苯乙腈锂盐 | 58477-04-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 苯乙腈锂盐
• 英文名称: phenylacetonitrile lithium salt
• CAS: 58477-04-6
• 化学式: C₈H₆N*Li
• 分子量: 123.083
• InChiKey: SOIITMWYFLHDPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.23
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯乙腈锂盐 、 (2R,4S,5R)-2-O-(N,N-dimethylhydroxylamino)-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one 以 四氢呋喃 为溶剂， 生成 α-N,N-二甲氨基苯乙腈
  参考文献：
  名称：

  手性试剂在亲电胺化反应中诱导不对称

  摘要：

  由（-）-麻黄碱制备手性胺化试剂（-）- ，通过X-射线结构分析对其构型进行确定，并与碳亲核试剂反应以产生具有高达44％ee的旋光胺。

  DOI：

  10.1016/0040-4039(82)80141-x
• 作为产物：
  描述：

  苯乙腈 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 苯乙腈锂盐 、
  参考文献：
  名称：

  Study of the Lithiated Phenylacetonitrile Monoanions and Dianions Formed According to the Lithiated Base Used (LHMDS, LDA, or n-BuLi). 1. Evidence of Heterodimer (“Quadac”) or Dianion Formation by Vibrational Spectroscopy

  摘要：

  It is evidenced through vibrational spectroscopy that a heterodimer or "Quadac" is formed when an excess of base (LHMDS, LDA, or n-BuLi) is added to PhCH2CN in THF, THF-hexane, or THF-toluene solution. The amount of heterodimer increases with the pK(Ha) of the lithiated base. A dianionic species may be formed through decomposition of this heterodimer if the pK(Ha) of the base is sufficiently high, as in the case of n-BuLi. With LDA, only a very small amount of dianion is observed, and with LHMDS, no dianion is detected. The predominant dianionic species observed are the linear and bridged separated ion pairs of the dilithiated dianion. The presence of the amine in the medium is of paramount importance. The PhCHCNLi monomer-dimer equilibrium is entropy driven toward the dimer solvated by the amine.

  DOI：

  10.1021/jo020492t

文献信息

• Stereoselective synthesis of some cis 2,3- disubstituted cyclanones
  作者：E. Hatzigrigoriou、L. Wartski、J. Seyden-Penne、E. Toromanoff

  DOI：10.1016/s0040-4020(01)96751-1

  日期：1985.1

  2-cyclopentenone, followed by acidic quench, under kinetic control, leads to different ratios of cis and trans 2,3-disubstituted cyclanones according to ring size. From 2-methyl and 2-phenyl 2-cyclohexenone, the cis isomer is highly predominant (85 to 98%). From 2-methyl 2-cyclopentenone a cis/trans mixture is obtained: the cis isomer only predominates when a bulky reagent (1c) is used (80%); in the other cases

  将由芳基或苯基硫代乙腈1a-1c和2形成的碳负离子试剂共轭添加到2-甲基和2-苯基2-环己烯酮或2-甲基2-环戊烯酮中，然后在动力学控制下进行酸性淬灭，导致不同的比率的顺式和反式，根据环的大小2,3-二取代cyclanones。由2-甲基和2-苯基2-环己烯酮组成的顺式异构体占主导地位（85％至98％）。由2-甲基2-环戊烯酮获得顺式/反式混合物：仅当使用大体积试剂（1c）（80％）时，顺式异构体占主导。在其他情况下，将获得接近1：1的混合物。
• Reaction of Metalated Nitriles with Enones
  作者：Hans J. Reich、Margaret M. Biddle、Robert J. Edmonston

  DOI：10.1021/jo0478050

  日期：2005.4.1

  There have been a number of reports of the kinetic conjugate (1,4) addition of metalated arylacetonitriles to enones. Several proposals have been made to explain this behavior based on nucleophile structure or aggregation state or on the HSAB properties of the reactants. A reexamination of these studies showed that in each case the 1,4 adducts resulted from equilibration of the kinetically formed 1

  已有许多关于将金属化的芳基乙腈加到烯酮上的动力学共轭（1,4）的报道。基于亲核体的结构或聚集状态或反应物的HSAB特性，已经提出了一些建议来解释这种行为。对这些研究的重新检查表明，在每种情况下，1,4加合物是由动力学形成的1,2加合物平衡为更稳定的1,4加合物所致。因此，无法从这些实验中得出关于1,4选择性起源的结论。检查了亚硫基苯基乙腈在亚苄基丙酮中的1,2加成，retro-1,2加成，1,4加成和retro-1,4加成，并构建了反应的自由能级图。
• Infrared spectra and structure of carbanions
  作者：I.N. Juchnovski、I.G. Binev

  DOI：10.1016/s0022-328x(00)86355-x

  日期：1975.10

  The structure of the lithium derivatives of phenyl acetonitrile and acetonitrile is discussed in terms of their IR spectra. It has been found from new and already-published data that the IR spectra [ν(CN) region] of the lithium, sodium, potassium and chlormagnesyl derivatives of phenyl acetonitrile in various solvents, and in the solid state, are similar. They are characterized by very strong ν(CN)

  根据它们的IR光谱讨论了苯基乙腈和乙腈的锂衍生物的结构。从新的和已经公开的数据中发现，在各种溶剂中和在固态下，苯基乙腈的锂，钠，钾和氯镁基衍生物的红外光谱[ν（CN）区域]相似。它们的特征是在2068–2102 cm -1区域具有非常强的ν（CN）谱带，并对应于消旋苯基乙腈碳负离子。
• First examples of lithium reagents addition in cyanine dyes series
  作者：Lilia Viteva、Yuri Stefanovski、Tzveta Gospodova、Marie Rose Mazières、Jean Gérard Wolf

  DOI：10.1016/s0040-4039(00)00205-7

  日期：2000.4

  The reactivity of the cyanine dyes towards nucleophilic reagents is currently being tested. As in the case of phosphine derivatives, carbanions attack the electrophilic C3 carbon of the pentamethine chain to give, with a good yield, new functionalized podands with cyano, keto, amino, amido, or enol-ether moieties.

  花青染料对亲核试剂的反应性目前正在测试中。与膦衍生物一样，碳负离子侵蚀五甲胺链的亲电C3碳，从而以良好的收率得到具有氰基，酮基，氨基，酰胺基或烯醇醚基团的新型官能化Podands。