3-甲基戊-3,4-二烯-2-酮 | 30515-36-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3-甲基戊-3,4-二烯-2-酮
• 英文名称: 3-methylpenta-3,4-dien-2-one
• 英文别名: 3-methyl-3,4-pentadien-2-one；3,4-Pentadien-2-one, 3-methyl-
• CAS: 30515-36-7
• 化学式: C₆H₈O
• 分子量: 96.1289
• InChiKey: QCRQRJTVWNHEJP-UHFFFAOYSA-N

物化性质

• 沸点：
  148.9±7.0 °C(Predicted)
• 密度：
  0.812±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-甲基戊-3,4-二烯-2-酮 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到3-methyl-3,4-pentadien-2-ol
  参考文献：
  名称：

  Efficient Synthesis of 4-(2‘-Alkenyl)-2,5-dihydrofurans and 5,6-Dihydro-2H-pyrans via the Pd-Catalyzed Cyclizative Coupling Reaction of 2,3- or 3,4-Allenols with Allylic Halides

  摘要：

  In the absence of a base, palladium(II) catalysts, such as PdCl2, PdCl2(CH3CN)(2), Pd(OAc)(2), and [(pi-C3H5)PdCl](2), can catalyze the cyclizative coupling reaction of 2,3- or 3,4-allenols with allylic halides in DMA at room temperature to provide 2,5-dihydrofurans and 5,6-dihydro-2H-pyrans, respectively, in moderate to good yields. Under similar reaction conditions, nonsubstituted 2,3-allenol 1s affords bimolecular cyclizative coupling product 5s as the major product. The scope of the reaction and its mechanism have been studied briefly. On the basis of the experimental results, the transformation was believed to proceed via a divalent palladium-catalyzed pathway.

  DOI：

  10.1021/jo0163997
• 作为产物：
  描述：

  4-bromo-3-methylpent-3-en-2-one 在 三乙胺 作用下， 以 乙腈 为溶剂， 生成 3-甲基戊-3,4-二烯-2-酮
  参考文献：
  名称：

  Hydrohalogenation Reaction of 1,2-Allenyl Ketones Revisited. Efficient and Highly Stereoselective Synthesis of β,γ-Unsaturated β-Haloketones

  摘要：

  DOI：

  10.1021/jo9903205

文献信息

• Palladium-Catalyzed Cyclization Reaction of Allylic Bromides with 1,2-Dienyl Ketones. An Efficient Synthesis of 3-Allylic Polysubstituted Furans
  作者：Shengming Ma、Lintao Li

  DOI：10.1021/ol0055871

  日期：2000.4.1

  3-Allylic polysubstituted furans were synthesized via a palladium-catalyzed cyclization reaction of allylic bromides with differently substituted 1,2-allenyl ketones. This process may occur via the reaction of a furanyl palladium intermediate with allylic bromide.

  3-烯丙基多取代的呋喃是通过钯催化的烯丙基溴与不同取代的1,2-烯基酮的环化反应合成的。该过程可以通过呋喃基钯中间体与烯丙基溴的反应而发生。
• Baylis–Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one
  作者：Gui-Ling Zhao、Min Shi

  DOI：10.1039/b510572b

  日期：——

  The attempted Baylis–Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one gave the corresponding Baylis–Hillman adducts 3 and 6 in moderate to good yields in the presence of DMAP in DMSO, respectively. In the case of the aza-Baylis–Hillman reactions of N-tosyl aldimines with 3-methylpenta-3,4-dien-2-one catalyzed by PBu3, the corresponding aza-Baylis–Hillman derivatives 4 and 5 were formed at the same time.

  N-甲苯磺酰亚胺与芳基醛在DMSO中，以DMAP为催化剂进行的Baylis-Hillman反应中，3-甲基戊-3,4-二烯-2-酮参与反应，分别以中等至良好的产率得到了相应的Baylis-Hillman加合物3和6。而在PBu3催化的N-甲苯磺酰亚胺与3-甲基戊-3,4-二烯-2-酮的aza-Baylis-Hillman反应中，同时生成了相应的aza-Baylis-Hillman衍生物4和5。
• Flash vacuum thermolysis of β-keto-trimethylsilyl-enol-ethers
  作者：J. Jullien、J.M. Pechine、F. Perez、J.J. Piade

  DOI：10.1016/0040-4020(82)80222-6

  日期：1982.1

  Thermolysis at 800° of a series of β-keto-trimethylsilyl-enol-ethers allows the elimination of a trimethylsilanol molecule through a 1,5 rearrangement. The reaction products are furanic derivatives, which are obtained in often good yields through an allenic intermediate, which has been isolated.

  一系列β-酮-三甲基甲硅烷基-烯醇醚在800°下热解可通过1,5重排消除三甲基甲硅烷醇分子。反应产物是呋喃衍生物，其通常通过已分离的烯丙基中间体以高收率获得。
• Pd0-Catalyzed Coupling Cyclization Reaction of Aryl or 1Alkenyl Halides with 1,2-Allenyl Ketones: Scope and Mechanism. An Efficient Assembly of 2,3,4-, 2,3,5-Tri- and 2,3,4,5-Tetrasubstituted Furans
  作者：Shengming Ma、Junliang Zhang、Lianghua Lu

  DOI：10.1002/chem.200204664

  日期：2003.6.6

  Described herein is the Pd(0)-catalyzed coupling cyclization reaction of 1,2-allenyl ketones with organic halides leading efficiently and conveniently to not only 2,3,4- and 2,3,5-trisubstituted furans but also 2,3,4,5-tetrasubstituted furans. Furthermore, this method showed high substituent-loading capability and tolerance of various substituents. The reactions of 1,2-allenyl ketones 1 e, 1 p, 1 q

  本文描述的是1,2-烯丙基酮与有机卤化物的Pd（0）催化的偶合环化反应，不仅有效且便捷地导致2,3,4-和2,3,5-三取代的呋喃，以及2,3 ，4,5-四取代的呋喃。此外，该方法显示出高的取代基负载能力和对各种取代基的耐受性。进行了1,2-烯基酮1e，1p，1q和氘代[D] 1c的反应，进行了机理研究，结果表明，该反应可能不是通过烯醇化途径，而是通过烯醇式中间体钯和分子内亲核试剂通过羰基氧攻击π-烯丙基钯中间体。
• Pd0-catalyzed cyclization reaction of aryl or alk-1-enyl halides with 1,2-dienyl ketones: a general and efficient synthesis of polysubstituted furans
  作者：Shengming Ma、Junliang Zhang

  DOI：10.1039/a908627g

  日期：——

  Under catalysis by Pd0 and Ag2CO3, the reaction of 1,2-allenyl ketones and organic halides in PhMe using Et3N as the base provides a new general access to polysubstituted furans with good to excellent yields.

  在 Pd0 和 Ag2CO3 的催化下，1,2-烯基酮和有机卤化物在 PhMe 中以 Et3N 为碱的反应提供了一种新的通用途径，可以得到具有良好至优异产率的多取代呋喃。