dimethyl 2-phenoxyfumarate | 4602-94-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 2-phenoxyfumarate
• 英文别名: dimethyl (Z)-2-phenoxy-2-butenedioate；Phenoxy-fumarsaeure-dimethylester；α-Phenoxy-fumarsaeure-dimethylester；1-Phenoxy-aethylen-trans-1.2-dicarbonsaeure-dimethylester；Dimethyl-phenoxyfumarat；dimethyl (Z)-2-phenoxybut-2-enedioate
• CAS: 4602-94-2
• 化学式: C₁₂H₁₂O₅
• 分子量: 236.224
• InChiKey: GNZSYALKRFIECS-NTMALXAHSA-N

物化性质

• 熔点：
  74-75 °C
• 沸点：
  330.6±32.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-phenoxyfumarate 、 丙醛 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以10.8%的产率得到2-Ethyl-5-oxo-4-phenoxy-2,5-dihydro-furan-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Feit, Ben-Ami; Haag, Brigitte; Kast, Juergen, Journal of the Chemical Society. Perkin transactions I, 1986, p. 2027 - 2036

  摘要：

  DOI：
• 作为产物：
  描述：

  丁炔二酸二甲酯 、 苯酚 在 水 、 potassium carbonate 作用下， 生成 dimethyl 2-phenoxyfumarate
  参考文献：
  名称：

  A green and rapid approach for the stereoselective vinylation of phenol, thiol and amine derivatives in water

  摘要：

  通过酚、硫醇和胺与活化炔烃的反应，实现了C−O、C−S和C−N键的选择性立体形成。这些反应在室温下水相中以优异的产率成功进行。该方法的优势在于后处理过程中无需使用有机溶剂、反应时间短以及温和的环境友好型反应条件。

  DOI：

  10.1039/c1gc15625j

文献信息

• A Selective and Versatile Synthesis of Substituted Chromones via Addition of Phenols to Dimethyl Acetylenedicarboxylate
  作者：MJ Stoermer、DP Fairlie

  DOI：10.1071/ch9950677

  日期：——

  Despite many published syntheses of chromones, none has been reported to be both selective for chromones and tolerant of ring substitution. The addition of substituted phenols to dimethyl acetylenedicarboxylate is now reported as a versatile high yield initial step in a simple three-step synthesis of chromone 2-carboxylic acids. Triethylamine being used to deprotonate the substituted phenol, the addition to dimethyl acetylenedicarboxylate proceeds under mild conditions and tolerates a wide range of functional groups on the phenol. Although not stereoselective, both fumarate and maleate aryloxy products of this addition can then be cyclized, according to a known method, to chromones without contamination by isomeric coumarins. Thus the addition reaction is a valuable component of a versatile and selective synthesis of substituted chromones.

  尽管已发表了许多色酮的合成方法，但还没有任何一种方法既对色酮具有选择性，又对环的取代具有耐受性。现在有报道称，将取代苯酚加到乙炔二甲酸二甲酯上是一种多功能的高产率初始步骤，可简单地三步合成铬酮 2-羧酸。使用三乙胺对取代的苯酚进行去质子化，与乙炔二甲酸二甲酯的加成反应在温和的条件下进行，并可容忍苯酚上的多种官能团。虽然不具有立体选择性，但根据已知的方法，这种加成反应的富马酸酯和马来酸酯芳氧基产物都可以环化成色酮，而不会受到异构香豆素的污染。因此，该加成反应是取代色酮的多功能选择性合成的重要组成部分。
• An efficient and green approach for the synthesis of vinyl aryl ethers in the presence of guanidine hydrochloride
  作者：SEYED MOHAMMAD VAHDAT、ROBABEH BAHARFAR

  DOI：10.3906/kim-1002-24

  日期：——

  A stereoselective procedure for vinyl aryl ether bond formation by direct coupling of dialkyl acetylenedicarboxylates and substituted phenols or naphthols under mild reaction conditions has been developed. Using guanidine hydrochloride as a new catalyst and water-acetone as green solvent, dialkyl acetylenedicarboxylates were reacted with substituted phenols or naphthols in room temperature to produce vinyl aryl ethers in good to excellent yields.

  开发了一种立体选择性的程序，通过在温和反应条件下直接耦合二烷基炔二酸酯和取代酚或萘醇来形成烯基芳醚键。采用盐酸胍作为新催化剂，水-丙酮作为绿色溶剂，二烷基炔二酸酯在室温下与取代酚或萘醇反应，产率良好到优秀。
• Stereoselective addition of phenols to dimethyl acetylenedicarboxylate adsorbed on alumina
  作者：Mitsuo Kodomari、Takaaki Sakamoto、Suehiko Yoshitomi

  DOI：10.1039/c39900000701

  日期：——

  Although phenols react with dimethyl acetylenedicarboxylate (DMAD) to give a mixture of both cis- and trans-addition products, the reaction with DMAD adsorbed on alumina gives cis-addition products stereoselectively.

  尽管苯酚与乙炔二甲酸二甲酯（DMAD）反应生成顺式和反式加成产物的混合物，但与DMAD吸附在氧化铝上的反应使立体选择性地生成顺式加成产物。
• Diastereoselective O-Vinylation of Phenols using DMAD under Mild Reaction Conditions
  作者：Ebrahim Kianmehr、Katayoun Tabatabai、Alireza Abbasi、Hamideh Shokouhi Mehr

  DOI：10.1080/00397910802219163

  日期：2008.7.24

  An efficient and straightforward pyridine-catalyzed method allowing selective O-vinylation of phenols with DMAD is reported. The reaction is diastereoselective and leads exclusively to (Z)-configuration in high yields.
• Synthesis of Functionalized Pyrrolizidines/Pyrrolidines Incorporating a Spirooxindole Motif through [3+2] Cycloaddition
  作者：Yaghoub Sarrafi、Marzieh Sadatshahabi、Mahshid Hamzehloueian、Kamal Alimohammadi、Mahgol Tajbakhsh

  DOI：10.1055/s-0033-1338492

  日期：——

  Dimethyl 2-(aryloxy)fumarates and dimethyl 2-(alkyl- or arylthio)fumarates are shown to be efficient dipolarophiles in 1,3-dipolar cycloaddition reaction with azomethine ylides, which are generated by the reaction of isatin with the secondary amino acids proline or sarcosine. In these reactions, dimethyl 2-(alkyl- or arylthio)fumarates afforded spirooxindolopyrrolizidines or -pyrrolidines in high yields with excellent regioselectivities, while dimethyl 2-(aryloxy)fumarates produced mixtures of regioisomers. DFT calculations at the B3LYP/6-31G(d,p) level were consistent with the observed results. Tri- and tetracyclic compounds were obtained through regio- and stereoselective intramolecular cycloaddition of O-vinylic salicylaldehyde with secondary amino acids.