2,2-di(prop-2-en-1-yl)cyclohexane-1,3-dione | 23438-66-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-di(prop-2-en-1-yl)cyclohexane-1,3-dione
• 英文别名: 2,2-diallyl-cyclohexane-1,3-dione；2,2-Diallyl-1,3-cyclohexandion；2,2-Diallylcyclohexan-1,3-dione；2,2-bis(prop-2-enyl)cyclohexane-1,3-dione
• CAS: 23438-66-6
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: OIQBPCZUCUEHAT-UHFFFAOYSA-N

物化性质

• 沸点：
  78 °C(Press: 2 Torr)
• 密度：
  1.0233 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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-di(prop-2-en-1-yl)cyclohexane-1,3-dione 在 N-(2,2,6,6-tetramethyl-1-oxopiperidin-1-ium-4-yl)acetamide tetrafluoroborate 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以48%的产率得到3,3-diallylcyclohex-5-ene-1,2,4-trione
  参考文献：
  名称：

  Access to Dienophilic Ene-Triketone Synthons by Oxidation of Diketones with an Oxoammonium Salt

  摘要：

  Here we describe the oxidation of 1,3-cyclohexanediones with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (Bobbitt's salt) to generate 5-ene-1,2,4-triones in moderate-to-good (40-80%) yields. This inexpensive oxidant facilitated an unprecedented cascade of oxidation and elimination to yield novel ene-triketones. The reactivity of these products was explored in the Diets-Alder reaction and provided moderate-to-good yields of cycloaddition products. The products described in this study represent unique, densely functionalized, and versatile building blocks for the synthesis of more complex molecules.

  DOI：

  10.1021/ol2030873
• 作为产物：
  描述：

  1,3-环己二酮 、 3-溴丙烯 在 四丁基硫酸氢铵 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 以62%的产率得到2,2-di(prop-2-en-1-yl)cyclohexane-1,3-dione
  参考文献：
  名称：

  Fischer吲哚环化，烯烃易位和Suzuki-Miyaura交叉偶联反应的多样性导向方法

  摘要：

  通过克莱森重排，费歇尔吲哚环化，闭环易位和铃木-宫浦交叉偶联反应，已组装了一系列含有吲哚部分的芳基取代螺环。这些分子中的一些包含螺环系统或茚并[1,2- b ]吲哚骨架，它们存在于各种生物活性靶标中。在这里，我们使用了简单易用的起始材料来生成螺环化合物库，其中螺环化合物的结构具有吲哚单元。

  DOI：

  10.1016/j.tet.2014.11.024

文献信息

• Copper-Mediated Radical 1,2-Bis(trifluoromethylation) of Alkenes with Sodium Trifluoromethanesulfinate
  作者：Bin Yang、Xiu-Hua Xu、Feng-Ling Qing

  DOI：10.1021/acs.orglett.5b00601

  日期：2015.4.17

  An efficient chemoselective 1,2-bis(trifluoromethylation) of alkenes with CF3SO2Na promoted by t-BuOOH/CuCl was developed. This protocol provided the first convenient preparation of 1,2-bis(trifluoromethylated) compounds by the vicinal difunctionalization of alkenes. The chemoselectivity of this reaction was accomplished by increasing the concentration of the CF3 radical.

  开发了由t- BuOOH / CuCl促进的具有CF 3 SO 2 Na的烯烃的高效化学选择性1,2-双（三氟甲基化）烯烃。该方案通过烯烃的邻位双官能化提供了第一种方便的1,2-双（三氟甲基化）化合物的制备方法。该反应的化学选择性通过增加CF 3基的浓度来实现。
• Ionic liquid as catalyst and solvent: the remarkable effect of a basic ionic liquid, [bmIm]OH on Michael addition and alkylation of active methylene compounds
  作者：Brindaban C. Ranu、Subhash Banerjee、Ranjan Jana

  DOI：10.1016/j.tet.2006.10.077

  日期：2007.1

  ketones, carboxylic esters and nitriles. It further catalyzes the addition of thiols to α,β-acetylenic ketones and alkylation of 1,3-dicarbonyl and -dicyano compounds. The Michael addition to α,β-unsaturated ketones proceeds in the usual way, giving the monoaddition products, whereas addition to α,β-unsaturated esters and nitriles leads exclusively to the bis-addition products. The α,β-acetylenic ketones

