1-(2,5-二甲氧基-4-甲基苯基)乙酮 | 13720-58-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-(2,5-二甲氧基-4-甲基苯基)乙酮
• 英文名称: 1-(2,5-Dimethoxy-4-methyl-phenyl)-ethanone
• 英文别名: 2,5-dimethoxy-4-methylacetophenone；1-(2,5-dimethoxy-4-methylphenyl)ethan-1-one；1-(2,5-dimethoxy-4-methylphenyl)ethanone
• CAS: 13720-58-6
• 化学式: C₁₁H₁₄O₃
• mdl: MFCD00156672
• 分子量: 194.23
• InChiKey: SVRFSXJNHLDZGD-UHFFFAOYSA-N

物化性质

• 熔点：
  76°C
• 沸点：
  296.8±35.0 °C(Predicted)
• 密度：
  1.048±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.363
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2914509090

反应信息

• 作为反应物：
  描述：

  1-(2,5-二甲氧基-4-甲基苯基)乙酮 在 吡啶 、 甲醇 、 Porcine pancreas lipase type II 、 dimethyl sulfide borane 、 对甲苯磺酸 、 对苯二酚 、 sodium hydroxide 作用下， 以 四氢呋喃 、 乙醚 、 甲基叔丁基醚 、 二甲基亚砜 、 苯 为溶剂， 反应 13.5h， 生成 (3R)-3-(2,5-dimethoxy-4-methylphenyl)butanenitrile
  参考文献：
  名称：

  Lipase-mediated resolution of substituted 2-aryl-propanols: application to the enantioselective synthesis of phenolic sesquiterpenes

  摘要：

  A comprehensive study of the lipase-mediated resolution of substituted 2-aryl-propanols is reported. The latter alcohols were submitted to the irreversible acetylation catalyzed either by PPL, CRL, or lipase PS. The enantioselectivity of these transformations was dependent on the type of lipase used. The type of substituents and particularly their position on the aromatic ring strongly affected the selectivity of the reaction. The experiments described prove that PPL is the more versatile lipase catalyzing the acetylation with an enantiomeric ratio (E) value that ranges from 1 up to 144, depending on the substrate used. Conversely, the same transformations were catalyzed by CRL and lipase PS with an enantiomeric ratio value, which is always less than 5. The remarkable behavior of PPL was exploited in the large scale resolution of some substituted 2-aryl-propanols whose enantiomeric forms are relevant building blocks in the enantioselective synthesis of phenolic sesquiterpenes. By these means, the synthesis of (S)-turmeronol B and the formal syntheses of (R)-curcumene, (R)-curcuphenol, (R)-xanthorrhizol, and (R)-curcuhydroquinone were accomplished. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.03.012
• 作为产物：
  描述：

  甲基氢醌 在 potassium carbonate 、 tin(ll) chloride 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 14.0h， 生成 1-(2,5-二甲氧基-4-甲基苯基)乙酮
  参考文献：
  名称：

  贝克酵母介导的双倍半硼烷倍半萜（+）-姜酚，（+）-黄姜酚，（-）-姜酚和（+）-姜氢醌的对映选择性合成

  摘要：

  发酵面包酵母转化不饱和酵母 醛类 5a–c进入饱和状态酒类 分别为6a–c。吸附在非极性树脂上的底物的微生物饱和度以高化学收率进行，并且在（S）-（+）异构体的形成过程中显示出完全的对映选择性。Enantiopure 6a–c是通用的手性构件，可用于合成比沙泊烷 倍半萜。它们的有用性示于（制备小号） - （+） - curcuphenol，（小号） - （+） - xanthorrhizol，（小号） - （ - ） - curcuquinone和（小号） - （+） - curcuhydroquinone。

  DOI：

  10.1039/b006141g

文献信息

• Application of the lithiation–borylation reaction to the rapid and enantioselective synthesis of the bisabolane family of sesquiterpenes
  作者：Varinder K. Aggarwal、Liam T. Ball、Simon Carobene、Rickki L. Connelly、Matthew J. Hesse、Benjamin M. Partridge、Philippe Roth、Stephen P. Thomas、Matthew P. Webster

  DOI：10.1039/c2cc32176a

  日期：——

  The expedient enantioselective synthesis of 5 bisabolane sesquiterpenes has been achieved using a common, one-pot lithiation-borylation reaction of secondary benzylic carbamates and either protodeboronation or oxidation to give the natural products in fewer than 5 steps, with high yield and >94 : 6 er.

