3,3,5,5,7-pentamethyl-7-octenyl 2-bromo-2-methylpropionate | 1356928-80-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3,3,5,5,7-pentamethyl-7-octenyl 2-bromo-2-methylpropionate
• CAS: 1356928-80-7
• 化学式: C₁₇H₃₁BrO₂
• 分子量: 347.336
• InChiKey: FHYFRMYGNCCQAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  20.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3,3,5,5,7-pentamethyl-7-octenyl 2-bromo-2-methylpropionate 在 盐酸 作用下， 以93.5%的产率得到3,3,5,5,7-pentamethyl-7-chlorooctyl 2-bromo-2-methylpropionate
  参考文献：
  名称：

  Effect of Structure on Cationic Initiation Efficiency of a Carbocatonic/ATRP Dual Initiator

  摘要：

  The dual initiator, 3,3,5,5,7-pentamethyl-7-chlorooctyl 2-bromo-2-methylpropionate (IB3BMP), possessing initiating sites for both living carbocationic polymerization (LCP) and atom transfer radical polymerization (ATRP), was synthesized to overcome the low initiation efficiency of previously reported dual initiators such as 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate (IB2BMP). Low initiation efficiency of the latter and similar initiators has been attributed to complexation between the Lewis acid polymerization catalyst and the ester carbonyl group of the initiator. IB3BMP was synthesized by reacting IB2BMP with 2-methallyltrimethylsilane at low temperature, followed by hydrochlorination. IB3BMP, which differs from IB2BMP by the inclusion of one additional isobutylene (IB) repeating unit, showed quantitative initiation efficiency (I-eff similar to 1) in TiCl4-co-initiated LCP of TB under various reaction conditions, including low temperature (-70 degrees C) and low monomer/initiator ratios (48-164). I-eff and polydispersity index of the resulting polyisobutylenes were identical to those obtained with the commonly used, monofunctional cationic initiators 2-chloro-2,4,4-trimethylpentane (TMPCl) and 2-chloro-2,4,4,6,6-pentamethylheptane (PMHCl). The superiority of IB3BMP compared to IB2BMP in carbocationic initiation was attributed to increased separation between the tert-chloride initiating site and the TiCl4:carbonyl complex at the ATRP initiating site. A PIB macroinitiator prepared from IB3BMP was used to initiate ATRP of methyl acrylate. Efficiency of radical initiation was quantitative, the targeted poly(methyl acrylate) block length was obtained, and the resulting block copolymer possessed narrow polydispersity.

  DOI：

  10.1021/ma202682w
• 作为产物：
  描述：

  异丁烯基三甲基硅烷 、 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以45.3%的产率得到3,3,5,5,7-pentamethyl-7-octenyl 2-bromo-2-methylpropionate
  参考文献：
  名称：

  Effect of Structure on Cationic Initiation Efficiency of a Carbocatonic/ATRP Dual Initiator

  摘要：

  The dual initiator, 3,3,5,5,7-pentamethyl-7-chlorooctyl 2-bromo-2-methylpropionate (IB3BMP), possessing initiating sites for both living carbocationic polymerization (LCP) and atom transfer radical polymerization (ATRP), was synthesized to overcome the low initiation efficiency of previously reported dual initiators such as 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate (IB2BMP). Low initiation efficiency of the latter and similar initiators has been attributed to complexation between the Lewis acid polymerization catalyst and the ester carbonyl group of the initiator. IB3BMP was synthesized by reacting IB2BMP with 2-methallyltrimethylsilane at low temperature, followed by hydrochlorination. IB3BMP, which differs from IB2BMP by the inclusion of one additional isobutylene (IB) repeating unit, showed quantitative initiation efficiency (I-eff similar to 1) in TiCl4-co-initiated LCP of TB under various reaction conditions, including low temperature (-70 degrees C) and low monomer/initiator ratios (48-164). I-eff and polydispersity index of the resulting polyisobutylenes were identical to those obtained with the commonly used, monofunctional cationic initiators 2-chloro-2,4,4-trimethylpentane (TMPCl) and 2-chloro-2,4,4,6,6-pentamethylheptane (PMHCl). The superiority of IB3BMP compared to IB2BMP in carbocationic initiation was attributed to increased separation between the tert-chloride initiating site and the TiCl4:carbonyl complex at the ATRP initiating site. A PIB macroinitiator prepared from IB3BMP was used to initiate ATRP of methyl acrylate. Efficiency of radical initiation was quantitative, the targeted poly(methyl acrylate) block length was obtained, and the resulting block copolymer possessed narrow polydispersity.

  DOI：

  10.1021/ma202682w