4-ethyl-1-methyl mesaconate | 82701-15-3

• 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: 4-ethyl-1-methyl mesaconate
• 英文别名: methyl ethyl mesaconate；1-methyl 4-ethyl mesaconate；1-Ethyl 4-methyl (E)-3-methylbutenedioate；1-ethyl 4-methyl (E)-3-methylbutanedioate；methyl-fumaric acid-4-ethyl ester-1-methyl ester；Methyl-fumarsaeure-4-aethylester-1-methylester；4-O-ethyl 1-O-methyl (E)-2-methylbut-2-enedioate
• CAS: 82701-15-3
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: GERHSFWFMNSNCM-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  4-ethyl-1-methyl mesaconate 在 双氧水 、 (R,R)-N,N’-dimethyl-N,N’-bis(2-methylquinolin-8-yl)-1,2-diphenylethane-1,2-diamine iron(II) bis(triflate) 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 以94%的产率得到
  参考文献：
  名称：

  铁催化的三取代烯烃与H2 O2的高对映选择性顺二羟基化反应。

  摘要：

  缺乏可靠的三取代烯烃对映选择性顺式-二羟基化方法。具有二齿N 4配体（Me 2 -BQPN =（R，R）-N，N'的铁（II）顺式-α-[Fe II（2-Me 2 -BQPN）（OTf）2 ]制备并表征了N-二甲基N，N'-双（2-甲基喹啉-8-基）-1,2-二苯乙烷-1,2-二胺。使用这种络合物作为催化剂，可将多种三取代的缺电子烯烃有效地氧化为手性顺式当在温和条件下使用过氧化氢（H 2 O 2）作为氧化剂时，二醇的收率可达98％，ee高达99.9％。进行了实验研究（包括18 O-标记，ESI-MS，NMR，EPR和UV / Vis分析）和DFT计算，以获取机理上的见解，这表明可能涉及手性顺式-Fe V（O）2反应中间体作为活性氧化剂。这种顺式[Fe II（手性N 4配体）] 2+ / H 2 O 2方法可能是现有OsO 4的可行绿色替代方法/补充方法基于方法的不对称烯烃二羟基化反应。

  DOI：

  10.1002/anie.202002866
• 作为产物：
  描述：

  ethyl trans-2,2-dimethoxy-3-methylcyclopropane-1-carboxylate 在 吡啶 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 38.0h， 生成 4-ethyl-1-methyl mesaconate
  参考文献：
  名称：

  Ring-Opening Reactions of Cyclopropanes. Part 6. A Facile Synthesis of Dialkyl Sulfenylbutanedioates

  摘要：

  DOI：

  10.1055/s-1999-3617

文献信息

• Oxidative scission of ethyl 2,2-dimethoxycyclopropanecarboxylates with lead tetraacetate. Synthesis of the unusual anhydride bis-acetals
  作者：M.Liliana Graziano、Vincenzo Piccialli

  DOI：10.1016/s0040-4039(99)01776-1

  日期：1999.11

  The reaction of ethyl 2,2-dimethoxycyclopropanecarboxylates 1–3 with lead tetraacetate (Pb(OAc)4, LTA) in benzene leads to the oxidative scission of the C1C2 bond. Monoalkylated fumric acid diesters 4 and 5 are obtained from 3-alkylcyclopropanes 1 and 2, respectively, along with dimeric species for which we propose the unusual anhydride bis-acetal structure 6 or 7, respectively. Reaction of 3,3-dimethylcyclopropane

  乙基2,2- dimethoxycyclopropanecarboxylates的反应1-3用四乙酸铅（铅（OAC）4在苯引线，LTA）到C的氧化断链1 C 2键。单烷基化的烟酸二酯4和5分别从3-烷基环丙烷1和2以及二聚体得到，我们分别针对二聚体提出了不同寻常的酸酐双缩醛结构6或7。3，3-二甲基环丙烷3与LTA的反应产生3-乙酰基琥珀酸酯衍生物8作为唯一的反应产物。
• Ring-opening reactions of cyclopropanes. Part 7.1 Selenenylation and cyanoselenenylation of ethyl 2,2-dimethoxycyclopropanecarboxylates
  作者：M. Liliana Graziano、M. Rosaria Iesce、Flavio Cermola、Giovanni Caputo、Fulvio De Lorenzo

