isopropylideneketene | 63364-70-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: isopropylideneketene
• 英文别名: 3-methyl-buta-1,2-dien-1-one；1,2-Butadienone, 3-methyl-
• CAS: 63364-70-5
• 化学式: C₅H₆O
• 分子量: 82.102
• InChiKey: CULFHGAEORKRLD-UHFFFAOYSA-N

物化性质

• 沸点：
  90.1±7.0 °C(Predicted)
• 密度：
  0.778±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  isopropylideneketene 800.0 ℃ 、0.13 Pa 条件下， 生成 3-甲基丁-1,3-二烯-1-酮
  参考文献：
  名称：

  羧乙烯基乙烯酮、亚甲基乙烯酮、乙烯基乙烯酮和羟基乙炔之间的相互关系

  摘要：

  通过快速真空热解 2,2-二甲基-5-亚烷基-1,3-二恶烷-4,6-二酮，首次选择性地、顺序地获得异构纯的羧基（乙烯基）烯酮、亚烷基烯酮和乙烯基烯酮（Meldrum 的酸衍生物）在受控条件下。每种乙烯酮通过红外光谱直接观察并用甲醇或苯胺捕获。高度不稳定的化合物被认为是亚烷基和乙烯基烯酮的羟基乙炔异构体，这是首次被观察到。

  DOI：

  10.1021/ja00214a035
• 作为产物：
  描述：

  2,2-二甲基-5-(1-甲基亚乙基)-1,3-二噁烷-4,6-二酮 800.0 ℃ 、0.13 Pa 条件下， 生成 isopropylideneketene
  参考文献：
  名称：

  羧乙烯基乙烯酮、亚甲基乙烯酮、乙烯基乙烯酮和羟基乙炔之间的相互关系

  摘要：

  通过快速真空热解 2,2-二甲基-5-亚烷基-1,3-二恶烷-4,6-二酮，首次选择性地、顺序地获得异构纯的羧基（乙烯基）烯酮、亚烷基烯酮和乙烯基烯酮（Meldrum 的酸衍生物）在受控条件下。每种乙烯酮通过红外光谱直接观察并用甲醇或苯胺捕获。高度不稳定的化合物被认为是亚烷基和乙烯基烯酮的羟基乙炔异构体，这是首次被观察到。

  DOI：

  10.1021/ja00214a035

文献信息

• Flash vacuum pyrolysis of 2-diazo-8-oxabicyclo[3.2.1]Oct-6-en-3-ones. A new method for the preparation of propadienones.
  作者：John C Brahms、William P Dailey

  DOI：10.1016/s0040-4039(00)88811-5

  日期：——

  When diazoketones 3a and 3b are pyrolysed at 430°C and 10−4 torr, they undergo loss of N2 followed by Wolff rearrangement and loss of furan by retro Diels-Alder reaction to yield the desired propadienones 1(a,b). If argon is added to the pyrolysate mixture, these reactive compounds can be trapped under matrix isolation conditions at 22 K and observed by FTIR. Upon photolysis, 1b yields carbon monoxide

  当重氮酮3a和3b在430°C和10 -4托下热解时，它们会经历N 2的损失，随后的Wolff重排和呋喃酮的逆Diels-Alder反应的损失，从而生成所需的丙二烯酮1（a，b）。如果将氩气添加到热解产物混合物中，这些反应性化合物可以在22 K的基质分离条件下被捕集并通过FTIR观察。光解后，1b生成一氧化碳和2-丁炔。
• Mohmand, Shamsher; Hirabayashi, Takakuni; Bock, Hans, Chemische Berichte, 1981, vol. 114, # 7, p. 2609 - 2621
  作者：Mohmand, Shamsher、Hirabayashi, Takakuni、Bock, Hans

  DOI：——

  日期：——
• Photochemical Generation and Matrix-Isolation Detection of Dimethylvinylidene
  作者：Sasha C. Reed、Gregory J. Capitosti、Zhendong Zhu、David A. Modarelli

  DOI：10.1021/jo001464i

  日期：2001.1.1

  We report the spectroscopic characterization of dimethylvinylidene, (CH3)(2)C=C:, generated within an argon matrix at 14 K from a bisperoxyester precursor. The carbene was identified by comparison of the experimental IR spectrum with vibrational frequencies computed at the B3LYP/6-31G(d) level. Chemical trapping of the carbene within a 9% CO/Ar matrix to form dimethylpropadienone supports this analysis. Additional products produced during photolysis were identified by comparison to the appropriate computed vibrational frequencies. The potential energy surface of dimethylvinylidene and its intramolecular rearrangement products, 2-butyne and methylcyclopropene, were also investigated computationally at the B3LYP/6-31G(d) level. A spin-state analysis of this carbene using a variety of computational methods (CCSD(T), B3LYP, MP2) indicates the singlet state is more stable than the triplet by similar to 45 kcal mol(-1). We anticipate the bisperoxyester precursor used here will be a convenient and general way for initiating future studies of alkylvinylidenes under matrix-isolation conditions.
• Synthese et reactivite comparee d'alkoxy et de thioalkoxymethylenecetenes
  作者：A. Ben Cheikh、H. Dhimane、J.C. Pommelet、J. Chuche

  DOI：10.1016/s0040-4039(00)82226-1

  日期：1988.1
• Unsaturated ketenes: A study of their formation and rearrangement by tandem mass spectrometry and low-temperature infrared spectroscopy
  作者：André Maquestiau、Pascal Pauwels、Robert Flammang、Primož Lorenčak、Curt Wentrup

  DOI：10.1002/oms.1210210505

  日期：1986.5

  AbstractA combination of collisional activation mass spectrometry and low‐temperature infrared spectroscopy has been used to monitor the production and isomerization of vinyl‐ and methylene‐ketenes. Vinyl‐ and 2‐propenyl‐ketenes were produced by flash vacuum pyrolysis of β,γ‐unsaturated acid chlorides. Vinyl(carboxyl)ketenes, vinylketenes and methyleneketenes were obtained from Meldrum's acid derivatives (5‐alkylidene‐1,3‐dioxane‐4,6‐diones). The formation of methyleneketenes by pyrolysis of α, β‐unsaturated acid chlorides is only indicated in the mass spectrometry experiments. Carbonylcyclopropane was obtained by pyrolysis of cyclopropylcarbonyl chloride or the corresponding Meldrum's acid derivative. The methyleneketenes isomerize to vinylketenes in the gas phase, particularly under conditions involving long contact times. Carbonylcyclopropane thermally decarbonylates to allene, not methylacetylene. Molecular ions of vinylketenes are obtained via pyrolysis of either acid chlorides or Meldrum's acid derivatives. Molecular ions of alkylmethyleneketenes are obtained pure only by electron impact induced fragmentation of Meldrum's acid derivatives.