ethyl (2Z,4E)-2-methyl-5-phenylpenta-2,4-dienoate | 111193-91-0

• 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: ethyl (2Z,4E)-2-methyl-5-phenylpenta-2,4-dienoate
• 英文别名: Uphjcawjzcdvim-rlcsyuecsa-
• CAS: 111193-91-0
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: UPHJCAWJZCDVIM-RLCSYUECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl (2Z,4E)-2-methyl-5-phenylpenta-2,4-dienoate 在 manganese(IV) oxide 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (3E,5E)-3-Methyl-1,1,1-tris-methylsulfanyl-6-phenyl-hexa-3,5-dien-2-ol
  参考文献：
  名称：

  Stereocontrolled syntheses of strobilurin a and its (9)-isomer

  摘要：

  DOI：

  10.1016/s0040-4039(00)95760-5
• 作为产物：
  描述：

  反式肉桂醛 、 2-[二(2,2,2-三氟乙氧基)磷酰]丙酸乙酯 在 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以96%的产率得到ethyl (2Z,4E)-2-methyl-5-phenylpenta-2,4-dienoate
  参考文献：
  名称：

  A comparison of the Still–Gennari and Ando HWE-methodologies with α,β-unsaturated aldehydes; unexpected results with stannyl substituted systems

  摘要：

  Still-Gennari reactions have been carried out on a range of E- and Z-3-substituted propenals. In all cases, with the exception of Z-3-stannyl systems, good Z-stereoselectivity was observed. By contrast, the Ando procedure gives reasonable Z-stereoselectivity with all systems studied, including those with a cis-disposed stannyl substituent. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.095

文献信息

• Rasta Resin-PPh3 and its Use in Chromatography-Free Wittig Reactions
  作者：Patrick Toy、Peter Leung、Yan Teng

  DOI：10.1055/s-0030-1258130

  日期：2010.8

  Rasta resin-PPh3 (RR-PPh3), a new heterogeneous polystyrene-based phosphine, has been synthesized and used in one-pot Wittig olefination reactions of aldehydes. In these reac- tions an excess of RR-PPh3 was used for the in situ generation of the phosphorane reactant, and allowed for isolation of a high yield of very pure alkene product after only filtration and solvent re- moval. The excellent results

  Rasta 树脂-PPh3 (RR-PPh3) 是一种新型多相聚苯乙烯基膦，已被合成并用于醛的单锅 Wittig 烯化反应。在这些反应中，过量的 RR-PPh3 用于原位生成正膦反应物，并允许在仅过滤和去除溶剂后分离出高产率的非常纯的烯烃产物。本研究中获得的优异结果归因于 rasta 树脂结构的柔韧性，这使得它比以前用于在 Wittig 反应中支持膦试剂的其他异质聚苯乙烯材料更少依赖于溶胀。碳-碳双键构成有机化学中的中心官能团之一，合成这种键的重要方法是Wittig反应。这种转化涉及使用磷烷试剂将亚烷基转移到醛或酮基团，同时将原始羰基氧转移到磷（方案 1）。1 通常，正膦是通过叔膦（通常为 PPh3）与卤代烷反应制备的，然后用适当的碱对由此形成的鏻盐进行去质子化。
• Correlation of Hydrolysis and Desilylation of 2-[(Trimethylsilyl)methyl]acrylate Derivatives in Aqueous Alkali Solutions
  作者：Chiaki Kuroda、Takeshi Sunakawa、Yuichi Muguruma

  DOI：10.1002/hlca.200890093

  日期：2008.5

  Hydrolysis and desilylation reaction of 2-[(trimethylsilyl)methyl]acrylate (=2-[(trimethylsilyl)methyl]prop-2-enoate) derivatives were studied to evaluate the effect of the presence/absence of a further conjugating substituent (Schemes 3 and 4 and Tables 1 and 2). The substrates having a nonconjugating substituent at the acrylate moiety were stable to dilute alkali conditions, and afforded simple hydrolysis

