4-methyl-3,5-dioxopimelic acid dimethyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 4-methyl-3,5-dioxopimelic acid dimethyl ester
• 英文别名: dimethyl 4-methyl-3,5-dioxoheptanedioate；Dimethyl 4-methyl-3,5-dioxoheptanedioate
• 化学式: C₁₀H₁₄O₆
• 分子量: 230.218
• InChiKey: VMXQEMOEXGGTHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-methyl-3,5-dioxopimelic acid dimethyl ester 、 甲基肼 以 乙醇 为溶剂， 以50%的产率得到dimethyl 2,2'-(1,4-dimethyl-1H-pyrazole-3,5-diyl)diacetate
  参考文献：
  名称：

  3,5-Dioxopimelates as new synthetic building blocks. Cyclocondensation with 1,2-, 1,3- and 1,4-dinucleophiles

  摘要：

  Cyclocondensation reactions of 3,5-dioxopimelates, new and versatile synthetic building blocks, with hydrazines, urea, thiourea and phenylene-1,2-diamines allow for a convenient synthesis of various heterocycles containing two ester-substituted side-chains. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.05.119
• 作为产物：
  描述：

  丙二酸甲酯酰氯 、 1,3-bis(trimethylsiloxy)-1-methoxypenta-1,3-diene 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以20%的产率得到4-methyl-3,5-dioxopimelic acid dimethyl ester
  参考文献：
  名称：

  通过1,3-双-甲硅烷基烯醇醚的酰化反应合成3,5-二氧羰基链烷酸酯，3,5-二氧庚二酸酯和2,4-二氧己二酸酯

  摘要：

  3，5-二氧代链烷酸酯，3，5-二氧代庚二酸酯和2，4-二氧代己二酸酯是通过将1，3-双甲硅烷基烯醇醚与羧酸氯化物，3-氯-3-氧代丙酸甲酯和2-氯-2乙酯酰化制备的。 -氧代乙酸盐。

  DOI：

  10.1016/j.tetlet.2005.09.134

文献信息

• Synthesis and solution structure of 3,5-dioxopimelic acid diesters—stable 1,3,5,7-tetracarbonyl derivatives
  作者：Stefanie Reim、Dirk Michalik、Klaus Weisz、Zhou Xiao、Peter Langer

  DOI：10.1039/b805808c

  日期：——

  A variety of 3,5-dioxopimelic acid diesters, stable 1,3,5,7-tetracarbonyl derivatives, were prepared by catalytic condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with methyl malonyl chloride. The keto–enol tautomerization of these compounds has been investigated by NMR spectroscopy. One keto and up to four enolic tautomers could be detected in chloroform solution and the influence of the substituents on the tautomeric equilibria has been studied.

  通过1,3-双(三甲基硅氧基)-1,3-丁二烯与甲基丙二酰氯的催化缩合反应，制备了一系列稳定的3,5-二氧代庚二酸二酯1,3,5,7-四羰基衍生物。利用核磁共振光谱研究了这些化合物的酮-烯醇互变异构现象。在氯仿溶液中，可以检测到一个酮式异构体和多达四个烯醇式异构体，并研究了取代基对互变异构平衡的影响。
• Synthesis of 3,5-dioxoalkanoates, 3,5-dioxopimelates and 2,4-dioxoadipates by acylation of 1,3-bis-silyl enol ethers
  作者：Stefanie Reim、Van Thi Hong Nguyen、Uwe Albrecht、Peter Langer

  DOI：10.1016/j.tetlet.2005.09.134

  日期：2005.11

  3,5-Dioxoalkanoates, 3,5-dioxopimelates and 2,4-dioxoadipates were prepared by acylation of 1,3-bis-silyl enol ethers with carboxylic chlorides, methyl 3-chloro-3-oxopropanoate and ethyl 2-chloro-2-oxoacetate, respectively.

  3，5-二氧代链烷酸酯，3，5-二氧代庚二酸酯和2，4-二氧代己二酸酯是通过将1，3-双甲硅烷基烯醇醚与羧酸氯化物，3-氯-3-氧代丙酸甲酯和2-氯-2乙酯酰化制备的。 -氧代乙酸盐。
• Experimental and Theoretical Study of the Keto-Enol Tautomerization of 3,5-Dioxopimelates
  作者：Silke Erfle、Stefanie Reim、Dirk Michalik、Haijun Jiao、Peter Langer

  DOI：10.1002/ejoc.201100292

  日期：2011.8

  Substituted 3,5-dioxopimelic acid diesters, stable 1,3,5,7-tetracarbonyl derivatives, were prepared by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with methyl malonyl chloride. The influence of the substituents and the solvent on the keto–enol tautomerization of these compounds was investigated by NMR spectroscopy. For the parent compound, the experimental findings were compared with

  取代的 3,5-二氧庚二酸二酯，稳定的 1,3,5,7-四羰基衍生物，通过 1,3-双（三甲基甲硅烷氧基）-1,3-丁二烯与甲基丙二酰氯缩合制备。通过核磁共振光谱研究了取代基和溶剂对这些化合物的酮-烯醇互变异构化的影响。对于母体化合物，将实验结果与计算结果进行比较。
• NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates
  作者：Dirk Michalik、Haijun Jiao、Peter Langer

  DOI：10.1002/mrc.5272

  日期：2022.8

  4-(3H,5H)diylidene)diacetate (1a) and dimethyl 2,2′-(7,8-dichloro-3-methyl-1H-benzo[b][1,4]diazepine-2,4-(3H,5H)diylidene)diacetate (1b) was investigated by 1H, 13C and 15N nuclear magnetic resonance (NMR) spectroscopy. In CDCl3 solution, inversion of the diazepine ring was observed, whereas in (D6)DMSO and (D7)DMF solution, besides the ring inversion, a partial cleavage of one chelate ring appeared connected

  2,2'-(7,8-dichloro-1 H -benzo[ b ][1,4]diazepine-2,4-(3 H ,5 H )diylidene) 二乙酸二甲酯 ( 1a ) 和二甲基 2的异构体,2'-(7,8-dichloro-3-methyl-1 H -benzo[ b ][1,4]diazepine-2,4-(3 H ,5 H )diylidene) diacetate ( 1b ) 由1 H、13 C 和15 N 核磁共振 (NMR) 光谱。在 CDCl 3溶液中，观察到二氮杂环倒置，而在 ( D 6 )DMSO 和 ( D 7)DMF 溶液，除了环反转外，一个螯合环的部分裂解出现与环外 C=C 键之一的( E / Z ) 异构化有关。基于 B3PW91-SCRF/ZVP DFT 计算计算吉布斯自由能 (ΔG) 和自由活化能 (ΔG ≠ )。发现 NMR 数据和密度泛函理论 (DFT)
• Synthesis and characterization of permethylated 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds
  作者：Silke Erfle、Thomas Rahn、Franziska Bendrath、Wolfgang Baumann、Dirk Michalik、Haijun Jiao、Anke Spannenberg、Armin Börner、Peter Langer

  DOI：10.1016/j.tet.2011.08.065

  日期：2011.11

  Permethylated 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds were prepared and structurally characterized. 2,2,4,4-Tetramethyl-3,5-dioxoesters were prepared by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with acid chlorides and subsequent reaction with methyl iodide. 2,2,4,4,6,6-Hexa-substituted 3,5-dioxopimelates were prepared by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with methyl 3-chloro-3-oxopropanoate and subsequent methylation. The use of caesium carbonate as the base for the methylation proved to be important to achieve good yields. The conformation of the products was studied by experimental and theoretical methods (DFT calculations). (C) 2011 Elsevier Ltd. All rights reserved.