ethyl 3-(diethylamino)-3-oxopropanoate | 33567-70-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-(diethylamino)-3-oxopropanoate
• 英文别名: 3-(diethylamino)-3-oxo-propanoic acid ethyl ester；3-(Diethylamino)-3-oxopropanoic acid ethyl ester；ethyl 3-diethylamino-3-oxopropanoate；N,N-diethyl-malonamic acid ethyl ester；N,N-Diaethyl-malonamidsaeure-aethylester；N,N-diethyl-(ethoxy-carbonyl-methyl)-formamide
• CAS: 33567-70-3
• 化学式: C₉H₁₇NO₃
• mdl: MFCD25962450
• 分子量: 187.239
• InChiKey: XKLDZTZOYOPIMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.777
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-(diethylamino)-3-oxopropanoate 在 bis(triphenylphosphine)carbonyliridium(I) chloride 、 1,1,3,3-四甲基二硅氧烷 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以92%的产率得到(E)-3-(二乙基氨基)-2-丙酸乙酯
  参考文献：
  名称：

  Ir催化的β-酰胺基酯的化学选择性还原：β-烯胺基酯的一种通用方法

  摘要：

  对于某些生物碱和相关药物的合成方法，β-酰胺基酯向β-烯氨基酯的转化是必不可少的步骤。用于这种转化的已知方法不仅是逐步的，而且以低原子效率进行。本文中，我们报道了一种直接且通用的方法，其特征在于用1,1,3,3-四甲基二硅氧烷（TMDS）进行Ir催化的β-酰胺基酯的化学选择性还原。另外，在某些脂环族β-烯胺酯的13 C NMR光谱中观察到缺少某些信号。这揭示了文献中长期存在但被忽略的现象。

  DOI：

  10.1016/j.tet.2018.12.024
• 作为产物：
  描述：

  1,3-丙酮二羧酸二乙酯 在 三乙胺 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 336.0h， 生成 ethyl 3-(diethylamino)-3-oxopropanoate
  参考文献：
  名称：

  Transacylation of α-Aryl-β-keto Esters

  摘要：

  The acyl group of an alpha-aryl-beta-keto ester was readily transferred to N-, O-, and S-nucleophiles. The transacylation from arylated diethyl 3-oxoglutarate to amines led to unsymmetrical malonic acid amide esters in high yields. The present reaction proceeded under mild conditions without formation of detectable byproducts. Only simple experimental manipulations were required. This reaction was also found to be sensitive to steric factors, which enabled the chemoselective monoacylation of diamines and amino alcohols without any modifications such as protection.

  DOI：

  10.1021/jo0344642

文献信息

• Substrate-Directable Electron Transfer Reactions. Dramatic Rate Enhancement in the Chemoselective Reduction of Cyclic Esters Using SmI₂–H₂O: Mechanism, Scope, and Synthetic Utility
  作者：Michal Szostak、Malcolm Spain、Kimberly A. Choquette、Robert A. Flowers、David J. Procter

  DOI：10.1021/ja4078864

  日期：2013.10.23

  showing dramatic rate acceleration in the Sm(II)-mediated reduction of cyclic esters that is enabled by transient chelation between a directing group and the lanthanide center. This process allows unprecedented chemoselectivity in the reduction of cyclic esters using SmI2-H2O and for the first time proceeds with a broad substrate scope. Initial studies on the origin of selectivity and synthetic application

  底物导向反应在有机合成中起着关键作用，但在通过自由基机制进行的反应中并不常见。在此，我们提供了实验证据，表明 Sm(II) 介导的环酯还原速率显着加速，这是通过导向基团和镧系元素中心之间的瞬时螯合实现的。该过程在使用 SmI2-H2O 还原环酯时具有前所未有的化学选择性，并且首次在广泛的底物范围内进行。还公开了对形成碳-碳键的选择性起源和合成应用的初步研究。
• Co2(CO)8-induced domino reactions of ethyl diazoacetate, carbon monoxide and ferrocenylimines leading to 2-(1-ferrocenyl-methylidene)-malonic acid derivatives
  作者：János Balogh、Tamás Kégl、Ferenc Ungváry、Rita Skoda-Földes

  DOI：10.1016/j.tetlet.2009.06.035

  日期：2009.8

  Novel 2-(1-ferrocenyl-methylidene)-malonic acid derivatives are obtained upon reacting ethyl diazoacetate, carbon monoxide and ferrocenylimines in the presence of Co2(CO)8 as catalyst under mild conditions. Presumably, the reaction involves three steps taking place in a domino fashion, (i) carbonylation of ethyl diazoacetate leading to a ketene derivative, (ii) [2+2] cycloaddition of the ketene with

