dimethoxyphenyl)-4-ethylmer-captopyrrolidine hydrochloride, m.p. 184–185 °C; from this an unidentified mercury complex, m.p. 109 °C. decomp.; 4,4′dibenzyloxy-3,3′-dimethoxy-desoxybenzoin, m.p. 141–142 °C; and its oxime, m.p. 137.5 °C.

  Fritsch在硫酸中对N-(α-芍药碱基芍药碱亚甲基)-氨基乙醛进行环化反应，结果显示产率为1.1%的罂粟碱和23%的异构体，熔点为164.5–165.5°C；盐酸盐，熔点为212°C分解。这种异构体被认为是4,5-双(3,4-二甲氧基苯基)-2H-吡咯烯，通过乙醛或相应醛与活性甲基的内部缩合产生。 Schlittler和Müller制备的另一种未知异构体也提出了类似的结构。Fritsch的亚甲基环化反应产生了N-(α-芍药碱基芍药碱)-氨基乙醛，熔点为69.5–70°C，它被环化成一种碱，熔点为155.5–156°C；N-乙酰衍生物，熔点为203.5–204°C，被确定为2,3-双(3,4-二甲氧基苯基)-3-吡咯烯。假定为中间醛和醛缩合物的物质被分离为无色油状物。芍药碱的新的两步合成方法包括芍药碱基芍药碱与氨基乙醛的缩合，随后对粗产品进行环化反应，产率为8%。将后者还原为罂粟碱是已知的。其他结晶化合物包括芍药碱基单苯胺，熔点为172–173°C；α,α′-双(芍药碱基)-氨基乙醛，熔点为101–102°C；一种被确定为2,3-双(3,4-二甲氧基苯基)-4-乙基巯基吡咯啉盐酸盐的化合物，熔点为184–185°C；从中得到的未知汞络合物，熔点为109°C分解；4,4′-二苄氧基-3,3′-二甲氧基-去氧苯酮，熔点为141–142°C；以及它的肟，熔点为137.5°C。