3-ethyl-1,5-dimethyl-3-cyanopentane-1,3,5-tricarboxylate | 58774-06-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-ethyl-1,5-dimethyl-3-cyanopentane-1,3,5-tricarboxylate
• 英文别名: triethyl 3-cyanopentane-1,3,5-tricarboxylate；3-cyano-pentane-1,3,5-tricarboxylic acid triethyl ester；3-Cyan-pentan-1,3,5-tricarbonsaeure-triaethylester
• CAS: 58774-06-4
• 化学式: C₁₅H₂₃NO₆
• mdl: MFCD08273448
• 分子量: 313.351
• InChiKey: KWGZTKPIPLQODU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  22
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-ethyl-1,5-dimethyl-3-cyanopentane-1,3,5-tricarboxylate 在 potassium chloride 、 苄基三乙基氯化铵 作用下， 以 二甲基亚砜 为溶剂， 反应 11.0h， 以77%的产率得到diethyl 4-cyanopimelate
  参考文献：
  名称：

  Synthesis of polyfunctional aliphatic carbonyl compounds under phase-transfer conditions

  摘要：

  We have studied mono- and dialkylation of malonic, acetoacetic, and cyanoacetic esters with esters of haloacetic and beta-halopropionic acids and addition of the CH acids mentioned and their analogs to methyl and ethyl acrylate under phase-transfer catalysis conditions, and also deethoxycarbonylation of the obtained products. We have demonstrated for the first time the possibility of Dieckmann cyclization under phase-transfer catalysis conditions and have developed a simple method for the synthesis of 2,3-di(ethoxycarbonyl)cyclopentanone, a key intermediate in the syntheis of deoxyprostaglandins, by cyclization of triethyl 1,2,4-butanetricarboxylate.

  DOI：

  10.1007/bf00961357
• 作为产物：
  描述：

  丙烯酸乙酯 在 苄基三乙基氯化铵 氢氧化钾 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 3-ethyl-1,5-dimethyl-3-cyanopentane-1,3,5-tricarboxylate
  参考文献：
  名称：

  Synthesis of polyfunctional aliphatic carbonyl compounds under phase-transfer conditions

  摘要：

  We have studied mono- and dialkylation of malonic, acetoacetic, and cyanoacetic esters with esters of haloacetic and beta-halopropionic acids and addition of the CH acids mentioned and their analogs to methyl and ethyl acrylate under phase-transfer catalysis conditions, and also deethoxycarbonylation of the obtained products. We have demonstrated for the first time the possibility of Dieckmann cyclization under phase-transfer catalysis conditions and have developed a simple method for the synthesis of 2,3-di(ethoxycarbonyl)cyclopentanone, a key intermediate in the syntheis of deoxyprostaglandins, by cyclization of triethyl 1,2,4-butanetricarboxylate.

  DOI：

  10.1007/bf00961357

文献信息

• A simple, efficient and green procedure for Michael addition catalyzed by [C4dabco]OH ionic liquid
  作者：Sanjoy Keithellakpam、Warjeet S. Laitonjam

  DOI：10.1016/j.cclet.2014.01.032

  日期：2014.5

  liquid, 1-butyl-4-aza-1-azaniabicyclo[2.2.2]octane hydroxide, has been developed as a catalyst for a convenient and rapid method for the Michael addition of active methylene compounds to α , β -unsaturated carboxylic esters and nitriles. The method is very simple, and the yields are very high. The catalyst can be recycled several times without much loss of activity.

  摘要已开发出基于dabco的碱性离子液体1-丁基-4-氮杂-1-氮杂双环[2.2.2]辛烷氢氧化​​物，作为一种方便快捷的方法，用于将活性亚甲基化合物迈克尔加成的方法，β-不饱和羧酸酯和腈。该方法非常简单，并且产率很高。催化剂可以循环使用几次而不会损失很多活性。
• Binary caesium–lanthanum oxide supported on MCM-41: A new stable heterogeneous basic catalyst
  作者：K. R. Kloetstra、M. van Laren、H. van Bekkum

  DOI：10.1039/a606766b

  日期：——

  Heterogeneous mesoporous stable basic catalysts have been prepared by wet or solid-state impregnation of MCM-41 with caesium acetate and lanthanum nitrate followed by thermal decomposition. 133 Cs MAS NMR data of CsLa/MCM-41 show an increase in the Cs–O bond length in the CsLa mixed oxides compared with that in Cs oxides supported on MCM-41. A small difference in chemical shift between the hydrated and dehydrated materials is observed, indicating a weak interaction of water with Cs + cations. CO 2 temperature-programmed desorption (TPD) suggests that these materials possess small oxide clusters of mild basicity. The thermal stability of the materials, which is independent of the framework aluminium content, is reflected by an unaffected CO 2 desorption and BET surface area on successive thermal cycles. Alkali metal–lanthanum binary oxides of the Na, K and Rb-type appear to be thermally less stable, in the sense of a significantly smaller CO 2 desorption indicative of particle clustering. 23 Na MAS NMR shows several resonances for the NaLaO x materials. The presence of the single Rb-oxide component in the RbLaO x materials is confirmed by 87 Rb MAS NMR. The mild base strength of the CsLaO x /MCM-41 is demonstrated by its ability to remove a proton from enolates having a pK a ⩽10.2. The presence of lanthanum and the mesoporous framework govern the activity and product selectivity in the liquid-phase Michael addition of ethyl cyanoacetate to ethyl acrylate. The Knoevenagel addition of enolates to benzaldehyde in aqueous media is also catalysed by the CsLa-oxide/MCM-41 system. The catalyst is re-usable after regeneration at high temperature without loss of activity.

