2,3-dihydro-3-hydroxymethyl-3-methyl-4H-benzopyran-4-one | 104416-48-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2,3-dihydro-3-hydroxymethyl-3-methyl-4H-benzopyran-4-one
• 英文别名: 3-(hydroxymethyl)-3-methyl-chroman-4-one；3-Hydroxymethyl-3-methyl-4-chromanone；3-(Hydroxymethyl)-3-methyl-2,3-dihydro-4H-chromen-4-one；3-(hydroxymethyl)-3-methyl-2H-chromen-4-one
• CAS: 104416-48-0
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: RRKSQWWDODIWDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,3-dihydro-3-hydroxymethyl-3-methyl-4H-benzopyran-4-one 在 氯化亚砜 、 N,N-二甲基甲酰胺 作用下， 以 二甲基亚砜 为溶剂， 反应 8.0h， 生成 2-(3-methyl-4-oxochroman-3-yl)acetonitrile
  参考文献：
  名称：

  Hydroxymethylation of 2-Hydroxypropiophenones in Aqueous Medium: Synthesis of 3-Hydroxymethyl-3-methyl-4-chromanones and Their Conversion to 3-Methyl-4-chromanone-3-acetic Acids

  摘要：

  o-羟基丙基苯酮（1a）与水相甲醛在氢氧化钠溶液中反应，生成了单羟甲基化的化合物2a和/或双羟甲基化的衍生物3a，以及3-甲基-4-氢化色酮（4a）和/或3-甲基-3-羟甲基-4-氢化色酮（5a），具体生成物的比例取决于所用试剂的比例。文中也展示了从1a形成5a的机制。化合物5a及其6-氯衍生物5b（同样从5-氯-2-羟基丙基苯酮（1b）制备）通过标准程序转化为相应的3-甲基-4-氢化色酮-3-乙酸（8a、b）。

  DOI：

  10.1055/s-1985-31368
• 作为产物：
  描述：

  3a-methyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazole 在 镍 氢气 、 硼酸 作用下， 以 甲醇 、 水 为溶剂， 以75%的产率得到2,3-dihydro-3-hydroxymethyl-3-methyl-4H-benzopyran-4-one
  参考文献：
  名称：

  通过腈氧化物的分子内 1,3-偶极环加成合成功能化苯并吡喃

  摘要：

  摘要 通过一系列反应合成了各种功能化的苯并吡喃衍生物，收率良好。腈氧化物的分子内环化、还原裂解和乙酰化。

  DOI：

  10.1080/00397910802138744

文献信息

• Enantiomeric scaffolding of α-tetralone and related scaffolds by EKR (Enzymatic Kinetic Resolution) and stereoselective ketoreduction with ketoreductases
  作者：Rajib Bhuniya、Samik Nanda

  DOI：10.1039/c1ob06545a

  日期：——

  Stereochemically pure compounds containing an all carbon quaternary stereocenter based on 1-tetralone, 1-indanone and 4-chromanone scaffolds have been synthesized by employing Lipase PS (Burkholderia cepacia) catalyzed kinetic resolution. These scaffolds are further functionalized by microbial ketoreductase enzymes (Geotrichum candidum, Candida parapsilosis and Aspergillus niger) to access stereochemically pure diols which, on further synthetic manipulation, yield novel cyclic compounds.

  基于1-四氢萘酮、1-茚酮和4-克罗莫酮骨架的立体化学纯化合物，含有全碳四元立体中心，已通过采用脂肪酶PS（来自布尔克霍尔德菌）催化的动力学分离合成。这些骨架进一步通过微生物酮还原酶（来自地霉菌、帕氏酵母和黑曲霉）进行了功能化，以获得立体化学纯的二醇，经过进一步的合成操作，得到新型环状化合物。
• Dimethyl Sulfoxide Provides Three Different Units in Synthesis of Chroman-4-ones Containing Sulfur and a Quaternary Carbon Center under HOAc Conditions
  作者：Lihong Xu、Anan Wang、Xu Shi、Qian He、Tao-Shan Jiang

  DOI：10.1021/acs.joc.3c00832

  日期：2023.10.6

  enones and DMSO is described. In these unique reactions, DMSO is activated by HOAc and provides three different units (CH2, CH2OH, and CH2SMe) in the target molecules. This reaction displays good substrate scope and reaction yields with a series of substitutes. The mechanism showed that the three units were formed in sequential order.

  描述了直接从邻羟基苯乙酮和 DMSO直接由 HOAc 促进的具有硫原子和 α-羰基季碳中心的色满-4-酮的构建。在这些独特的反应中，DMSO 被 HOAc 激活并在目标分子中提供三种不同的单元（CH 2、CH 2 OH 和 CH 2 SMe）。该反应显示出良好的底物范围和一系列替代物的反应产率。该机制表明，这三个单元是按顺序形成的。
• Chemoenzymatic synthesis and resolution of compounds containing a quaternary stereocenters adjacent to a carbonyl group
  作者：Tridib Mahapatra、Nandan Jana、S. Nanda

  DOI：10.1016/j.tetasy.2008.04.024

  日期：2008.5

  Racemic compounds containing a quaternary stereocenter (having hydroxymethyl and alkyl group adjacent to keto functionality) based on chromanone, alpha-tetralone, and indalone scaffolds have been synthesized. An enzymatic irreversible transesterification approach has been applied to generate the pure enantiomers in a stereocontrolled fashion. The pure enantiomers of some alpha,alpha-dialkylated carbonyl compounds have been synthesized by this method. (C) 2008 Elsevier Ltd. All rights reserved.
• BARLOCCO, D.;CIGNARELLA, G.;CURZU, M. M., SYNTHESIS, BRD, 1985, N 9, 876-878
  作者：BARLOCCO, D.、CIGNARELLA, G.、CURZU, M. M.

  DOI：——

  日期：——
• Hydroxymethylation of 2-Hydroxypropiophenones in Aqueous Medium: Synthesis of 3-Hydroxymethyl-3-methyl-4-chromanones and Their Conversion to 3-Methyl-4-chromanone-3-acetic Acids
  作者：Daniela Barlocco、Giorgio Cignarella、Maria Michela Curzu

  DOI：10.1055/s-1985-31368

  日期：——

  Reaction of o-hydroxypropiophenone (1a) with aqueous formaldehyde in sodium hydroxide solution led to the mono-hydroxymethylated 2a and/or the bis-hydroxymethylated derivative 3a, as well as to 3-methyl-4-chromanone (4a) and/or 3-methyl-3-hydroxymethyl-4-chromanone (5a), according to the ratio of the reagents employed. The mechanism of formation of 5a from 1a was also demonstrated. Compound 5a and its 6-chloro derivative 5b, similarly prepared from 5-chloro-2-hydroxypropiophenone (1b), were converted by standard procedure to the corresponding 3-methyl-4-chromanone-3-acetic acids 8a, b.

  o-羟基丙基苯酮（1a）与水相甲醛在氢氧化钠溶液中反应，生成了单羟甲基化的化合物2a和/或双羟甲基化的衍生物3a，以及3-甲基-4-氢化色酮（4a）和/或3-甲基-3-羟甲基-4-氢化色酮（5a），具体生成物的比例取决于所用试剂的比例。文中也展示了从1a形成5a的机制。化合物5a及其6-氯衍生物5b（同样从5-氯-2-羟基丙基苯酮（1b）制备）通过标准程序转化为相应的3-甲基-4-氢化色酮-3-乙酸（8a、b）。