2-cyanoprop-2-yl 1-dithionaphthalate | 488112-82-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-cyanoprop-2-yl 1-dithionaphthalate
• 英文别名: 2-Cyanopropan-2-yl naphthalene-1-carbodithioate
• CAS: 488112-82-9
• 化学式: C₁₅H₁₃NS₂
• 分子量: 271.407
• InChiKey: ZUZNFFVDQKJTHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  81.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-溴甲基萘 在 sodium methylate 、 sulfur 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 3.0h， 生成 2-cyanoprop-2-yl 1-dithionaphthalate
  参考文献：
  名称：

  Searching for More Effective Agents and Conditions for the RAFT Polymerization of MMA:  Influence of Dithioester Substituents, Solvent, and Temperature

  摘要：

  A series of tertiary dithiobenzoates differently substituted on the phenyl group (Z) were synthesized in order to investigate the RAFT-mediated polymerization of MMA. The chain-transfer agent 2-eyanoprop-2-yl dithiobenzoate, although an excellent RAFT agent for polymerization of MMA, does not yield a very narrow polydispersed polymer at low conversion. The introduction of electron-withdrawing substituents on the dithiobenzoate aromatic ring improves the activity of the chain-transfer agent narrowing the molecular weight distribution, especially in the first 2 h of the process; conversely, electron-donating substituents deteriorate the performance of the process in the early stages. Substituents on the dithiobenzoate that, for reasons of steric hindrance reduce the conjugation of the phenyl with the C=S double bond of the dithiogroup, diminish the effectiveness of the chain-transfer agent. The nature of the leaving group (R) also has a strong influence on the process: the substitution of 2-cyanoprop-2-yl with the bulkier 2-cyano-4-methylpent-2-yl as leaving group improves remarkably the MMA polymerization, especially in the early stages. The solvent effect on MMA RAFT polymerization using benzene, acetonitrile, and DMF was also investigated. The lower propagation rate constant of MMA in benzene gives rise to reduced rates of polymerization but narrower polydispersities of the polymer, especially at low conversions. The RAFT polymerizations of MMA were carried out at 60 and 90 degrees C to assess the temperature dependence of the process. The higher temperature increases both the rate of polymerization and the transfer constant of the RAFT agent, resulting in lower polydispersities at a given conversion. Ab initio calculations confirmed the observed experimental results.

  DOI：

  10.1021/ma0480650

文献信息

• Developing a Synthetic Approach with Thermoregulated Phase-Transfer Catalysis: Facile Access to Metal-Mediated Living Radical Polymerization of Methyl Methacrylate in Aqueous/Organic Biphasic System
  作者：Liangjiu Bai、Lifen Zhang、Jinlong Pan、Jian Zhu、Zhenping Cheng、Xiulin Zhu

  DOI：10.1021/ma4000489

  日期：2013.3.26

  A novel strategy via thermoregulated phase-transfer catalysis (TRPTC) to separating catalyst in aqueous/organic biphasic system has been successfully established in a copper-mediated activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) of methyl methacrylate (MMA), using a thermoresponsive PEG-supported dipyridyl ligand (PSDL) as the ligand and an alkyl pseudohalogen

  催化剂配合物可以在反应温度（90°C）下从初始催化剂水溶液转移到有机相中，以催化MMA的均相聚合，然后再从有机相转移到水溶液中，一旦催化剂从聚合溶液中分离出来冷却至室温（25°C），同时在有机层中保留良好控制的产品（PMMA）。另外，聚合可以在有限量的空气存在下进行，这不仅不牺牲聚合的可控性，而且仅通过简单地有效改变温度就可以使催化剂再循环。
• US9683160B1
  申请人：——

  公开号：US9683160B1

  公开（公告）日：2017-06-20
• US9701884B1
  申请人：——

  公开号：US9701884B1

  公开（公告）日：2017-07-11
• Searching for More Effective Agents and Conditions for the RAFT Polymerization of MMA:  Influence of Dithioester Substituents, Solvent, and Temperature
  作者：Massimo Benaglia、Ezio Rizzardo、Angelo Alberti、Maurizio Guerra

  DOI：10.1021/ma0480650

  日期：2005.4.1

  A series of tertiary dithiobenzoates differently substituted on the phenyl group (Z) were synthesized in order to investigate the RAFT-mediated polymerization of MMA. The chain-transfer agent 2-eyanoprop-2-yl dithiobenzoate, although an excellent RAFT agent for polymerization of MMA, does not yield a very narrow polydispersed polymer at low conversion. The introduction of electron-withdrawing substituents on the dithiobenzoate aromatic ring improves the activity of the chain-transfer agent narrowing the molecular weight distribution, especially in the first 2 h of the process; conversely, electron-donating substituents deteriorate the performance of the process in the early stages. Substituents on the dithiobenzoate that, for reasons of steric hindrance reduce the conjugation of the phenyl with the C=S double bond of the dithiogroup, diminish the effectiveness of the chain-transfer agent. The nature of the leaving group (R) also has a strong influence on the process: the substitution of 2-cyanoprop-2-yl with the bulkier 2-cyano-4-methylpent-2-yl as leaving group improves remarkably the MMA polymerization, especially in the early stages. The solvent effect on MMA RAFT polymerization using benzene, acetonitrile, and DMF was also investigated. The lower propagation rate constant of MMA in benzene gives rise to reduced rates of polymerization but narrower polydispersities of the polymer, especially at low conversions. The RAFT polymerizations of MMA were carried out at 60 and 90 degrees C to assess the temperature dependence of the process. The higher temperature increases both the rate of polymerization and the transfer constant of the RAFT agent, resulting in lower polydispersities at a given conversion. Ab initio calculations confirmed the observed experimental results.