cyclobutylidenemethanone | 59078-45-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cyclobutylidenemethanone
• 英文别名: carbonylcyclobutane；Methanone, cyclobutylidene-
• CAS: 59078-45-4
• 化学式: C₅H₆O
• 分子量: 82.102
• InChiKey: KKECPQIBFZWDLC-UHFFFAOYSA-N

物化性质

• 沸点：
  82.0±7.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  cyclobutylidenemethanone 在 lithium aluminium tetrahydride 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 49.0h， 生成 1-isopropyl-2-azaspiro[3.3]heptane
  参考文献：
  名称：

  1位取代的2位氮杂螺环[3.3]庚烷：被忽略的药物开发主题

  摘要：

  在药物（18种FDA批准的药物）中发现了2个取代的哌啶核心，但是，它们的螺环类似物仍然未知。这里描述的是2-取代哌啶的螺环类似物的合成及其在药物发现中的验证。

  DOI：

  10.1002/anie.201703801
• 作为产物：
  描述：

  环丁基甲酸 在 氯化亚砜 、 N,N-二异丙基乙胺 作用下， 以 正己烷 为溶剂， 反应 2.0h， 生成 cyclobutylidenemethanone
  参考文献：
  名称：

  1位取代的2位氮杂螺环[3.3]庚烷：被忽略的药物开发主题

  摘要：

  在药物（18种FDA批准的药物）中发现了2个取代的哌啶核心，但是，它们的螺环类似物仍然未知。这里描述的是2-取代哌啶的螺环类似物的合成及其在药物发现中的验证。

  DOI：

  10.1002/anie.201703801

文献信息

• Correlation of rates of uncatalyzed and hydroxide-ion catalyzed ketene hydration. A mechanistic application and solvent isotope effects on the uncatalyzed reaction
  作者：John Andraos、A Jerry Kresge

  DOI：10.1139/v00-032

  日期：2000.4.1

  Rates of hydration of a number of ketenes were measured in neutral and basic solution using flash photolytic techniques, and rate constants for their uncatalyzed, k_uc, and hydroxide-ion catalyzed, k_HO, reactions were determined. These results, plus additional data from the literature, were found to provide the remarkably good correlation log k_uc= -3.21 + 1.14 log k_HO, which spans 10 orders of magnitude in reactivity and includes 31 ketenes. This good correlation implies that uncatalyzed and hydroxide-ion catalyzed ketene hydraton occur by similar reaction mechanisms, which for the hydroxide-ion catalyzed process is known to involve nucleophilic attack on the carbonyl carbon atom of the ketene. Rate constants for phenylhydroxyketene, on the other hand, do not fit this correlation, which suggests that the mechanistic assignment upon which these rate constants are based may not be correct. Solvent isotope effects on these uncatalyzed ketene hydrations are weak; most are less than k_H/k_D= 2. It is argued that these isotope effects are largely, if not entirely, secondary in nature and that they are consistent with both a reaction mechanism in which nucleophlic attack of a single water molecule on the ketene carbonyl carbon atom produces a zwitterionic intermediate and also a mechanism that avoids this intermediate by passing through a cyclic transition state involving several water molecules.Key words: ketene hydration, rate correlation, nucleophilic attack, solvent isotope effects, phenylhydroxyketene.

  一些酮烯的水合速率在中性和碱性溶液中使用闪光光解技术进行了测量，确定了它们的非催化反应速率常数k_uc和羟基离子催化反应速率常数k_HO。这些结果以及来自文献的额外数据发现，提供了非常好的相关性log k_uc= -3.21 + 1.14 log k_HO，涵盖了10个数量级的反应性，并包括31个酮烯。这种良好的相关性意味着非催化和羟基离子催化的酮烯水合反应通过类似的反应机制发生，对于羟基离子催化的过程已知涉及对酮烯的羰基碳原子的亲核攻击。另一方面，苯羟基酮烯的速率常数不符合这种相关性，这表明这些速率常数所基于的机械分配可能不正确。这些非催化酮烯水合反应的溶剂同位素效应较弱；大多数小于k_H/k_D= 2。据认为，这些同位素效应在很大程度上，如果不是完全地是次要的性质，并且它们与既涉及单个水分子对酮烯羰基碳原子的亲核攻击产生带电中间体的反应机制一致，也与通过涉及几个水分子的环状过渡态而避免这种中间体的机制一致。关键词：酮烯水合，速率相关性，亲核攻击，溶剂同位素效应，苯羟基酮烯。
• Ring strain release as a strategy to enable the singlet state photodecarbonylation of crystalline 1,4-cyclobutanediones
  作者：Gregory Kuzmanich、Miguel A. Garcia-Garibay

  DOI：10.1002/poc.1902

  日期：2011.10

  is essential to slow down the combination of the intermediate acyl–alkyl biradical back to the starting ketone. Relatively long triplet acyl–alkyl biradical lifetimes give a chance for the loss of CO to occur. Looking for additional strategies to generate transient biradicals in solids, we studied the solid state photochemistry of four aliphatic, dispiro‐substituted 1,4‐cyclobutandiones (1a–d) that

  挑战大多数化学家的直觉，利用环状酮的光脱羰基化可以在固态下可靠地生成高反应性的二烷基双自由基。但是，已经表明，在前体的α-碳上具有共振解离能力的自由基稳定基团是促进α裂解反应所必需的，并且三重态反应性对于减慢中间酰基的结合是必不可少的。烷基双自由基回到起始酮。相对较长的三重态酰基-烷基双自由基寿命为发生CO损失提供了机会。为了寻找在固体中生成瞬态双基的其他策略，我们研究了预期从单线态反应的四种脂族，双螺取代的1,4-环丁二酮（1a–d）的固态光化学。我们假设小环羰基释放出环应变将使反向酰基-烷基组合不利，从而使CO的损失得以有效且不可逆地发生。我们在这里报告在溶液，块状（粉末）晶体和纳米晶体光化学中进行的研究结果。我们最近表明，对二螺环己基-1,3-环丁二酮1c的激发导致中间羟基烯丙基的捕获，其半衰期约为42分钟。我们对其他三种结晶衍生物的研究表明，尽管它们均能有效反应，但羟烯丙基的超长寿
• Direct observation of .alpha.-oxo ketenes from the photolysis of .alpha.-diazo .beta.-diketones
  作者：Regis Leung-Toung、Curt Wentrup

  DOI：10.1021/jo00044a019

  日期：1992.8

  Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazo-cyclohexane-1,3-dione (I 1), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the alpha-oxo ketenes 12,20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.
• 1-Substituted 2-Azaspiro[3.3]heptanes: Overlooked Motifs for Drug Discovery
  作者：Alexander A. Kirichok、Iryna Shton、Maria Kliachyna、Iryna Pishel、Pavel K. Mykhailiuk

  DOI：10.1002/anie.201703801

  日期：2017.7.17

  The 2‐substituted piperidine core is found in drugs (18 FDA‐approved drugs), however, their spirocyclic analogues remain unknown. Described here is the synthesis of spirocyclic analogues for 2‐substituted piperidines and a demonstration of their validation in drug discovery.

  在药物（18种FDA批准的药物）中发现了2个取代的哌啶核心，但是，它们的螺环类似物仍然未知。这里描述的是2-取代哌啶的螺环类似物的合成及其在药物发现中的验证。