diethyl citrylidenemalonate | 52567-20-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: diethyl citrylidenemalonate
• 英文别名: diethyl (3,7-dimethyl-2,6-octadienylidene)malonate；ethyl 5,9-dimethyl-2-ethoxycarbonyl-2,4,8-decatrienoate；4,8-Dimethyl-nonatrien-1,3,7-dicarbonsaeure-diethylester；(3,7-dimethyl-octa-2,6-dienylidene)-malonic acid diethyl ester；2-(3,7-dimethyl-octa-2,6-dienylidene)malonic acid diethyl ester；(3,7-Dimethyl-octa-2,6-dienyliden)-malonsaeure-diaethylester；Diethyl (3,7-dimethylocta-2,6-dien-1-ylidene)propanedioate；diethyl 2-(3,7-dimethylocta-2,6-dienylidene)propanedioate
• CAS: 52567-20-1
• 化学式: C₁₇H₂₆O₄
• 分子量: 294.391
• InChiKey: UDFKZBBVSIDXIL-UHFFFAOYSA-N

物化性质

• 沸点：
  142-143.5 °C(Press: 0.35 Torr)
• 密度：
  0.993±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  diethyl citrylidenemalonate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以46%的产率得到monoethyl citrylidenemalonate
  参考文献：
  名称：

  Mechanism of cyclocondensation of isoprenoid acyclic ?,?-enals with monoethyl malonate under the conditions of the Knoevenagel reaction

  摘要：

  It was shown that the formation of the di- and trisubstituted derivatives of 1.3-cyclohexadiene-1-carboxylic acid during the condensation of 3-methyl-2-butenal, citral, and farnesal with monoethyl malonate in the presence of secondary amines takes place through the enamines corresponding to these aldehydes, which add to the monoesters of the respective alkenylidenemalonic acids (the "normal" products of the Knoevenagel reaction) by a mechanism of [4 + 2]-cycloaddition. The free carboxyl group in the dienophile is required for the spontaneous transformation of the intermediate [4 + 2]-cycloadducts into the derivatives of cyclohexadiene-1-carboxylic acid in which the catalyst of the process (the secondary amine) is regenerated.

  DOI：

  10.1007/bf00961358
• 作为产物：
  描述：

  丙二酸二乙酯 、 柠檬醛 在 哌啶 作用下， 以 苯 为溶剂， 反应 12.0h， 以50%的产率得到diethyl citrylidenemalonate
  参考文献：
  名称：

  Mechanism of cyclocondensation of isoprenoid acyclic ?,?-enals with monoethyl malonate under the conditions of the Knoevenagel reaction

  摘要：

  It was shown that the formation of the di- and trisubstituted derivatives of 1.3-cyclohexadiene-1-carboxylic acid during the condensation of 3-methyl-2-butenal, citral, and farnesal with monoethyl malonate in the presence of secondary amines takes place through the enamines corresponding to these aldehydes, which add to the monoesters of the respective alkenylidenemalonic acids (the "normal" products of the Knoevenagel reaction) by a mechanism of [4 + 2]-cycloaddition. The free carboxyl group in the dienophile is required for the spontaneous transformation of the intermediate [4 + 2]-cycloadducts into the derivatives of cyclohexadiene-1-carboxylic acid in which the catalyst of the process (the secondary amine) is regenerated.

  DOI：

  10.1007/bf00961358

文献信息

• Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups
  作者：Fanke Meng、Xiben Li、Sebastian Torker、Ying Shi、Xiao Shen、Amir H. Hoveyda

