5-(2-fluoro-benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione | 23160-08-9

• 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: 5-(2-fluoro-benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione
• 英文别名: 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione；o-Fluor-benzylidenmeldrumsaeure；o-Fluorbenzyliden-meldrumsaeure；5-[(2-fluorophenyl)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione
• CAS: 23160-08-9
• 化学式: C₁₃H₁₁FO₄
• mdl: MFCD02253217
• 分子量: 250.226
• InChiKey: AGFHYOYOMHKHSM-UHFFFAOYSA-N

物化性质

• 熔点：
  140-141 °C
• 沸点：
  470.0±45.0 °C(Predicted)
• 密度：
  1.303±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-(2-fluoro-benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione 在 N-甲基吗啉 、 potassium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 1.0h， 生成 2-(ethylselanyl)-4-(2-fluorophenyl)-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitrile
  参考文献：
  名称：

  Synthesis and reactions of 1,2-bis[3-cyano-4-(2-fluorophenyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]diselane

  摘要：

  The interaction of 2-fluorobenzaldehyde, cyanoselenoacetamide and Meldrum's acid in the presence of N-methylmorpholine gives 1,2-bis[3-cyano-4-(2-fluorophenyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]di-selane, which also is the product of the reaction of cyanoselenoacetamide with 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione. The diselane obtained interacts with alkyl halides in the presence of a base, forming the corresponding 4-(2-fluorophenyl)-2-(2-R-methylselanyl)-6-oxo-1,4,5,6-tetra-hydropyridine-3-carbonitriles.

  DOI：

  10.1007/s10593-012-1092-1
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 、 2-氟苯甲醛 以 苯 为溶剂， 以93%的产率得到5-(2-fluoro-benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  Sc（OTf）3催化的亚烷基Meldrum酸的共轭烯丙基化

  摘要：

  在温和的Sc（OTf）3催化条件下，烯丙基锡亲核试剂以共轭方式烯丙基亚烷基Meldrum的酸。该加成是官能团耐受的，并且与非外消旋亚烷基的反应是高度非对映选择性的。衍生自α-酮酸酯的亚烷基的烯丙基化会产生全碳的季立体中心。

  DOI：

  10.1021/ol9003959

文献信息

• Synthesis of new Guanidium-Meldrum acid zwitterionic salts and dynamic NMR study of rotational energy barrier around C-NH bond of guanidine moiety
  作者：Ali Aminkhani

  DOI：10.13005/ojc/300439

  日期：2014.12.31

  Guanidium-Meldrum acid zwitterionic salts was developed through a three component reaction of 2, 2-dimethyl-1, 3-dioxane-4, 6-dione (Meldrum acid), aromatic aldehydes and N, N, N’, N’-Tetramethyl-guanidine in benzen at room temperature. These reaction conditions allow the preparation of stable zwitterionic salts in good yields. A dynamic NMR effect is observed as a result of restricted rotation around the C-NH bond

  通过2、2-二甲基-1、3-二恶烷-4、6-二酮（Meldrum酸），芳族醛和N，N，N'，N的三组分反应开发了胍基-马德鲁姆酸两性离子盐的合成室温下苯中的β-四甲基胍。这些反应条件允许以高收率制备稳定的两性离子盐。在这些化合物的1H NMR光谱中，由于绕C-NH键旋转受限而观察到动态NMR效应。此过程的活化自由能（G＃）对于4b为66±2 kJmol -1。
• A general and practical preparation of alkylidene Meldrum’s acids
  作者：Aaron M. Dumas、Adam Seed、Alexander K. Zorzitto、Eric Fillion

  DOI：10.1016/j.tetlet.2007.08.012

  日期：2007.10

  Although many methods have been reported for the Knoevenagel condensation of aldehydes and Meldrum's acid, most are not general or use unconventional reagents and conditions. We have found that alkylidene Meldrum's acids form readily in benzene solution under mild pyrrolidinium acetate catalysis, and that this reaction is general, highly functional group compatible, and can be scaled-up easily. (c) 2007 Elsevier Ltd. All rights reserved.
• Sc(OTf)₃-Catalyzed Conjugate Allylation of Alkylidene Meldrum’s Acids
  作者：Aaron M. Dumas、Eric Fillion

  DOI：10.1021/ol9003959

  日期：2009.5.7

  Alkylidene Meldrum’s acids are allylated in a conjugate fashion by allyltin nucleophiles under mild Sc(OTf)3-catalyzed conditions. The addition is functional group tolerant and reactions with nonracemic alkylidenes are highly diastereoselective. Allylation of alkylidenes derived from α-ketoesters yield all-carbon quaternary stereocenters.

  在温和的Sc（OTf）3催化条件下，烯丙基锡亲核试剂以共轭方式烯丙基亚烷基Meldrum的酸。该加成是官能团耐受的，并且与非外消旋亚烷基的反应是高度非对映选择性的。衍生自α-酮酸酯的亚烷基的烯丙基化会产生全碳的季立体中心。
• Synthesis and reactions of 1,2-bis[3-cyano-4-(2-fluorophenyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]diselane
  作者：K. A. Frolov、V. V. Dotsenko、S. G. Krivokolysko

  DOI：10.1007/s10593-012-1092-1

  日期：2012.10

  The interaction of 2-fluorobenzaldehyde, cyanoselenoacetamide and Meldrum's acid in the presence of N-methylmorpholine gives 1,2-bis[3-cyano-4-(2-fluorophenyl)-6-oxo-1,4,5,6-tetrahydropyridin-2-yl]di-selane, which also is the product of the reaction of cyanoselenoacetamide with 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione. The diselane obtained interacts with alkyl halides in the presence of a base, forming the corresponding 4-(2-fluorophenyl)-2-(2-R-methylselanyl)-6-oxo-1,4,5,6-tetra-hydropyridine-3-carbonitriles.