bis(2,6-dimethylthiobenzoyl) disulfide

• 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: bis(2,6-dimethylthiobenzoyl) disulfide
• 英文别名: (2,6-Dimethylbenzenecarbothioyl)sulfanyl 2,6-dimethylbenzenecarbodithioate；(2,6-dimethylbenzenecarbothioyl)sulfanyl 2,6-dimethylbenzenecarbodithioate
• 化学式: C₁₈H₁₈S₄
• 分子量: 362.605
• InChiKey: TUVMYABGXXWGBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(2,6-dimethylthiobenzoyl) disulfide 、 偶氮二异丁腈 以 乙酸乙酯 为溶剂， 反应 16.0h， 以96%的产率得到2-cyanoprop-2-yl 2,6-dimethyldithiobenzoate
  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
• 作为产物：
  描述：

  二硫化碳 、 2,6-二甲基溴苯 在 碘 、 magnesium 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 6.0h， 以91.8%的产率得到bis(2,6-dimethylthiobenzoyl) disulfide
  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

• CURABLE COMPOSITION
  申请人：CEMEDINE CO., LTD.

  公开号：EP2412756B1

  公开（公告）日：2016-12-21
• US9745406B2
  申请人：——

  公开号：US9745406B2

  公开（公告）日：2017-08-29
• 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.