  碱性离子液体1-甲基-3-丁基咪唑鎓氢氧化物[bmIm] OH催化活性亚甲基化合物与共轭酮，羧酸酯和腈的迈克尔加成反应。它进一步催化将硫醇添加到α，β-炔基酮上，并使1,3-二羰基和-二氰基化合物烷基化。α，β-不饱和酮的迈克尔加成反应以通常的方式进行，得到单加成产物，而α，β-不饱和酯和腈的加成仅导致双加成产物。α，β-炔基酮与硫醇进行双重共轭加成，生成β-酮基1,3-二硫代衍生物。在烷基化反应中，无环的1，3-二酮被单烷基化，而环状酮在相同条件下进行二烷基化。所有这些反应均在没有任何有机溶剂的情况下进行。
• Solvent-Controlled Highly Selective Bis- and Monoallylation of Active Methylene Compounds by Allyl Acetate with Palladium(0) Nanoparticle
  作者：Brindaban C. Ranu、Kalicharan Chattopadhyay、Laksmikanta Adak

  DOI：10.1021/ol702099v

  日期：2007.10.1

  catalyst for the allylation of active methylene compounds. Very efficient bisallylation is achieved for a variety of active methylene compounds by allyl acetate and its derivatives in one stroke in THF solvent. The reaction in water provides monoallylated product selectively by allyl acetate only. The recovered Pd(0) nanoparticle is recycled. A probable mechanism is suggested.

  钯（0）纳米颗粒已被用作有效的催化剂，用于活性亚甲基化合物的烯丙基化。在THF溶剂中，一次通过乙酸烯丙酯及其衍生物就可以对多种活性亚甲基化合物实现非常有效的双烯丙基化。在水中的反应仅通过乙酸烯丙酯选择性地提供单烯丙基化的产物。回收的Pd（0）纳米颗粒被回收。建议一种可能的机制。
• MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl Compounds
  作者：Samuthirarajan Senthilkumar、Cheirmakani Thangapriya、Raman Alagumurugayee、Mayilvasagam Kumarraja

  DOI：10.1007/s10562-017-2185-3

  日期：2017.11

  An alternative method to Pd-catalyzed Tsuji–Trost reaction is developed and it provides a simpler route for the selective synthesis of a broad range of mono-/bis-allylated and cinnamylated 1,3-dicarbonyl compounds using MMZNiY catalyst at room temperature. Product selectivity can be controlled by the proper choice of catalyst. The catalyst was also well characterized by SEM, TEM, HRTEM, EDAX and X-ray

  开发了 Pd 催化的 Tsuji-Trost 反应的替代方法，它为使用 MMZNiY 催化剂在室温下选择性合成广泛的单/双烯丙基化和肉桂基化 1,3-二羰基化合物提供了一种更简单的途径。产品选择性可以通过正确选择催化剂来控制。该催化剂还通过 SEM、TEM、HRTEM、EDAX 和 X 射线分析得到了很好的表征。还强调了催化剂的其他优点，如易于制备、功能耐受性和可重复使用性。图形摘要
• Ruthenium-Catalyzed One-Pot Double Allylation/Cycloisomerization of 1,3-Dicarbonyl Compounds Leading toexo-Methylenecyclopentanes
  作者：Yoshihiko Yamamoto、Yu-ichiro Nakagai、Kenji Itoh

  DOI：10.1002/chem.200305340

  日期：2004.1.5

  tion of 1,3-diketones and methyl acetoacetate gave exo-methylenecyclopentanes in moderate to good yields with high isomer selectivity. The double allylation step effectively proceeded in the presence of a Ru(II) precatalyst, [Cp*RuCl(cod)], in 1,2-dichloroethane at 90 degrees C. The subsequent cycloisomerization was carried out upon addition of triethylsilane as a hydride source without purification

  钌催化的1，3-二酮和乙酰乙酸甲酯的一锅双烯丙基化/环异构化反应以中等到良好的收率得到了高亚甲基环戊烷的异构体选择性。双重烯丙基化步骤在Ru（II）预催化剂[Cp * RuCl（cod）]存在下于1,2-二氯乙烷中于90摄氏度下有效地进行。随后的环异构化反应是在加入三乙基硅烷作为氢化物后进行的。源，无需纯化1,6-二烯中间体。通过（1）NMR光谱对反应进行的详细检查显示，三乙基甲硅烷基甲基醚对于将在双烯丙基化步骤中形成的钌（IV）烯丙基络合物转化成环异构化所需的钌（II）物种起着重要作用。