methyl phenylselenomalonitrile | 141439-28-3

• 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: methyl phenylselenomalonitrile
• 英文别名: methyl(phenylseleno)malonodinitrile；2-Methyl-2-(phenylseleno)malononitrile；methyl(phenylseleno)malononitrile；Methyl(phenylselanyl)propanedinitrile；2-methyl-2-phenylselanylpropanedinitrile
• CAS: 141439-28-3
• 化学式: C₁₀H₈N₂Se
• 分子量: 235.147
• InChiKey: NYKQOHZANIATFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl phenylselenomalonitrile 、 乙烯基乙醚 在 偶氮二异丁腈 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以99%的产率得到(2-ethoxy-2-(phenylseleno)ethyl)methylpropanedinitrile
  参考文献：
  名称：

  Group Transfer Addition Reactions of Methyl (phenylseleno)malononitrile to Alkenes

  摘要：

  Results of a detailed study of group transfer additions of methyl(phenylseleno)propanedinitrile (4) to a wide variety of alkenes are reported. For example, heating of 4 (60 degrees C) with 1-hexene and AIBN produces (2-(phenylseleno)-hexyl)methylpropanedinitrile in 97% yield. Reagent 4 adds in high yields to monosubstituted styrenes, enol ethers, enol acetates, enol sulfides, enamides, and enol imidazoles and carbazoles. Additions to many classes of 1,2-disubstituted alkenes also occur, and modest to good levels of 1,2-asymmetric induction are observed in the selenium transfer step. Oxygen- and sulfur-substituted alkenes produce anti products, and N-substituted alkenes produce syn products. The proposed mechanism involves radical addition followed by phenylselenium group transfer, and it is shown that radical additions to certain classes of disubstituted alkenes can be reversible. Additions to trisubstituted alkenes fair, probably because of this reversibility. Competition studies provide a relative reactivity scale of alkenes toward the electrophilic methylpropanedinitrile radical. Finally, a series of transformations serve to illustrate some synthetic possibilities for the products of these selenium transfer addition reactions.

  DOI：

  10.1021/ja00089a017
• 作为产物：
  描述：

  1-异喹啉硼酸 、 苯基溴化硒 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以77%的产率得到methyl phenylselenomalonitrile
  参考文献：
  名称：

  Rate constants for chalcogen group transfers in bimolecular substitution reactions with primary alkyl radicals

  摘要：

  Rate constants for group transfers of the MeS, PhS, PhSe, and PhTe groups from chalcogen-substituted acetate, acetonitrile, malonate, and malononitrile compounds, from N-(phenylthio) phthalimide and from Me2S2 and Ph2S2 to primary alkyl radicals, have been determined by competition kinetics using PTOC esters as the radical precursors and competing trapping agents. Thio group transfers from malononitrile derivatives are marginally faster than the corresponding group transfer from the symmetrical disulfide, and the rate constant for PhSe group transfer from PhSeSePh is greater than those from the derivatives studied here. Substituent effects suggest that the chalcogen transfer reactions may be concerted. For three cases in which direct comparisons can be made, the rate constants for reactions of phenylchalcogenides are approximately equal to those for halogen atom transfer when the chalcogen and halide are in the same row of the periodic table and the radical resulting from displacement is the same. The rate constants reported in this work will be useful for the rational design of synthetic schemes based on homolytic group transfer chemistry.

  DOI：

  10.1021/jo00069a036

文献信息

• Generation and Trapping of Radicals Derived from Cyclobutadieneiron Tricarbonyl
  作者：Jeffrey H. Byers、Stephen F. Sontum、Tina S. Dimitrova、Sumaya Huque、Benjamin M. Zegarelli、Yong Zhang、Jerry P. Jasinski、Raymond J. Butcher

  DOI：10.1021/om060263n

  日期：2006.7.1

  Trapping products consistent with the formation of radical intermediates α to and on the ring carbon of cyclobutadieneiron tricarbonyl have been synthesized. These examples constitute the first strong experimental evidence for the formation of radicals derived from cyclobutadieneiron tricarbonyl.

  已经合成了与在环丁二烯三羰基的环碳上和在环碳上形成自由基中间体α一致的捕获产物。这些实例构成了形成源自环丁二烯三羰基的自由基的第一个有力的实验证据。
• Group transfer addition reactions of selenomalononitriles to chiral enol ethers. Asymmetric radical addition and selenium transfer reactions
  作者：Dennis P. Curran、Steven J. Geib、Lung Huang Kuo

  DOI：10.1016/s0040-4039(00)73400-9

  日期：1994.8

  Group transfer addition reactions of alkyl phenylselenomalononitriles to enol ethers derived from trans-2-phenylcyclohexanol and 8-phenylmenthol occur cleanly, and moderate to excellent stereoselection is observed in both the radical addition and phenylselenium transfer steps.

  烷基苯基硒烯丙二烯腈与衍生自反式-2-苯基环己醇和8-苯基薄荷醇的烯醇醚的基团转移加成反应完全发生，并且在自由基加成和苯基硒转移步骤中均观察到中度至优异的立体选择。
• Additions of malononitrile radicals to alkenes: new examples of 1,2-asymmetric induction in iodine and phenylselenium transfer reactions
  作者：Dennis P. Curran、Gebhard Thoma

  DOI：10.1021/ja00037a080

  日期：1992.5
• Curran Dennis P., Geib Steven J., Lung Huang Kuo, Tetrahedron Lett, 35 (1994) N 34, S 6235-6238
  作者：Curran Dennis P., Geib Steven J., Lung Huang Kuo

  DOI：——

  日期：——
• Group Transfer Addition Reactions of Methyl (phenylseleno)malononitrile to Alkenes
  作者：Dennis P. Curran、Eugen Eichenberger、Maree Collis、Michael G. Roepel、Gebhard Thoma

  DOI：10.1021/ja00089a017

  日期：1994.5

  Results of a detailed study of group transfer additions of methyl(phenylseleno)propanedinitrile (4) to a wide variety of alkenes are reported. For example, heating of 4 (60 degrees C) with 1-hexene and AIBN produces (2-(phenylseleno)-hexyl)methylpropanedinitrile in 97% yield. Reagent 4 adds in high yields to monosubstituted styrenes, enol ethers, enol acetates, enol sulfides, enamides, and enol imidazoles and carbazoles. Additions to many classes of 1,2-disubstituted alkenes also occur, and modest to good levels of 1,2-asymmetric induction are observed in the selenium transfer step. Oxygen- and sulfur-substituted alkenes produce anti products, and N-substituted alkenes produce syn products. The proposed mechanism involves radical addition followed by phenylselenium group transfer, and it is shown that radical additions to certain classes of disubstituted alkenes can be reversible. Additions to trisubstituted alkenes fair, probably because of this reversibility. Competition studies provide a relative reactivity scale of alkenes toward the electrophilic methylpropanedinitrile radical. Finally, a series of transformations serve to illustrate some synthetic possibilities for the products of these selenium transfer addition reactions.