  DOI：10.1038/nature19063

  日期：2016.9

  Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable

  碳阴离子物质与 α,β-不饱和羰基化合物的共轭（或 1,4-）加成对于有机和药物化学研究至关重要，并且有几种手性催化剂可促进亲核试剂对烯酸酯的催化对映选择性加成。尽管如此，催化对映选择性 1,6-共轭加成并不常见，将易于官能化的部分（如炔丙基或烯丙基）结合到无环 α,β,γ,δ-双不饱和受体中的那些是未知的。可以在二烯酸酯的 C6 位置产生新键的化学转化是特别可取的，因为可以对所得产物进行进一步的修饰。然而，这种反应，尤其是当二烯酸酯含有两个等量取代的烯烃时，稀少且仅限于由膦-铜催化剂（与烷基格氏试剂、二烷基锌或三烷基铝化合物）、二烯-铱催化剂（与芳基环硼烷）或双膦-钴催化剂（与单甲硅烷基-乙炔）促进的反应。1,6-共轭添加另外仅限于在 C4 位置有完全取代的底物。目前尚不清楚为什么某些催化剂有利于在 C6 上形成键，并且——尽管存在少量催化对映选择性共轭烯丙基加成——相关的 1,6-加成
• Regioselective Tandem Dimethylsulfonium Methylide Addition−Eliminative Olefination of Diendioates:  A Novel Route to 1,3-Butadien-2-ylmalonates
  作者：Rekha Singh、Sunil K. Ghosh

  DOI：10.1021/ol702384s

  日期：2007.11.1

  The appropriate choice of dimethylsulfonium methylide generation conditions enables the highly regioselective tandem ylide addition-eliminative olefination to 1,3-dienedioates providing 1,3-butadien-2-ylmalonates, a novel class of 2-substituted 1,3-dienes suitable for quick assembly of precursors for type 2 intramolecular Diels-Alder reactions.

  的二甲基锍甲基氧生成条件的适当选择使高度选择性串联叶立德加成消去烯1,3- dienedioates提供1,3-丁二烯-2- ylmalonates，一类新的2-取代的1,3-二烯适合快速组装用于2型分子内Diels-Alder反应的前体。
• A dimethylsulfonium methylide mediated highly regioselective olefination of conjugated polyolefin 1,1-dioates to conjugated polyene-2-yl-malonates and their applications in Diels–Alder reactions
  作者：Rekha Singh、Sunil K. Ghosh

  DOI：10.1016/j.tet.2010.02.013

  日期：2010.3

  dienophile generation led to quick assembly of precursors for type 2 intramolecular Diels–Alder reaction. Syntheses of functionalized bicyclo[n.3.1] alkenes (n=5 or 6) with the double bond at the bridgehead position have been achieved via the IMDA. An asymmetric version of this reaction has been developed using a MacMillan's imidazolidinone catalyst, which provided a bicyclo[5.3.1] alkene with very

  在特定条件下，二甲基s甲基化物与1,3-二烯-或1,3,5-三烯-1,1-二酸酯之间的反应可实现高度区域选择性的串联内酯加成-消除烯烃化反应，从而提供1,3-丁二烯-2-基-或1,3,5-己三烯-2-基丙二酸酯。1,3-丁二烯-2-基丙二酸在丙二酸次甲基碳上的烷基化与合适的具有内置功能的烷基卤化物可用于生成亲二烯体，可快速组装用于2型分子内Diels-Alder反应的前体。官能化的双环[ n .3.1]烯烃的合成（n= 5或6）通过IMDA实现了在桥头位置的双键连接。该反应的不对称形式是使用MacMillan的咪唑烷酮催化剂开发的，该催化剂可提供具有很高对映选择性的双环[5.3.1]烯烃。1,3,5-己三烯-2-基丙二酸在丙二酸次甲基碳上进行原位甲基化，然后与N-甲基马来酰亚胺进行分子间Diels-Alder反应，为环加合物提供了完全的区域控制和非对映选择性。
• Interphase catalysis in Michael and Knoevenagel reactions with ?,?-unsaturated aldehydes
  作者：G. V. Kryshtal'、V. V. Kul'ganek、V. F. Kucherov、L. A. Yanovskaya

  DOI：10.1007/bf00941112

  日期：1978.12
• Kasatkin, A.N.; Biktimirov, R.Kh.; Kulak, A.N., Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 4.1, p. 613 - 620
  作者：Kasatkin, A.N.、Biktimirov, R.Kh.、Kulak, A.N.、Tolstikov, G.A.

  DOI：——

  日期：——