  DOI：10.1039/b109480g

  日期：2002.2.22

  1a. The presence of TiCl4 influences the stereochemistry of the reaction with chloride 3 while it is essential for reaction of the less reactive PhSeCN 4. With this electrophile the reactions lead to α,α-dimethoxycarbonitriles 13a–d while only 1a and 1b give also the expected cyanoselenenyl derivatives 12a and 12b. Moreover, from 1b compound syn- 5b is obtained, and 1a gives, via the alkene 2a, esters

  C3取代的未催化反应 环丙烷 1b–d与苯硒烯基氯3生成1-乙基4-甲基2-（苯基硒代）丁二酸酯5b–d，而未取代的1a得到3-苯基硒代衍生物6a。的形成图5b-d发生区域选择性和立体选择性地通过的电开环1而图6a从的所述selenenylation结果烯烃 通过1a的异构化形成2a。TiCl 4的存在会影响与氯化物3的反应的立体化学，而这对于反应性较低的PhSeCN 4的反应必不可少。通过这种亲电试剂，反应生成α，α-二甲氧基腈13a-d，而只有1a和1b也给出了预期的氰基亚烯基衍生物12a和12b。此外，从图1b化合物顺-图5b中获得，和1a中给出，通过所述烯烃 2A，酯类 14a和6a。机理解释表明，稳定的偶极物质9的中间体应通过路易斯酸与碳酸的配位而形成。羰1的氧和随后的开环。
• Anschuetz, Justus Liebigs Annalen der Chemie, 1907, vol. 353, p. 144,178
  作者：Anschuetz

  DOI：——

  日期：——
• Stereospecific alcohol elimination from dialkyl mesaconates under electron impact: Another example of a hidden hydrogen transfer
  作者：Daniel Bornstein、Adrian Weisz、Asher Mandelbaum

  DOI：10.1002/oms.1210210410

  日期：1986.4

  AbstractUnder electron impact dimethyl and diethyl mesaconates give rise to abundant [M  MeOH]+ and [M  EtOH]+ ions, respectively. The geometrically isomeric citraconates yield [M  MeO]+ and [M  EtO]+ ions. Mixed methyl ethyl mesaconates eliminate both methanol and ethanol. These findings, together with the results of a deuterium labelling study, indicate that the elimination of alcohol from the molecular ions of the mesaconates is partially preceded by a hidden hydrogen transfer step.
• Mechanism of electron impact ionization-induced halogen elimination from 2-methyl-2-bromosuccinates
  作者：D. Bornstein、A. Mandelbaum、I. Vidavsky、B. Domon、D. R. Mueller、W. J. Richter

  DOI：10.1002/oms.1210280315

  日期：1993.3

  AbstractThe electron impact‐induced halogen elimination from 2‐methyl‐2‐bromosuccinates occurs only in the one of the two isomeric methyl ethyl esters in which the ethoxycarbonyl group is remote from the halogen, in analogy with the corresponding previously reported halosuccinates. However, the occurrence of debromination in dimethyl 2‐methyl‐2‐bromosuccinate contrasts with the behaviour of dimethyl bromosuccinate, indicating different mechanisms for this process in the two systems. Collision‐induced dissociation (CID) and deuterium labelling studies led to the conclusion that a hydrogen transfer from the 2‐methyl group to a carbonyl precedes the elimination of Br˙ from dimethyl 2‐methyl‐2‐bromosuccinate, resulting in a protonated dimethyl itaconate structure for the [M – Br]+ ion. An analogous process is the major route leading to [M – Br]+ ion from 1‐methyl‐4‐ethyl 2‐methyl‐2‐bromosuccinate. In this case deuterium labelling and CID measurements indicated a significant contribution of methyl ethyl citraconate and possibly mesaconate owing to partial operation of a mechanism similar to that reported for 1‐methyl‐4‐ethyl 2‐bromosuccinate.