cyanomethyl (4-fluorophenyl)-(pyridin-4-yl)carbamodithioate | 1374852-37-5

• 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: cyanomethyl (4-fluorophenyl)-(pyridin-4-yl)carbamodithioate
• 英文别名: cyanomethyl N-(4-fluorophenyl)-N-pyridin-4-ylcarbamodithioate
• CAS: 1374852-37-5
• 化学式: C₁₄H₁₀FN₃S₂
• 分子量: 303.384
• InChiKey: JPMHHLHWIRNYPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  97.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-氯吡啶 、 4-氟苯胺 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 potassium tert-butylate 、 1,3-双(2,6-二异丙基苯基)氯化咪唑鎓 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 61.0h， 生成 cyanomethyl (4-fluorophenyl)-(pyridin-4-yl)carbamodithioate
  参考文献：
  名称：

  Chain Transfer Kinetics of Acid/Base Switchable N-Aryl-N-Pyridyl Dithiocarbamate RAFT Agents in Methyl Acrylate, N-Vinylcarbazole and Vinyl Acetate Polymerization

  摘要：

  The structures of the "Z" and "R" substituents of a RAFT agent (Z-C(S)S R) determine a RAFT agent's ability to control radical polymerization. In this paper we report new acid/base switchable N-aryl-N-pyridyl dithiocarbamates (R = -CH2CN, Z = -N(Py)(Ar)) which vary in substituent at the 4-position of the aryl ring and the use of these to control molecular weight and dispersity. In their protonated form, the new RAFT agents are more effective in controlling polymerization of the more activated monomer, methyl acrylate (MA), whereas in their neutral form they provide more effective control of the polymerization of less activated monomers, N-vinyl carbazole (NVC) and vinyl acetate (VAc). For each polymerization, the apparent chain transfer coefficient (C-tr(aPP)) shows a good correlation with Hammett parameters. Dithiocarbamates with more electron-withdrawing aryl ring substituents have the higher C-tr(aPP). This demonstrates the influence of polar effects on C-tr(aPP) and supports the hypothesis that the activity of these RAFT agents is determined by the availability of the lone pair of the dithiocarbamate nitrogen.

  DOI：

  10.1021/ma300616g

文献信息

• Chain Transfer Kinetics of Acid/Base Switchable <i>N</i>-Aryl-<i>N</i>-Pyridyl Dithiocarbamate RAFT Agents in Methyl Acrylate, <i>N</i>-Vinylcarbazole and Vinyl Acetate Polymerization
  作者：Daniel J. Keddie、Carlos Guerrero-Sanchez、Graeme Moad、Roger J. Mulder、Ezio Rizzardo、San H. Thang

  DOI：10.1021/ma300616g

  日期：2012.5.22

  The structures of the "Z" and "R" substituents of a RAFT agent (Z-C(S)S R) determine a RAFT agent's ability to control radical polymerization. In this paper we report new acid/base switchable N-aryl-N-pyridyl dithiocarbamates (R = -CH2CN, Z = -N(Py)(Ar)) which vary in substituent at the 4-position of the aryl ring and the use of these to control molecular weight and dispersity. In their protonated form, the new RAFT agents are more effective in controlling polymerization of the more activated monomer, methyl acrylate (MA), whereas in their neutral form they provide more effective control of the polymerization of less activated monomers, N-vinyl carbazole (NVC) and vinyl acetate (VAc). For each polymerization, the apparent chain transfer coefficient (C-tr(aPP)) shows a good correlation with Hammett parameters. Dithiocarbamates with more electron-withdrawing aryl ring substituents have the higher C-tr(aPP). This demonstrates the influence of polar effects on C-tr(aPP) and supports the hypothesis that the activity of these RAFT agents is determined by the availability of the lone pair of the dithiocarbamate nitrogen.