dimethyl (E)-2-(but-2-en-1-ylidene)malonate | 133445-84-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl (E)-2-(but-2-en-1-ylidene)malonate
• 英文别名: dimethyl 2-((E)-but-2-enylidene)malonate；1-Carboxysorbic acid dimethyl ester；dimethyl (E)-2-butenylidenemalonate；dimethyl but-2-enylidenemalonate；dimethyl 2-[(E)-but-2-enylidene]propanedioate
• CAS: 133445-84-8
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: LPOZQNLOUFXDEB-SNAWJCMRSA-N

物化性质

• 沸点：
  209.4±13.0 °C(Predicted)
• 密度：
  1.076±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl (E)-2-(but-2-en-1-ylidene)malonate 在 吡啶 、 氢氧化钾 作用下， 以 甲醇 为溶剂， 生成 山梨酸
  参考文献：
  名称：

  New conversions of substituted vinylcyclopropanes under the effect of complexes of rhodium and palladium

  摘要：

  Methods have been developed for the synthesis of the dimethyl ester of 1-carboxysorbic acid, 2-methyl-3-acetyl-5-vinyl- and 2-methyl-3-ethylcarboxy-5-vinyldihydrofurans by isomerization, respectively, of 1,1-dimethylcarboxy-2-vinyl-1, 1,1-diacetyl-2-vinyl-, and 1-acetyl-l-ethylcarboxy-2-vinylcyclo-propanes under the effect of Rh- and Pd-containing catalysts promoted with AcOH or CF3COOH.

  DOI：

  10.1007/bf00957856
• 作为产物：
  描述：

  2-乙烯基环丙烷-1,1-二羧酸二甲酯 在 Wilkinson's catalyst 、 溶剂黄146 作用下， 反应 0.17h， 以99%的产率得到dimethyl (E)-2-(but-2-en-1-ylidene)malonate
  参考文献：
  名称：

  New conversions of substituted vinylcyclopropanes under the effect of complexes of rhodium and palladium

  摘要：

  Methods have been developed for the synthesis of the dimethyl ester of 1-carboxysorbic acid, 2-methyl-3-acetyl-5-vinyl- and 2-methyl-3-ethylcarboxy-5-vinyldihydrofurans by isomerization, respectively, of 1,1-dimethylcarboxy-2-vinyl-1, 1,1-diacetyl-2-vinyl-, and 1-acetyl-l-ethylcarboxy-2-vinylcyclo-propanes under the effect of Rh- and Pd-containing catalysts promoted with AcOH or CF3COOH.

  DOI：

  10.1007/bf00957856

文献信息

• 1,6-Addition of Tertiary Carbon Radicals Generated From Alcohols or Carboxylic Acids by Visible-Light Photoredox Catalysis
  作者：Samir Y. Abbas、Peng Zhao、Larry E. Overman

  DOI：10.1021/acs.orglett.7b04034

  日期：2018.2.2

  The addition of tertiary carbon radicals generated by an Ir-catalyzed visible-light photocatalyst to electron-deficient 1,3-dienes proceeds in good yields to append a δ-substituted β,γ-unsaturated carbonyl fragment to a tertiary alcohol or carboxylic acid precursor and construct a new quaternary carbon center.

  将Ir催化的可见光光催化剂产生的叔碳自由基加到缺电子的1,3-二烯上，收率很高，可以将δ-取代的β，γ-不饱和羰基片段附加到叔醇或羧酸前体上并建设一个新的四级碳中心。
• A deconjugative alkylation/Diels-Alder cycloaddition strategy to synthesize 2-substituted bicyclic scaffolds
  作者：Wei Zhang、Ion Ghiviriga、Alexander J. Grenning

  DOI：10.1016/j.tet.2016.11.055

  日期：2017.7

  Knoevenagel adducts derived from α,β-unsaturated aldehydes and a malonic acid derivative can undergo deconjugative alkylation using dienophile-functionalized alkyl iodides. The single step reaction is two-fold significant: (a) The electron-deficient diene (α,β-unsaturated aldehyde Knoevenagel adduct) is deconjugated from the esters, resulting in an electronically neutral diene and (b) tethers the diene

  衍生自α，β-不饱和醛和丙二酸衍生物的Knoevenagel加合物可以使用亲双烯体官能化的烷基碘进行去共轭烷基化。一步反应有两个重要意义：（a）酯中解离缺电子的二烯（α，β-不饱和醛Knoevenagel加合物），生成电子中性的二烯，以及（b）束缚二烯和亲二烯体，它们允许分子内环加成到在2-位带有丙二酸衍生物的双环系统。因此，该序列将简单的试剂转化为天然产物相关的双环支架。我们还公开了由于丙二酸酯在2-位的位置而导致的意想不到的Diels-Alder环加成/芳族CC裂解反应。
• Tellurium-Assisted Cyclopropanation and Alkylidenation of α,β-Unsaturated Carbonyl Compounds with Dibromomalonic Esters
  作者：Toshiaki Matsuki、Nan Xing Hu、Yoshio Aso、Tetsuo Otsubo、Fumio Ogura

  DOI：10.1246/bcsj.62.2105

  日期：1989.6

  Dibutyl telluride assists cyclopropanation of α,β-unsaturated ketone, ester, and nitrile with dibromomalonic esters without solvent at room temperature. In addition, it effects alkylidenation of aldehydes including α,β-unsaturated aldehyde with the same reagent.

  在室温下，二丁基碲化物有助于 α,β-不饱和酮、酯和腈与二溴丙二酸酯的环丙烷化反应。此外，它还可以用相同的试剂进行醛的烷基化，包括α，β-不饱和醛。
• Studies for control of the nickel tetracarbonyl promoted carbonylative cycloaddition allyl halides and acetylenes
  作者：Francisco Camps、Josep Coll、Josep M. Moreto、Josep Torras

  DOI：10.1021/jo00269a041

  日期：1989.4
• Novel Synthesis of Conjugated Dienes Attached to a Quaternary Carbon Center via Pd(0)-Catalyzed Deconjugative Allylation of Alkenylidenemalonates
  作者：Yoshihiro Sato、Yoshihiro Oonishi、Miwako Mori

  DOI：10.1021/jo0353334

  日期：2003.12.1

  Palladium(0)-catalyzed deconjugative allylation of alkenylidenemalonates and alkylidenemalonates was achieved for the first time. Reactions of dimethyl 2-((E)-but-2-enylidene)malonate with various allylic acetates using LHMDS as a base in DMF in the presence of Pd(2)dba(3) (2.5 mol %) and PPh3 (10 mol %) proceeded at room temperature to give the corresponding alpha-allylation products in good yields in a regio- and stereoselective manner. This reaction can also be used for allylation of dimethyl ethylidenemalonate or dimethyl 2-((E)-pent-2-enylidene)malonate and give the desired a-allylation products in good yields.