dimethyl (E)-2-<(4-methylphenyl)methylene>butanedioate | 100046-96-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: dimethyl (E)-2-<(4-methylphenyl)methylene>butanedioate
• 英文别名: methyl (E)-4-(4-methylphenyl)-3-methoxycarbonylbut-3-enoate；E-methyl 4-(4-methylphenyl)-3-methoxycarbonylbut-3-enoate；dimethyl 2-(4-methylbenzylidene)succinate；E-Dimethyl-4-tolyl-methylensuccinat；Butanedioic acid, [(4-methylphenyl)methylene]-, dimethyl ester, (2E)-(9CI)；dimethyl (2E)-2-[(4-methylphenyl)methylidene]butanedioate
• CAS: 100046-96-6
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: GNVKZHPTPKBSNV-XYOKQWHBSA-N

物化性质

• 沸点：
  155-160 °C(Press: 1.1 Torr)
• 密度：
  1.131±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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-<(4-methylphenyl)methylene>butanedioate 在 sodium ethanolate 、 乙酸酐 作用下， 以 乙醚 为溶剂， 反应 50.0h， 生成 (Z,Z)-2-<(4-methylphenyl)methylene>-3-(2-thienylmethylene)succinic anhydride
  参考文献：
  名称：

  Guirguis, Nadia R.; Awad, Boshra M.; Saad, Hanaa A., Liebigs Annalen der Chemie, 1986, # 6, p. 1003 - 1011

  摘要：

  DOI：
• 作为产物：
  描述：

  丁二酸二甲酯 在 potassium tert-butylate 、 potassium carbonate 作用下， 以 丙酮 、 叔丁醇 为溶剂， 反应 0.75h， 生成 dimethyl (E)-2-<(4-methylphenyl)methylene>butanedioate
  参考文献：
  名称：

  Guirguis, Nadia R.; Awad, Boshra M.; Saad, Hanaa A., Liebigs Annalen der Chemie, 1986, # 6, p. 1003 - 1011

  摘要：

  DOI：

文献信息

• Novel Base-Free Catalytic Wittig Reaction for the Synthesis of Highly Functionalized Alkenes
  作者：Marie-Luis Schirmer、Sven Adomeit、Anke Spannenberg、Thomas Werner

  DOI：10.1002/chem.201503744

  日期：2016.2.12

  base‐free catalytic Wittig reactions has been developed and optimized. Initially, several potential (pre)catalysts as well as different silanes as reducing agents were screened. A system based on a readily available phosphine oxide as precatalyst and trimethoxy silane as reducing agent proved to be optimal. The effect of various Brønsted acidic additives was studied. Subsequently, the reaction conditions were

  已开发并优化了一种用于无碱催化Wittig反应的高效催化剂体系。最初，筛选了几种潜在的（预）催化剂以及不同的硅​​烷作为还原剂。基于容易获得的氧化膦作为前催化剂和三甲氧基硅烷作为还原剂的体系被证明是最佳的。研究了各种布朗斯台德酸性添加剂的效果。随后，优化反应条件并确定标准反应条件。在这些条件下，对该新协议的范围进行了评估。将九种活化烯烃和33种醛转化为42种高度官能化的烯烃。值得注意的是，可以将芳族，脂族和杂芳族醛进行转化，从而以高达99％的分离产率得到所需产物，并具有良好至优异的分离度。E / Z选择性。考虑到反应混合物的复杂性以及在一个罐中并行进行的四个反应步骤，这些结果强调了该方案的显着效率。
• Silver sequestration of halides for the activation of Pd(OAc) ₂ catalyzed Mizoroki‐Heck reaction of 1,1 and 1,2 ‐ Disubstituted alkenes
  作者：Pronnoy G. Bangar、Priyanka R. Jawalkar、Swapnil R. Dumbre、Dharmaraj J. Patil、Suresh Iyer

  DOI：10.1002/aoc.4159

  日期：2018.3

  A ligand free catalytic system consisting of Pd(OAc)2 (cat) and stoichiometric quantities of silver salts, AgOAc or AgBF4, exhibit high efficiency in the Mizoroki‐Heck arylation, transforming aryl iodides and 1,1 as well as 1,2 disubstituted alkenes into 1,1,2 – trisubstituted aryl alkenes in excellent yields in very short reaction times.

  由Pd（OAc）2（cat）和化学计量的银盐AgOAc或AgBF 4组成的无配体催化体系在Mizoroki-Heck芳基化反应中表现出高效率，可转化芳基碘化物和1,1以及1,2在非常短的反应时间内，双取代的烯烃就可以以优异的收率转化成1,1,2-三取代的芳基烯烃。
• Phosphine-Catalyzed Cross-Coupling of Benzyl Halides and Fumarates
  作者：Tingting Yan、Kaki Raveendra Babu、Yong Wu、Yang Li、Yuhai Tang、Silong Xu

  DOI：10.1021/acs.orglett.1c01214

  日期：2021.6.18

  A phosphine-catalyzed olefinic cross-coupling between benzyl halides and fumarates is described, which affords trisubstituted alkenes in good yields and excellent E-selectivity under metal-free conditions. Mechanistic studies suggest a catalytic cycle involving phosphorus ylide formation, Michael addition, water-assisted hydrogen transfer, and phosphine elimination.

  描述了苄基卤化物和富马酸酯之间的膦催化的烯烃交叉偶联，其在无金属条件下以良好的产率和优异的E选择性提供三取代的烯烃。机理研究表明催化循环涉及磷叶立德形成、迈克尔加成、水辅助氢转移和膦消除。
• Synthesis of 6-deoxymollugins and their inhibitory activities on tyrosinase
  作者：Jing Lu Liang、Umair Javed、Seung Ho Lee、Jae Gyu Park、Yurngdong Jahng

  DOI：10.1007/s12272-013-0240-1

  日期：2014.7

  A series of 6-deoxymollugins were prepared five steps from benzaldehyde and its derivatives via phenylboronic acid-catalyzed chromenylation as a key step. Their inhibitory activities against tyrosinase from mushroom were evaluated to show that the parent, methyl 2,2-dimethyl-2H-benzo[h]chromene-5-carboxylate (9a) showed best and promising inhibitory activity at IC50 = 18.3 μM.

  以苯甲醛及其衍生物为原料，通过苯硼酸催化的铬化反应为关键步骤，分五个步骤制备了一系列6-脱氧毛蕊花素。结果表明，母体 2,2-二甲基-2H-苯并[h]色烯-5-羧酸甲酯（9a）的抑制活性最好，IC50 = 18.3 μM。
• Sequential Transformation of Diethyl Phosphite. A Convenient Synthesis of Substituted (E)-3-Alkoxycarbonyl-β,γ-unsaturated Esters
  作者：Yanchang Shen、Zenghong Zhang

  DOI：10.1039/a803769h

  日期：——

  The sequential reaction of diethyl phosphite with sodium alkoxide, dimethyl maleate and aldehydes affords substituted (E)-3-alkoxycarbonyl-β,γ-unsaturated esters in 63–73% yields.

  亚磷酸二乙酯与醇钠，马来酸二甲酯和醛的顺序反应，以63-73％的收率得到取代的（E）-3-烷氧基羰基-β，γ-不饱和酯。