  使用仲氨基甲酸苄酯的常见的一锅锂化-硼化反应以及原脱硼烷或氧化反应可在不到5个步骤的情况下以高收率和大于94：6的比例获得天然产物，从而实现了5种双倍半硼烷倍半萜的便捷对映选择性合成。嗯
• Highly Enantioselective Iridium-Catalyzed Hydrogenation of α,β-Unsaturated Esters
  作者：Jia-Qi Li、Xu Quan、Pher G. Andersson

  DOI：10.1002/chem.201200907

  日期：2012.8.20

  α,β‐Unsaturated esters have been employed as substrates in iridium‐catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic‐ and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural

  在铱催化的不对称氢化反应中，α，β-不饱和酯已被用作底物。对于在手性碳上同时具有芳族和脂族取代基的多种底物，可实现完全转化和良好至优异的对映选择性（高达99％  ee）。氢化产物在多种天然产物和药物的合成中作为构建基非常有用。
• A Facile Demethylation of Ortho Substituted Aryl Methyl Ethers Promoted by AlCl₃
  作者：Zhen-Ting Du、Jing Lu、Hong-Rui Yu、Yan Xu、An-Pai Li

  DOI：10.3184/030823410x12708998015900

  日期：2010.4

  An efficient and practical demethylation of ortho substituted aryl methyl ethers using AlCl3 has been developed. This method gives a high conversion, is simple to operate and is cost-effective. A mechanism involving the complexation of AlCl3 with the OMe and the adjacent electron withdrawing group is proposed. Many functional groups can be tolerated in the demethylation process, and 29 examples gave

  已经开发出使用 AlCl3 对邻位取代的芳基甲基醚进行有效和实用的去甲基化。该方法转化率高，操作简单，成本低廉。提出了一种涉及 与 OMe 和相邻吸电子基团络合的机制。去甲基化过程中可以容忍许多官能团，29个例子以90-98％的产率得到了去甲基化产物。
• Synthetic approach towards cuparene-type sesquiterpenes via highly regioselective epoxide opening under acid catalysis
  作者：Camila B. Nascimento、Leandro A. Avelar、Danilo C. Arantes、Noêmia K. Ishikawa、Fernando Macedo

  DOI：10.1007/s00706-018-2199-6

  日期：2018.10

  AbstractObtaining cuparene-type sesquiterpenes is a significant synthetic challenge mainly because of the construction of the sterically hindered quaternary centres. We report herein the successful construction of such quaternary moiety by a highly regioselective opening of (+/−)-2,5-dimethoxy-4-methyl-α-methylstyrene oxide by the acetone silyl enol ether catalysed by Lewis acid. Additionally, an efficient

  摘要获得铜烯型倍半萜烯是一项重大的合成挑战，这主要是由于立体位阻四元中心的构建。我们在本文中报道了通过路易斯酸催化的丙酮甲硅烷基烯醇醚的（+/-）-2，5-二甲氧基-4-甲基-α-甲基苯乙烯氧化物的高度区域选择性开放来成功构建此类季基部分。另外，通过对二环氧乙烷促进的环氧化方案的修饰，实现了高度活化的2，5-二甲氧基-4-甲基-α-苯乙烯的有效环氧化。对这两个关键步骤的密集优化使所需支链高醛缩醛加合物的合成成为了针对烯醇单蛋白的短合成替代品的关键中间体。 图形概要
• Direct α-Benzylation of Methyl Enol Ethers with Activated Benzyl Alcohols: Its Rearrangement and Access to (±)-Tetrahydronyasol, Propterol A, and 1,3-Diarylpropane
  作者：Tapan Kumar Jena、Faiz Ahmed Khan

  DOI：10.1021/acs.joc.9b02064

  日期：2019.11.1

  Herein, we report a one-pot Lewis acid mediated synthesis of bi- and triarylpropanal derivatives and their corresponding isomeric ketones from aromatic enol ethers. This transformation takes place via nucleophilic attack of enol ethers to electron-rich benzyl alcohols. The substrate scope of this indicates that it might proceed via quinomethoxy methide as a key intermediate leading to propanal derivatives

  在本文中，我们报道了一锅路易斯酸介导的从芳族烯醇醚合成的二芳基和三芳基丙醛衍生物及其相应的异构酮的合成。这种转化是通过烯醇醚向富电子的苄醇的亲核攻击而发生的。该物质的底物范围表明它可能通过喹甲氧基甲基化物作为导致丙醛衍生物的关键中间体进行，并且它们的Wagner-Meerwein重排提供了异构体酮。此外，该方法学适用于（±）-四氢nyasol，丙醇A和1,3-二芳基丙烷的合成。