2,2-dimethyl-1-cyano-1-benzoylethene | 89809-90-5

• 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: 2,2-dimethyl-1-cyano-1-benzoylethene
• 英文别名: 2-benzoyl-3-methylbut-2-enenitrile；2-benzoyl-3-methyl-crotononitrile
• CAS: 89809-90-5
• 化学式: C₁₂H₁₁NO
• 分子量: 185.225
• InChiKey: WFOVANSRBZSLKD-UHFFFAOYSA-N

物化性质

• 熔点：
  210 °C(Solv: water (7732-18-5); methanol (67-56-1))
• 沸点：
  320.6±34.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-1-cyano-1-benzoylethene 在 naphthalen-1-yl-lithium 、 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 0.83h， 生成 Phenyl-(4,6,6-trimethyl-1-phenylselanylcyclohex-3-en-1-yl)methanone
  参考文献：
  名称：

  萘基锂诱导 α-氰基酮的还原硒基化：α-苯基硒基酮的区域控制过程和一锅法转化为烯酮系统

  摘要：

  利用萘基锂诱导的α-氰基酮系统的还原硒基化作为关键操作，已经开发了一种用于区域控制合成α-苯基硒酮的有效程序。此外，如此原位生成的硒酮，在随后用过氧化氢和乙酸处理后，可以以高度的区域选择性进一步转化为相应的烯酮，这可能是由于锂盐介导的硒氧化物同步消除过程。

  DOI：

  10.1055/s-2007-977448
• 作为产物：
  描述：

  苯甲酰乙腈 、 丙酮 在 哌啶 作用下， 生成 2,2-dimethyl-1-cyano-1-benzoylethene
  参考文献：
  名称：

  KLOSA, Pharmazie, 1952, vol. 7, # 5, p. 299 - 300

  摘要：

  DOI：

文献信息

• N-Heterocyclic Carbene-Catalyzed Construction of 1,3,5-Trisubstituted Benzenes from Bromoenals and α-Cyano-β-methylenones
  作者：Chun-Lin Zhang、Song Ye

  DOI：10.1021/acs.orglett.6b03306

  日期：2016.12.16

  A direct and efficient approach to 1,3,5-trisubstituted benzenes has been developed via N-heterocyclic carbene-catalyzed [2 + 4] annulation of α-bromoenals and α-cyano-β-methylenones. The reaction worked well for both aryl- and alkylenones.

  通过N-杂环卡宾催化的[2 + 4]环抱α-溴烯醛和α-氰基-β-甲基烯酮，已经开发出直接有效的1,3,5-三取代苯的方法。该反应对于芳基和烷基烯酮都很好。
• Direct Assembly of Polysubstituted Naphthalenes via a Tandem Reaction of Benzynes and α-Cyano-β-methylenones
  作者：Qiang Wang、Yi An、Guangfen Du、Zhi-Hua Cai、Bin Dai、Lin He

  DOI：10.1021/acs.joc.0c01975

  日期：2020.11.6

  A mild and transition-metal-free benzannulation reaction for the construction of the naphthalene skeleton has been described. Benzynes react with α-cyano-β-alkylenones through a tandem nucleophilic addition/cyclization/aromatization process to afford polysubstituted naphthalenes in 50–94% yields.

  已经描述了用于构建萘骨架的温和且无过渡金属的苯环反应。苯甲酮通过串联亲核加成/环化/芳构化过程与α-氰基-β-烷基烯酮反应，以50-94％的产率提供多取代的萘​​。
• Soto, Jose L.; Seoane, Carlos; Martin, Nazario, Heterocycles, 1984, vol. 22, # 1, p. 1 - 6
  作者：Soto, Jose L.、Seoane, Carlos、Martin, Nazario、Quinteiro, Margarita

  DOI：——

  日期：——
• Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine
  作者：Yiting Gu、Pengfei Hu、Chunjie Ni、Xiaofeng Tong

  DOI：10.1021/jacs.5b03273

  日期：2015.5.20

  Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of beta'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the beta'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, beta'C of allenoate 1 is an electrophilic center, and its beta'C and gamma C serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a gamma-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of gamma C and 1,3-dipole chemical behavior of beta C and beta'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.
• Tandem Cyclization of α-Cyano α-Alkynyl Aryl Ketones Induced by <i>tert</i>-Butyl Hydroperoxide and Tetrabutylammonium Iodide
  作者：Ying-Chieh Wong、Chen-Tso Tseng、Tzu-Ting Kao、Yu-Cheng Yeh、Kak-Shan Shia

  DOI：10.1021/ol3028972

  日期：2012.12.7

  The radical cascade protocol of the alpha-cyano alpha-TMS/aryl-capped alkynyl aryl ketones promoted by tert-butyl hydroperoxide under catalysis with tetrabutylammonium iodide in refluxing benzene has been developed, leading to the construction of a variety of highly functionalized [6,6,5] tricyclic frameworks in an efficient manner.