2-(2-甲基烯丙基)苯甲腈 | 97780-98-8

• 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: 2-(2-甲基烯丙基)苯甲腈
• 英文名称: 2-(2-methyl-2-propenyl)benzonitrile
• 英文别名: 2-(2-methylallyl)benzonitrile；3-(2-Cyanophenyl)-2-methyl-1-propene；2-(2-methylprop-2-enyl)benzonitrile
• CAS: 97780-98-8
• 化学式: C₁₁H₁₁N
• mdl: MFCD00671925
• 分子量: 157.215
• InChiKey: GBDRLTMHKWOQSX-UHFFFAOYSA-N

物化性质

• 沸点：
  246.7±9.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  2-(2-甲基烯丙基)苯甲腈 在 iron(III)-acetylacetonate 、 苯硅烷 、 盐酸 作用下， 以 异丙醇 、 丙醇 、 水 为溶剂， 反应 2.0h， 以91%的产率得到2,3-二氢-2,2-二甲基茚-1-酮
  参考文献：
  名称：

  氢原子转移介导的丁腈环化反应

  摘要：

  描述了使用PhSiH 3和催化Fe（acac）3的氢原子转移介导的烯烃与腈之间的分子内C-C偶联反应。这为闭环反应引入了新的战略性键断开连接，可通过亚胺中间体形成酮。值得注意的是反应的范围，包括空间位阻的酮，螺环和稠合的环状体系的形成。

  DOI：

  10.1002/chem.201805236
• 作为产物：
  描述：

  3-溴-2-甲基丙烯 、 2-溴苯腈 在 溴丁基-镁 、 正丁基锂 、 copper(I) cyanide di(lithium chloride) 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.16h， 生成 2-(2-甲基烯丙基)苯甲腈
  参考文献：
  名称：

  磷化氢催化的远程β-C ？烯烃三氟甲基化引发的胺的H功能化：双三氟甲基化酰胺和恶唑的一锅合成

  摘要：

  揭示了一种空前的膦催化的胺衍生物的远程β- CH官能化反应，该反应是由Togni's试剂将烯烃进行三氟甲基化而引发的。该反应通过未活化的烯烃的高度选择性和伴随的活化以及胺衍生物的β- CH键进行，从而以高收率提供了双三氟甲基化的酰胺，并具有良好的区域，化学和立体选择性。此外，新开发的单罐协议为有价值的三取代5-（三氟甲基）恶唑提供了便捷而经济的途径。机理研究表明，该反应可能是通过磷自由基阳离子通过未反应的烯烃的新的膦催化的自由基三氟甲基化而引发的。

  DOI：

  10.1002/anie.201412310

文献信息

• Photosubstitution of Dicyanobenzenes by Allylic Silanes, Germanes, and Stannanes via Photoinduced Electron Transfer
  作者：Kazuhisa Nakanishi、Kazuhiko Mizuno、Yoshio Otsuji

  DOI：10.1246/bcsj.66.2371

  日期：1993.8

  and -stannane, the photosubstitution occurred at both α- and γ-positions of the allylic moiety in a constant ratio, regardless of the kinds of metals. 1,3-Dicyanobenzene (m-DCB) was less reactive to the photosubstitution reaction. The reactivity of group 14 organometallic compounds increased in the order: Si- < Ge- < Sn-compounds. The photoreactions were sensitized by aromatic hydrocarbons such as

  在各种条件下研究了 1,2- 和 1,4- 二氰基苯（o-和 p-DCB）与烯丙基硅烷、锗烷和锡烷在乙腈中的光反应。在这些光反应中，o-和p-DCB 的氰基之一被烯丙基取代。对于三甲基（3-甲基-2-丁烯基）硅烷、-锗烷和-锡烷，无论金属种类如何，在烯丙基部分的α-和γ-位均以恒定比例发生光取代。1,3-二氰基苯 (m-DCB) 对光取代反应的反应性较低。第 14 族有机金属化合物的反应性按以下顺序增加：Si- < Ge- < Sn-化合物。光反应被芳烃如菲和苯并苯敏化，并且还通过添加 Mg (ClO4)2 和烷基苯来加速。取代产物形成的量子产率随着第 14 族有机金属化合物氧化电位的降低而增加。光反应的一个关键步骤是 d 的自由基阴离子的反应...
• Copper-Catalyzed Redox-Triggered Remote CH Functionalization: Highly Selective Formation of CCF₃ and CO Bonds
  作者：Taotao Li、Peng Yu、Jin-Shun Lin、Yonggang Zhi、Xin-Yuan Liu