  研究了2-[（（三甲基甲硅烷基）甲基]丙烯酸（= 2-[（（三甲硅烷基）甲基]丙-2-烯酸酯）衍生物的水解和脱甲硅基反应，以评估是否存在其他偶联取代基的效果（方案3和4以及表1和2）。在丙烯酸​​酯部分具有非共轭取代基的底物在稀碱条件下是稳定的，并在浓碱条件下提供简单的水解产物。相反，水解和去甲硅烷基化反应都发生在丙烯酸酯骨架上带有共轭取代基的底物上。反应性的差异可以用中间阴离子的稳定性来解释。
• Reactivity of substituted and unsubstituted diphenylphosphonium diylides towards carbonic acids derivatives
  作者：H.J. Cristau、M. Taillefer

  DOI：10.1016/s0040-4020(97)10360-x

  日期：1998.2

  delimit the scope of application of diphenylphosphonium diylides, their reactivity towards carbonic acid derivatives was investigated. Non-stabilized diylides react with ethyl carbonate to give new monoylide intermediates which lead, by in situ Wittig reaction with carbonyl compounds, to the synthesis of α,β-unsaturated esters or acids the double bond being di- or trisubstituted. The reaction proceeds in

  为了进一步限制二苯基phosph二烷基化物的应用范围，研究了它们对碳酸衍生物的反应性。未稳定的二亚烷基化物与碳酸乙酯反应，生成新的单酰化物中间体，该中间体通过与羰基化合物的原位Wittig反应，导致合成被双或三取代的双键的α，β-不饱和酯或酸。该反应在温和的条件下以高E立体选择性进行。稳定的二亚烷基对碳酸酯无活性，但半稳定的二亚烷基与碳酸乙酯反应，导致合成非官能化的烯烃，而不是α，β-不饱和酯或酸。
• Highly <i>E</i>-Selective Solvent-Free Horner-Wadsworth-Emmons Reaction for the Synthesis of α-Methyl-α,β-Unsaturated Esters Using Either LiOH·H₂O or Ba(OH)₂·8H₂O
  作者：Kaori Ando、Wakana Isomura、Nariaki Uchida、Kanae Mori

  DOI：10.1246/bcsj.20220052

  日期：2022.6.15

  Horner-Wadsworth-Emmons reaction, which stirs a mixture of aldehyde, phosphonate reagent 1, and a base without solvent. The reaction of aromatic aldehydes and triethyl 2-phosphonopropionate 1a using LiOH·H2O gave 95-99% E-selectivity in 83-97% yield. The reaction of 1a with aliphatic aldehydes gave 92-94% E-selectivity except for α-branched aldehydes, and the selectivity was improved to 97-98% using ethyl 2-(diis

  ( E )-α-甲基-α,β-不饱和酯通过Horner-Wadsworth-Emmons 反应制备，该反应在无溶剂的情况下搅拌醛、膦酸酯试剂1和碱的混合物。芳香醛和 2-膦酰基丙酸三乙酯1a使用 LiOH·H 2 O 反应得到 95-99% E-选择性，产率为 83-97%。1a与脂肪醛的反应产生92-94% E-选择性，除了 α-支链醛，使用 2-(二异丙基膦酰基)丙酸乙酯1b将选择性提高到 97-98% 。使用 2-膦酰基丙酸三异丙酯1c改善了与 α-支链脂肪醛的反应和Ba(OH) 2 ·8H 2 O，得到98->99%的E-选择性和高产率。在THF中使用Ba(OH) 2 ·8H 2 O的HWE反应也以高产率高度选择性地得到( E )-α-甲基-α,β-不饱和酯。
• Synthesis of α,β-Disubstituted Acrylates via Galat Reaction
  作者：Tania Xavier、Sylvie Condon、Christophe Pichon、Erwan Le Gall、Marc Presset

  DOI：10.1021/acs.orglett.9b02291

  日期：2019.8.2

  Galat reactions between aldehydes and substituted malonic acids half oxyester were found to be efficiently catalyzed by morpholine in refluxing toluene. This transformation allows the stereoselective synthesis of diverse alpha,beta-disubstituted acrylates in moderate to good yields. This method constitutes an attractive alternative to existing methods in terms of scope and eco-compatibility.