4-甲基二环[2.2.2]辛烷-2,6-二酮 | 119986-98-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-甲基二环[2.2.2]辛烷-2,6-二酮
• 英文名称: 4-methylbicyclo<2.2.2>octane-2,6-dione
• 英文别名: 4-Methylbicyclo[2.2.2]octane-2,6-dione
• CAS: 119986-98-0
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: MDSIHOJODTWKJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-甲基二环[2.2.2]辛烷-2,6-二酮 以51%的产率得到
  参考文献：
  名称：

  PAQUETTE, LEO A.;MALECZKA, ROBERT E. (JR);QIU, FA-YANG, J. ORG. CHEM., 56,(1991) N, C. 2455-2461

  摘要：

  DOI：
• 作为产物：
  描述：

  3-甲基-2-环己烯-1-酮 在 sodium 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 224.0h， 生成 4-甲基二环[2.2.2]辛烷-2,6-二酮
  参考文献：
  名称：

  INTRAMOLECULAR OXIDATIVE COUPLING OF A BISENOLATE: 4-METHYLTRICYCLO[2.2.2.03,5]OCTANE-2,6-DIONE

  摘要：

  DOI：

  10.15227/orgsyn.069.0173

文献信息

• Regio- and stereoselective oxidation of unsaturated bicyclo[2.2.2]octanones with selenium dioxide
  作者：Leo A. Paquette、Robert E. Maleczka、Fa Yang Qiu

  DOI：10.1021/jo00007a037

  日期：1991.3

  The selenium dioxide oxidation of several unsaturated bicyclo[2.2.2]octanones has been examined in connection with the projected utility of properly functionalized products in tandem oxyanionic Cope rearrangement-S(N') transformations. The oxidations studied proved to be regioselective, with attack in the olefinic sector of each molecule occurring to the exclusion of chemical reaction alpha to the carbonyl. Stereoselectivity was also often encountered, with steric factors appearing to contribute heavily to establishing the particular configuration of the newly introduced stereogenic center.
• INTRAMOLECULAR OXIDATIVE COUPLING OF A BISENOLATE: 4-METHYLTRICYCLO[2.2.2.03,5]OCTANE-2,6-DIONE
  作者：Poupart, Marc-André、Lassalle, Gilbert、Paquette, Leo A.

  DOI：10.15227/orgsyn.069.0173

  日期：——
• PAQUETTE, LEO A.;MALECZKA, ROBERT E. (JR);QIU, FA-YANG, J. ORG. CHEM., 56,(1991) N, C. 2455-2461
  作者：PAQUETTE, LEO A.、MALECZKA, ROBERT E. (JR)、QIU, FA-YANG

  DOI：——

  日期：——
• POUPART, MARC-ANDRE;PAQUETTE, LEO A., TETRAHEDRON LETT., 29,(1988) N 3, 269-272
  作者：POUPART, MARC-ANDRE、PAQUETTE, LEO A.

  DOI：——

  日期：——
• Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy
  作者：Leo A. Paquette、Marc Andre Poupart

  DOI：10.1021/jo00068a019

  日期：1993.7

  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.