3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate | 1215038-81-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate
• 英文别名: 3,3,5-Trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate；(5-chloro-3,3,5-trimethylhexyl) 2-bromo-2-methylpropanoate
• CAS: 1215038-81-5
• 化学式: C₁₃H₂₄BrClO₂
• 分子量: 327.689
• InChiKey: ZQMKMYCSFBDJAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  3,3-二甲基-4-戊烯酸甲酯 在 盐酸 、 硼烷四氢呋喃络合物 、 双氧水 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 为溶剂， 生成 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate
  参考文献：
  名称：

  新的双重引发剂，可组合碳阳离子聚合和原子转移自由基聚合

  摘要：

  新的双引发剂，包括3-溴丙酸3,3,5-三甲基-5-氯己酯（IB 2 BP）和含有3-溴丙酸3,3,5-三甲基-5-氯己基（IB 2 BMP）合成了用于碳阳离子聚合和原子转移自由基聚合（ATRP）的两个起始位点，并用于创建聚（异丁烯-b-丙烯酸甲酯）（PIB- b -PMA）二嵌段共聚物。引发剂合成涉及3,3-二甲基-4-戊烯酸甲酯与2当量的甲基溴化镁反应，然后对双键进行硼氢化-氧化，生成1,5-二羟基-3,3,5-三甲基己烷（DHTMH）。IB 2通过使DHTMH的伯羟基与2-溴丙酰溴反应，然后用无水HCl氯化叔羟基来合成BP。使用2-溴-2-甲基丙酰基溴类似地合成IB 2 BMP。两种引发剂均显示出异丁烯的缓慢阳离子引发，导致在低温（-70°C）和低单体/引发剂比率（82）下具有中等引发效率（0.50 < I eff <0.80）。当温度升高至-50°C和/或单体/引发剂比率增加时，观察到更高的阳离子引发效率（0

  DOI：

  10.1021/ma1011655

文献信息

• New Dual Initiators To Combine Quasiliving Carbocationic Polymerization and Atom Transfer Radical Polymerization
  作者：Yaling Zhu、Robson F. Storey

  DOI：10.1021/ma1011655

  日期：2010.9.14

  New dual initiators, 3,3,5-trimethyl-5-chlorohexyl 2-bromopropionate (IB2BP) and 3,3,5-trimethyl-5-chlorohexyl 2-bromo-2-methylpropionate (IB2BMP), which contain initiating sites for both carbocationic polymerization and atom transfer radical polymerization (ATRP), were synthesized and used to create poly(isobutylene-b-methyl acrylate) (PIB-b-PMA) diblock copolymers. Initiator synthesis involved reaction

  新的双引发剂，包括3-溴丙酸3,3,5-三甲基-5-氯己酯（IB 2 BP）和含有3-溴丙酸3,3,5-三甲基-5-氯己基（IB 2 BMP）合成了用于碳阳离子聚合和原子转移自由基聚合（ATRP）的两个起始位点，并用于创建聚（异丁烯-b-丙烯酸甲酯）（PIB- b -PMA）二嵌段共聚物。引发剂合成涉及3,3-二甲基-4-戊烯酸甲酯与2当量的甲基溴化镁反应，然后对双键进行硼氢化-氧化，生成1,5-二羟基-3,3,5-三甲基己烷（DHTMH）。IB 2通过使DHTMH的伯羟基与2-溴丙酰溴反应，然后用无水HCl氯化叔羟基来合成BP。使用2-溴-2-甲基丙酰基溴类似地合成IB 2 BMP。两种引发剂均显示出异丁烯的缓慢阳离子引发，导致在低温（-70°C）和低单体/引发剂比率（82）下具有中等引发效率（0.50 < I eff <0.80）。当温度升高至-50°C和/或单体/引发剂比率增加时，观察到更高的阳离子引发效率（0
• Effect of Structure on Cationic Initiation Efficiency of a Carbocatonic/ATRP Dual Initiator
  作者：Yaling Zhu、Robson F. Storey

  DOI：10.1021/ma202682w

  日期：2012.2.14

  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.