2,2,4-trimethylcyclohexane-1,3-dione | 20990-17-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2,4-trimethylcyclohexane-1,3-dione
• 英文别名: 2,2,4-trimethyl-1,3-cyclohexanedione
• CAS: 20990-17-4
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: FMSVYJVGRWXBIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• 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：

  2,2,4-trimethylcyclohexane-1,3-dione 在 氯仿 、 溴 作用下， 生成 2-bromo-4,5,5-trimethyl-cyclohexane-1,3-dione
  参考文献：
  名称：

  Crossley, Journal of the Chemical Society, 1901, vol. 79, p. 147

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲基-3-戊酮 在 盐酸 作用下， 生成 2,2,4-trimethylcyclohexane-1,3-dione
  参考文献：
  名称：

  胺化学。第三部分 αβ-不饱和酰氯与无环酮的烯胺反应。环己烷-1,3-二酮的制备

  摘要：

  丙烯酰，巴豆酰和甲基丙烯酰氯与二乙基酮的吗啉烯胺反应已显示出2,4-二甲基-，2,4,5-三甲基-和2,4,6-三甲基-环己烷-1， 3-二酮。中间体取代的3-吗啉代环己基-2-烯酮已被分离并表征为其高氯酸盐。乙基异丙基酮的丙烯酰氯和吗啉烯胺和二异丙基酮的二甲基胺烯胺分别得到2,2,4-三甲基-和2,2,4,4-四甲基-环己烷-1,3-二酮。二苄基酮的吗啉烯胺得到3-吗啉代-2，4-二苯基-环己二-2-烯酮，其不能水解为环己烷-1，3-二酮。讨论了反应机理。

  DOI：

  10.1039/j39680002599

文献信息

• Total Synthesis of (±)-Kellermanoldione: Stepwise Cycloaddition of a Functionalized Diene and Allenoate
  作者：Michael E. Jung、Jesus Cordova、Masayuki Murakami

  DOI：10.1021/ol901455q

  日期：2009.9.3

  The total synthesis of the diterpene kellermanoldione 1 is reported. Stepwise [4 + 2] cycloaddition of the ketal diene 8 and the allenoate 3 afforded the exo adduct 10x as the major product. It was converted into 1 via six steps, among them a key nonconjugative hydrolysis of a γ-methylene silyl enol ether.

  据报道，二萜kellermanoldione 1的全合成。缩酮二烯8和烯丙酸酯3的逐步[4 + 2]环加成提供了exo加合物10x作为主要产物。通过六个步骤将其转化为1，其中关键是γ-亚甲基甲硅烷基烯醇醚的非共轭水解。
• Process for the preparation of pure cis-cyclopropane carboxylic acids and intermediates therefor
  申请人：IMPERIAL CHEMICAL INDUSTRIES PLC

  公开号：EP0339815A2

  公开（公告）日：1989-11-02

  A process for the preparation of cis-­cyclopropane carboxylic acids which comprises the step of treating a derivative of a 4-­hydroxy-2,2-dimethyl bicyclo[3,1,0]hexan-2-one with a source of hydroxide ions.

  一种制备顺式环丙烷羧酸的工艺，包括用氢氧根离子源处理 4-羟基-2,2-二甲基双环[3,1,0]己-2-酮衍生物的步骤。
• Masters, John J.; Jung, David K.; Danishefsky, Samuel J., Angewandte Chemie, 1995, vol. 107, # 4, p. 495 - 498
  作者：Masters, John J.、Jung, David K.、Danishefsky, Samuel J.、Snyder, Lawrence B.、Park, Tae Kyo、et al.

  DOI：——

  日期：——
• Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates
  作者：Teruhiko Ishikawa、Ryuichiro Kadoya、Masaki Arai、Haruka Takahashi、Yumi Kaisi、Tomohiro Mizuta、Kazusa Yoshikai、Seiki Saito

  DOI：10.1021/jo010325d

  日期：2001.11.1

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].
• A Convenient Synthesis of 2,2,4-Trimethylcyclohexane-1,3-Dione: A Useful Precursor for The Taxoid a Ring
  作者：Miller, Michael L.、Ray, Partha S.

  DOI：10.1080/00397919708005921

  日期：1997.11

  A simple and inexpensive route to the title compound is described which should be readily amenable to large scale synthesis. Thus, reaction of 3-pentanone with methyl acrylate in the presence of sodium methoxide provided 2,4-dimethylcyclohexane-1,3-dione. Methylation with iodomethane gave the title compound in 63% overall yield.