diethyl 2-(1'-methyl-3'-oxocyclohexyl)malonate | 88710-73-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-(1'-methyl-3'-oxocyclohexyl)malonate
• 英文别名: Propanedioic acid, (1-methyl-3-oxocyclohexyl)-, diethyl ester；diethyl 2-(1-methyl-3-oxocyclohexyl)propanedioate
• CAS: 88710-73-0
• 化学式: C₁₄H₂₂O₅
• 分子量: 270.326
• InChiKey: OYJUCMYMVNQKKC-UHFFFAOYSA-N

物化性质

• 沸点：
  342.2±12.0 °C(Predicted)
• 密度：
  1.096±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-(1'-methyl-3'-oxocyclohexyl)malonate 在 盐酸 、 氢氧化钾 作用下， 生成 3-methylcyclohexanone-3-acetic acid
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019
• 作为产物：
  描述：

  3-甲基-2-环己烯-1-酮 、 丙二酸二乙酯 在 1,5-二氮杂双环[4.3.0]壬-5-烯 作用下， 以 乙腈 为溶剂， 25.0 ℃ 、1499.99 MPa 条件下， 反应 48.0h， 以71%的产率得到diethyl 2-(1'-methyl-3'-oxocyclohexyl)malonate
  参考文献：
  名称：

  高压下的有机反应。活化的无环供体与β，γ-二取代的烯酮受体的迈克尔加成。

  摘要：

  高压，15 kbar（1.5 GPa），在乙腈中带有1,5-二氮杂双环[4.3.0] non-5-ene的迈克尔将双活化无环供体与空间受阻的烯酮受体加成后，迈克尔加合物的收率为42-82％。

  DOI：

  10.1016/s0040-4039(00)94290-4

文献信息

• Organic reactions at high pressure. Michael addition of activated acyclic donors with β,⨿-disubstituted enone acceptors.
  作者：William G Dauben、John M Gerdes

  DOI：10.1016/s0040-4039(00)94290-4

  日期：1983.1

  High pressure, 15 kbar (1.5 GPa), Michael additions of doubly activated acyclic donors to sterically hindered enone acceptors with 1,5-diazabicyclo[4.3.0]non-5-ene in acetonitrile affords Michael adducts in 42–82% yield.

  高压，15 kbar（1.5 GPa），在乙腈中带有1,5-二氮杂双环[4.3.0] non-5-ene的迈克尔将双活化无环供体与空间受阻的烯酮受体加成后，迈克尔加合物的收率为42-82％。
• Highly Efficient 1,4-Addition of 1,3-Diesters to Conjugated Enones by In/TMSCl
  作者：Phil Ho Lee、Dong Seomoon、Kooyeon Lee、Yunkiu Heo

  DOI：10.1021/jo026600t

  日期：2003.3.1

  Organoindium reagents derived from indium and diethyl bromomalonates were added to a wide range of conjugated enones in a 1,4-fashion in the presence of TMSCl under mild conditions, and corresponding oxo-1,3-diesters were obtained in good to excellent yields.
• DAUBEN, W. G.;GERDES, J. M., TETRAHEDRON LETT., 1983, 24, N 36, 3841-3844
  作者：DAUBEN, W. G.、GERDES, J. M.

  DOI：——

  日期：——
• Process for the preparation of carbazoles and novel carbazole derivatives utilized therein
  申请人：F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft

  公开号：EP0008446B1

  公开（公告）日：1982-09-22
• US4158007A
  申请人：——

  公开号：US4158007A

  公开（公告）日：1979-06-12