pinacolone enolate anion | 64723-95-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: pinacolone enolate anion
• 英文别名: 1-tert-butylethenolate；pinacolone enolate ion；pinacolone enolate；3,3-dimethyl-butan-2-one; deprotonated form；3,3-dimethyl-but-1-en-2-olate
• CAS: 64723-95-1
• 化学式: C₆H₁₁O
• 分子量: 99.1527
• InChiKey: FRNJOTOPLMUCQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.44
• 重原子数：
  7.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  环己三烯 、 pinacolone enolate anion 生成 3,3-二甲基-1-苯基-2-丁酮
  参考文献：
  名称：

  The SRN1 Reaction: An Attempt to Calculate the Thermodynamic Driving Force for the Addition of Nucleophiles to Phenyl Radical.

  摘要：

  Phenyl radical is formed in the propagation chain of the aromatic SRN 1 reaction from cleavage of the radical anion of the precursor phenyl halide (PhX.-); subsequent addition of nucleophile Y- to Ph-. yields the radical anion of the substitution product (PhY.-). In this addition step, transfer of an electron from the nucleophile to Ph-. is concerted with bond formation, and the extra electron of the new two-center three-electron bond is, in general, located in a pi* MO of the aromatic moiety. Three factors mainly affect the efficiency of this addition step: (i) the energy of the new Ph-Y bond; (ii) the stability of the radical anion of the substitution product; (iii) the oxidation potential of the nucleophile. In keeping with these points, the energy of some Ph-Y bonds has been calculated, and the oxidation potential of Y- species, along with the reduction potential of the related PhY substitution products, have been determined. Calculation of the thermodynamic driving force of the nucleophile/radical addition step is reported for some significant nucleophiles. Finally, comparison of the thermodynamic driving force with experimental reactivity of the same nucleophile in the addition step is attempted.

  DOI：

  10.3891/acta.chem.scand.52-0067
• 作为产物：
  描述：

  频哪酮 在 lithium tert-butoxide 作用下， 以 六甲基磷酰三胺 为溶剂， 生成 pinacolone enolate anion
  参考文献：
  名称：

  Electron transfer process. 49. Radical and ionic reactions of (benzoylmethyl)mercurials

  摘要：

  DOI：

  10.1021/jo00290a050

文献信息

• A Radical and An Electron Transfer Process Are Compared in Their Regioselectivities Towards A Molecule with Two Different C−I Bonds: Effect of Steric Congestion
  作者：Barbara Branchi、Carlo Galli、Patrizia Gentili、Manuela Marinelli、Paolo Mencarelli

  DOI：10.1002/1099-0690(200007)2000:14<2663::aid-ejoc2663>3.0.co;2-y

  日期：2000.7

  bonding interaction of the hindered C−I bond of 2a. This causes a remarkable regioselectivity toward the weaker bond in dehalogenation by stannyl radicals. Conversely, a much lower regioselectivity is found for a process −a photostimulated SRN1 reaction with the enolate ion of a ketone − which requires the conversion of 2a into a radical anion. A calculation of the BDE of the C−I bond for aa ArI•− system

  1,4-二碘-2,6-二甲基苯 (2a) 中的空间压缩使甲基侧翼的 C-I 键比不受阻碍的 C-I 键弱得多（一种支撑效应）。计算还证实了 2a 的受阻 CI 键较弱的键合相互作用。这导致了对甲硅烷基自由基脱卤中较弱键的显着区域选择性。相反，发现一个过程的区域选择性要低得多 - 光刺激的 SRN1 反应与酮的烯醇离子 - 这需要将 2a 转化为自由基阴离子。提供了对 ArI•− 系统的 C−I 键的 BDE 计算。最后，由 2a•- 较弱的 C-I 键断裂产生的受阻芳基中间体在还原或取代之间显示出适度但可检测的区分，
• Addition of elemental selenium to phosphonate carbanions- - a key step in the synthesis of vinylphosphonates. A new synthetic approach to 1,4-dicarbonyl systems.
  作者：Marian Mikolajczyk、Slawomir Grzejszczak、Katarzyna Korbacz

  DOI：10.1016/s0040-4039(01)81837-2

  日期：1981.1

  A convenient synthesis of vinylphosphonates which involves addition of elemental selenium to phosphonate carbanions followed by alkylation and selenoxide elimination is described. A general approach to 1,4-dicarbonyl systems based on diethyl α-methylthiovinylphosphonate is also reported.

  描述了一种方便的乙烯基膦酸酯的合成方法，该方法包括将元素硒添加到膦酸酯碳负离子中，然后进行烷基化和亚硒酸酯消除。还报道了基于α-甲基硫代乙烯基膦酸二乙酯的1，4-二羰基体系的一般方法。
• Mechanistic studies on gas-phase negative ion unimolecular decompositions. Alkoxide anions
  作者：William. Tumas、Robert F. Foster、John I. Brauman

  DOI：10.1021/ja00217a003

  日期：1988.4

  Les ions alcoolates subissent une elimination de molecules neutres pour donner des ions enolates

  Les ion alcoolates subissent une demoles neutres pour donner des ions enolates
• Synthesis of Sterically Hindered β-Diketones via Condensation of Acid Chlorides with Enolates
  作者：Aaron S. Crossman、Alec T. Larson、Jake X. Shi、Sebastian M. Krajewski、Eser S. Akturk、Michael P. Marshak

  DOI：10.1021/acs.joc.9b00433

  日期：2019.6.7

  dipivaloylmethane (DPM) in steric demand, largely due to synthetic limitations of the Claisen condensation. This work demonstrates hindered acid chlorides to be selective electrophiles in noncoordinating solvents for condensations with enolates. An improved synthesis of DPM is described (90% yield), and crowded β-diketones featuring bulky o-biphenyl or m-terphenyl fragments were prepared in good to excellent

  大的β-二酮的空间需求很少超过二甲戊酰甲烷（DPM），这主要是由于克莱森缩合的合成限制。这项工作表明受阻的酰氯是非配位溶剂中与烯醇盐缩合的选择性亲电试剂。DPM的改进的合成被描述（90％产率），和拥挤β二酮配笨重ø -联苯或米良好制备以优异的产率-三联苯片段。预期这些化合物的空间分布远大于DPM。包括一般反应条件和机理考虑因素。
• The effect of substituents in SRNl reactions. Some synthetic applications
  作者：Joseph F. Bunnett、Eric Mitchel、Carlo Galli

  DOI：10.1016/s0040-4020(01)97188-1

  日期：1985.1

  Most of the ortho effects are slight, but there is evidence that large ortho substituents hinder attachment of the phosphite more than the enolate nucleophile. The methoxy and diethoxyphosphoryl substituents, when para to the site of substitution, respectively favour and disfavour the phosphite with respect to the enolate ion. SRNl reactions of ortho-substituted halobenzenes are, for some substituents

  几个邻位取代的iodobenzenes被允许反应，经由S RN升机构，用亚磷酸二乙酯和离子烯醇频哪酮离子的混合物。从产物组成数据，推算出两种亲核试剂的相对反应性。它们代表与芳基自由基中间体连接的相对反应性。大多数邻位作用是轻微的，但是有证据表明，较大的邻位取代基比亚油酸酯亲核试剂更阻碍亚磷酸酯的附着。当在取代位置的对位时，甲氧基和二乙氧基磷酰基取代基相对于烯醇酸根离子分别有利和不利于亚磷酸酯。小号RN对于某些取代基，邻位取代的卤代苯的反应是随后进行的其他反应，这些反应提供了具有合成意义的产物。