  通过醋酸铯和硝酸镧湿法或固态浸渍 MCM-41，然后进行热分解，制备出了异质介孔稳定碱性催化剂。 CsLa/MCM-41 的 133 Cs MAS NMR 数据显示，与 MCM-41 上支撑的铯氧化物相比，CsLa 混合氧化物中的 CsâO 键长度有所增加。水合材料和脱水材料之间的化学位移差异很小，这表明水与 Cs + 阳离子之间的相互作用很弱。CO 2 温度编程解吸（TPD）表明，这些材料具有温和碱性的小氧化物簇。这些材料的热稳定性与框架中的铝含量无关，在连续的热循环中，其 CO 2 解吸和 BET 表面积均不受影响。Na、K 和 Rb 型碱金属镧二元氧化物的热稳定性似乎较差，因为它们的 CO 2 解吸附量明显较小，这表明存在颗粒聚集现象。87 Rb MAS NMR 证实了 RbLaO x 材料中存在单一的铷氧化物成分。CsLaO x /MCM-41 能够从 pK a â½10.2 的烯醇中去除一个质子，这证明了它的弱碱强度。在氰乙酸乙酯与丙烯酸乙酯的液相迈克尔加成反应中，镧和介孔框架的存在决定了活性和产物选择性。CsLa-oxide/MCM-41 系统还能在水介质中催化烯醇类与苯甲醛的 Knoevenagel 加成反应。催化剂在高温下再生后可重复使用，且不会失去活性。
• A simple and highly efficient procedure for construction of quaternary carbons centers by tributylphosphine catalyzed bis-Michael addition
  作者：Da-Zhen Xu、Ming-Zhe Zhan、You Huang

  DOI：10.1016/j.tet.2013.11.103

  日期：2014.1

  The tributylphosphine-catalyzed bis-Michael addition reaction of various kinds of a,13-unsaturated carbonyl compounds with active methylenes is described. This is a convenient and rapid method for generating quaternary carbons centers and useful procedure for the synthesis of branched core and highly substituted trans cyclohexanones. All the reactions were completed in 60 min and afford the corresponding products in excellent yields. (C) 2013 Elsevier Ltd. All rights reserved.
• Ruthenium-catalyzed aldol and Michael reactions of nitriles. Carbon-carbon bond formation by .alpha.-C-H activation of nitriles.
  作者：Shun-Ichi Murahashi、Takeshi Naota、Hiroshi Taki、Masahiko Mizuno、Hikaru Takaya、Sanshiro Komiya、Yuji Mizuho、Naohiko Oyasato、Makiko Hiraoka

  DOI：10.1021/ja00155a008

  日期：1995.12

  The ruthenium(II)-catalyzed reaction of nitriles with carbonyl compounds proceeds highly efficiently under neutral and mild conditions to give alpha,beta-unsaturated nitriles. Under similar reaction conditions, nitriles react with olefins bearing electron-withdrawing groups to give the corresponding Michael adducts. The efficiency of the reaction is illustrated by the selective additions to alpha,beta-unsaturated aldehydes and acetylenes bearing electron-withdrawing groups, which are difficult to perform using conventional bases. Chemoselective aldol and Michael reactions of nitriles can be performed in the presence of other active methylene compounds. Tandem Michael and Michael-aldol condensations of nitriles 30 can be performed with high diastereoselectivity. These reactions can be rationalized by assuming oxidative addition of ruthenium(0) to the alpha=C-H bond of nitriles and subsequent insertions to carbonyl compounds or olefins. As the key intermediates and active catalysts hydrido(N-bonded enolato)ruthenium(II) complexes, mer-RuH(NCCHCO(2)R)(NCCH(2)CO(2)R)(PPh(3))(3) (R = Me (41a), Et (41b), n-Bu (41c) have been upon treatment of RuH2(PPh(3))(4) (3) or RuH(C2H4)(PPh(3))(2)(PPh(2)C(6)H(4)) (4) with alkyl cyanoacetates. Kinetic study of the catalytic aldol reaction of ethyl cyanoacetate with benzaldehyde indicates that the rate-determining step reaction of enolato complex 41 with aldehydes.
• 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Immobilized in MCM-41: A Strongly Basic Porous Catalyst
  作者：Yarlagadda V. Subba Rao、Dirk E. De Vos、Pierre A. Jacobs

  DOI：10.1002/anie.199726611

  日期：1997.12.15