  使重氮乙酸乙酯，一氧化碳和二茂铁基亚胺在作为催化剂的Co 2（CO）8存在下，在温和条件下反应，可获得新型2-（1-二茂铁基-亚甲基）-丙二酸衍生物。据推测，该反应涉及以多米诺骨牌方式进行的三个步骤：（i）重氮乙酸乙酯的羰基化生成烯酮衍生物，（ii）烯酮与反应混合物中存在的二茂铁亚胺的[2 + 2]环加成反应，从而得到β-内酰胺的形成和（iii）β-内酰胺环的N（1）-C（4）裂解。在大多数情况下，根据亚胺组分的结构，以E-和Z-异构体的可分离混合物的形式获得2-（1-二茂铁基-亚甲基）-丙二酸衍生物。
• Syntheses and antiinflammatory activity of malonamic acid, malonamate and malonamide derivatives of some heterocyclic compounds.
  作者：TOYOSHI KATAGI、MISAKO AOKI、MASAKO KASHIWAGI、KATSUYA OHATA、SHIGEKATSU KOHNO、TAMOTSU MURATA、TAKESHI INOI

  DOI：10.1248/cpb.33.4878

  日期：——

  Malonamate, malonic acid and malonamide derivatives of heterocyclic compounds were synthesized as part of a search for new biologically active compounds, e. g., those having antiinflammatory activity. Malonamates (1-17) were prepared by the reaction of amines containing heterocycles with malonic acid monoethyl ester. Hydrolysis of the malonamates gave the malonamic acids (18-24) in good yields. Malonamides (25-43) were synthesized by condensing amines with N-substituted malonamic acids. The antiinflammatory activity of these compounds was examined against carrageenin-induced rat paw edema. N-[2-(6-Methoxy) benzothiazolyl] malonamic acid (23) and its ethyl ester (7) showed significant activity.

  作为寻找新生物活性化合物（例如具有抗炎活性的化合物）的一部分，合成了异环化合物的丙二酸酯、丙二酸和丙二酰胺衍生物。通过将含异环的胺与丙二酸单乙酯反应制备了丙二酸酯（1-17）。丙二酸酯的水解得到丙二胺酸（18-24），产率良好。通过将胺与N取代的丙二胺酸缩合，合成了丙二胺（25-43）。这些化合物的抗炎活性在卡拉胶诱导的大鼠足部水肿中进行了测试。N-[2-(6-甲氧基)苯并噻唑基]丙二胺酸（23）及其乙基酯（7）显示出显著的活性。
• Nucleophilic Substitution Accompanying Carbon–Carbon Bond Cleavage Assisted by a Nitro Group
  作者：Yumi Nakaike、Noriko Taba、Shinobu Itoh、Yoshito Tobe、Nagatoshi Nishiwaki、Masahiro Ariga

  DOI：10.1246/bcsj.80.2413

  日期：2007.12.15

  A 2-nitrated 3-oxoester reacted with amines or alcohols to afford unsymmetrical malonic acid derivatives as a result of nucleophilic substitution accompanying C–C bond cleavage. The 2-nitrated 3-oxoester easily formed ammonium salts with amines. When the amine is liberated from the salt under equilibrium, nucleophilic amine and electrophilic keto ester locate close to each other. This intimate pair effect causes a pseudo intramolecular reaction to occur, giving rise to effective substitution under mild conditions.

  一种 2-硝化 3-氧代酯与胺或醇发生反应，生成不对称丙二酸衍生物，这是伴随着 C-C 键裂解的亲核取代反应的结果。2-硝化 3-氧代酯很容易与胺形成铵盐。当胺在平衡状态下从盐中释放出来时，亲核胺和亲电酮酯相互靠近。这种亲密的配对效应会导致发生伪分子内反应，从而在温和的条件下产生有效的取代反应。
• Stereoselective Intramolecular Carbene C–H Insertion Catalyzed by Rhodium(III) Porphyrin Complexes
  作者：Chi-Ming Che、Vanessa Lo、Hung-Yat Thu、Yu-Man Chan、Tsz-Lung Lam、Wing-Yiu Yu

  DOI：10.1055/s-0032-1317322

  日期：——

  Rhodium(III) porphyrin complexes [Rh(Por)Me] are catalytically active towards stereoselective intramolecular carbene C–H insertions of α-diazoacetamides to give cis-β-lactams or trans-γ-lactams in yields up to 99% with regioselectivities up to 100% and cis/trans ratios up to 83:17 for β-lactams.

  铑 (III) 卟啉复合物 [Rh(Por)Me] 对 α-重氮乙酰胺的立体选择性分子内卡宾 C–H 插入具有催化活性，以产生高达 99% 的产率和区域选择性至 100% 且 β-内酰胺的顺/反比高达 83:17。