  DOI：10.1002/cjoc.201500891

  日期：2016.5

  CH/unactivated alkenes functionalization reaction for the concomitant construction of CCF3 and CO bonds was described. An 1,5‐H radical transfer involving an sp3 CH bond adjacent to a nitrogen atom and an α‐CF3‐alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  铜催化的远程SP 3 Ç  H /未活化烯烃官能为C的伴随建筑反应 CF 3和C  O键进行了说明。涉及的SP的1,5--H自由基转移3 Ç 相邻氮原子和H键的α -CF 3 -烷基中间体从非活化烯烃观察并证实通过自由基处理进行衍生。
• Palladium(II)-Catalyzed Intramolecular Tandem Aminoalkylation via Divergent C(sp³)–H Functionalization
  作者：Wei Du、Qiangshuai Gu、Zhongliang Li、Dan Yang

  DOI：10.1021/ja5102739

  日期：2015.1.28

  We have developed a Pd(II)-catalyzed oxidative tandem aminoalkylation via divergent C(sp(3))-H functionalization, affording three- and five-membered-ring fused indolines in good yields under two optimized conditions, respectively. The mechanism studies have indicated that the benzylic C-H cleavage involved in the former transformation is the rate-determining step, while the cleavage of amide α-C-H in the latter is not. This is the first example of a Pd-catalyzed tandem reaction involving C(sp(3))-H activation without the employment of prefunctionalized reagents (e.g., halogenated and boron reagents) and directing groups, representing a green and economic protocol for the construction of N-containing heterocycles.
• Copper-Catalyzed Aminotrifluoromethylation of Unactivated Alkenes with (TMS)CF₃: Construction of Trifluoromethylated Azaheterocycles
  作者：Jin-Shun Lin、Xiang-Geng Liu、Xiao-Long Zhu、Bin Tan、Xin-Yuan Liu

  DOI：10.1021/jo5012619

  日期：2014.8.1

  The first example of a copper(I)-catalyzed intramolecular aminotrifluoromethylation of unactivated alkenes using (TMS)CF3 (trimethyl(trifluoromethyl)silane) as the CF3 source is described. A broad range of electronically and structurally varied substrates undergo convenient and step-economical transformations for the concurrent construction of a five- or six-membered ring and a C-CF3 bond toward different types of trifluoromethyl azaheterocycles. The methodology not only circumvents use of expensive electrophilic CF3 reagents or the photoredox strategy but also expands the scope to substrates that are difficult to access by the existing methods. Mechanistic studies are conducted, and a plausible mechanism is proposed.
• Intramolecular Oxidative Cyclization of Alkenes and Nitriles with Nickel(0)
  作者：Masato Ohashi、Masashi Ikawa、Sensuke Ogoshi

  DOI：10.1021/om2001603

  日期：2011.5.23

  The use of Me2AlCl as an additive was found to allow the oxidative addition of the Ar-CN bond in 2-(2-methylallyl)benzonitrile on nickel(0) in the presence of (PBu3)-Bu-n, giving a trans-arylnickelcyanide complex. In contrast, in the presence of PCy3, the intramolecular oxidative cyclization on nickel(0) took place to afford a nickeladihydropyrrole. Without the addition of Me2AlCl, the quantitative generation of an eta(2):eta(2)-5-ene-nitrile Ni(0) species, which was definitely converted to the nickeladihydropyrrole after treatment with Me2AlCl, was observed. In addition, TfOH also promoted the oxidative cyclization of the eta(2):eta(2)-5-ene-nitrile complex to yield the corresponding five-membered aza-nickelacycle. A similar intramolecular oxidative cyclization occurred when 2-allylbenzonitrile was used in the presence of a Lewis acid, such as Me2AlCl, Me2AlOTf, and Me3SiOTf, or of TfOH to give the corresponding nickeladihydropyrroles in quantitative yield. The molecular structures of a series of nickeladihydropyrroles were unambiguously determined by means of X-ray crystallography. The nickeladihydropyrrole derived from (2-methylallyl)benzonitrile and TfOH was found to react with HSiMe2Ph at 80 degrees C to furnish a silanamine derivative. The reaction was expanded to a Ni(0)/PCy3/TfOH-catalyzed coupling reaction of 5-ene-nitrile and HSiMe2Ph, yielding the corresponding silanamine in 84% yield.