β,β-dimethyl-α-phenylacrylonitrile | 18670-23-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: β,β-dimethyl-α-phenylacrylonitrile
• 英文别名: β-Methyl-α-phenylcrotononitrile；3-methyl-2-phenyl-but-2-enenitrile；3-methyl-2-phenylbut-2-enenitrile；3-methyl-2-phenyl-crotononitrile；3-Methyl-2-phenyl-crotononitril；β,β-dimethyl-α-cyanostyrene
• CAS: 18670-23-0
• 化学式: C₁₁H₁₁N
• 分子量: 157.215
• InChiKey: IWOSBVMKLPSAAJ-UHFFFAOYSA-N

物化性质

• 沸点：
  256.2±19.0 °C(Predicted)
• 密度：
  0.982±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  β,β-dimethyl-α-phenylacrylonitrile 在 硫酸 、 溶剂黄146 作用下， 生成 3-甲基-2-苯基丁-2-烯酸 、 3-甲基-2-苯基丁-2-烯酰胺
  参考文献：
  名称：

  Jarrousse, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1957, vol. 244, p. 2515,2516

  摘要：

  DOI：
• 作为产物：
  描述：

  苯乙腈 在 sodium hydroxide 作用下， 以60%的产率得到β,β-dimethyl-α-phenylacrylonitrile
  参考文献：
  名称：

  Preparation of nitriles

  摘要：

  α，β-不饱和腈是由羰基化合物制备而成，然后在铵盐存在下通过与烷醇和镁发生反应进行还原。

  公开号：

  US04132728A1

文献信息

• Hydrogenation reactions with hydridocobalt Tetracarbonyl
  作者：Theodore E. Nalesnik、John H. Freudenberger、Milton Orchin

  DOI：10.1016/s0022-328x(00)89054-3

  日期：1981.12

  The tetrasubstituted ethylene, bifluorenylidene, reacts very rapidly (4.06 X 10−2 1 mol−1 sec−1 at 0°C) with HCo(CO)4 to give bifluorenyl. α-Phenylacrylonitrile (atroponitrile) reacts even more rapidly under the same conditions (6.0 l mol−sec−1). Other highly substituted ethylenes react very slowly with HCo(CO)4, indicating considerable steric effects. The data are consistent with radical type intermediates

  四取代的乙烯，联芴基，与HCo（CO）4非常迅速地反应（0°C时为4.06 X 10 -2 1 mol -1 sec -1），得到联芴基。在相同的条件下（6.0 l mol - sec -1），α-苯基丙烯腈（a腈）的反应甚至更快。其他高度取代的乙烯与HCo（CO）4的反应非常缓慢，表明存在很大的空间效应。数据与自由基型中间体一致。
• Nickel/Lewis Acid-Catalyzed Carbocyanation of Alkynes Using Acetonitrile and Substituted Acetonitriles
  作者：Akira Yada、Tomoya Yukawa、Hiroaki Idei、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1246/bcsj.20100023

  日期：2010.6.15

  Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction of butyronitrile gives significant amounts of hydrocyanation products due possibly to β-hydride elimination of a propylnickel intermediate. The reaction of optically active α-phenylpropionitrile suggests a reaction mechanism that involves oxidative addition of a C–CN bond with retention of its absolute configuration.

  镍/路易斯酸双催化体系被发现能够有效地促进乙腈和取代乙腈与炔烃的碳氰化反应，生成一系列不同取代的丙烯腈。简要展示的丙腈与炔烃的加成反应也能高效地得到相应的乙基氰化产物，而丁腈参与的反应则因可能的丙基镍中间体β-氢消除作用而得到显著量的氢氰化产物。光学活性α-苯基丙腈的反应表明其反应机制涉及C–CN键的氧化加成，并保留其绝对构型。
• A general and stereoselective method for synthesis of tri- and tetrasubstituted alkenes
  作者：I Maciągiewicz、P Dybowski、A Skowrońska

  DOI：10.1016/s0040-4020(03)00977-3

  日期：2003.8

  A convenient, general and stereoselective synthesis of trisubstituted alkenes and tetrasubstituted alkenes containing a cyanide function as well as trisubstituted episulphides have been elaborated. Methodology described for the preparation of these compounds is based on the corresponding readily available selenophosphates 1 and thiophosphates 2.

  已经详细说明了具有氰化物官能团的三取代烯烃和四取代烯烃以及三取代环氧乙烷的方便，通用和立体选择性的合成方法。制备这些化合物所描述的方法是基于相应的易得的硒代磷酸酯1和硫代磷酸酯2。
• New Syntheses of Vinyl Sulfides and Unsaturated Nitriles<i>via</i>Quaternary Phosphonium Salts
  作者：Takanobu Kumamoto、Kazuo Hosoi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.41.2742

  日期：1968.11

  of vinyl sulfides and unsaturated nitriles via quaternary phosphonium salts have been established. The reaction of isopropylidenetriphenylphosphorane with S-ethyl thiobenzoate or substituted S-ethyl thiobenzoates afforded vinyl sulfides and triphenylphosphine oxide in good yields. Further, it was found that the reaction of α-benzoylalkylphosphonium salts with sodium ethylmercaptide or potassium cyanide

  已经建立了通过季鏻盐合成乙烯基硫化物和不饱和腈的新方法。异亚丙基三苯基正膦与硫代苯甲酸 S-乙酯或取代的硫代苯甲酸 S-乙酯反应以良好的收率得到乙烯基硫化物和氧化三苯膦。此外，发现α-苯甲酰基烷基鏻盐与乙基硫醇钠或氰化钾的反应分别以良好的产率得到烯烃，例如乙烯基硫化物或不饱和腈，和氧化三苯基膦。
• AN INTERPRETATION OF THE SUBSTITUENT EFFECT IN THE BLAISE REARRANGEMENT IN TERMS OF PI-ORBITALS
  作者：Yukio Abe、Tadashi Suehiro

  DOI：10.1246/cl.1983.389

  日期：1983.3.5

  The migratory aptitude of the substituent groups in the Blaise rearrangement can be explained in terms of the pi-electronic properties of the groups in the highest occupied molecular orbitals. The rates of the rearrangement reaction with relation to the substituent groups were also rationally understood based on the energy levels of the molecular orbitals.

  Blaise 重排中取代基的迁移能力可以用最高占据分子轨道中基团的 pi 电子特性来解释。基于分子轨道的能级，也可以合理地理解与取代基相关的重排反应速率。