α-Methyl-α,γ,γ-trichlor-methylbutyrat | 26459-55-2

• 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: α-Methyl-α,γ,γ-trichlor-methylbutyrat
• 英文别名: Methyl 2,4,4-trichloro-2-methylbutanoate
• CAS: 26459-55-2
• 化学式: C₆H₉Cl₃O₂
• 分子量: 219.495
• InChiKey: KUROOUULKKSQIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  α-Methyl-α,γ,γ-trichlor-methylbutyrat 在 盐酸 作用下， 反应 48.0h， 以91%的产率得到5-羟基-3-甲基-2(5H)-呋喃酮
  参考文献：
  名称：

  (PCy3)2Cl2RuCHPh Catalyzed Kharasch additions. Application in a formal olefin carbonylation

  摘要：

  (PCy3)(2)Cl2Ru=CHPh-catalyzed Kharasch additions of trihaloalkanes across olefins provide polyhalogenated adducts, which upon hydrolysis furnish alpha,beta-unsaturated ketones, aldehydes, or gamma-hydroxybutenolides. This two-step process represents an overall acylation or carbonylation of an olefin. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.06.066
• 作为产物：
  描述：

  甲基丙烯酸甲酯 在 tris(triphenylphosphine)ruthenium(II) chloride 异丙醇 作用下， 反应 6.0h， 生成 α-Methyl-α,γ,γ-trichlor-methylbutyrat
  参考文献：
  名称：

  Selective Transfer Hydrogenolysis of 1,1,1,3-Tetrachloro to 1,1,3-Trichloro Compounds

  摘要：

  DOI：

  10.1055/s-1975-23798

文献信息

• Atom-Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl2Cp*(PPh3)] and Magnesium
  作者：Katrin Thommes、Burçak Içli、Rosario Scopelliti、Kay Severin

  DOI：10.1002/chem.200700442

  日期：2007.8.17

  A new catalytic procedure for atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions is described. The combination of the ruthenium(III) complex [RuCl(2)Cp*(PPh3)] (Cp*: pentamethylcyclopentadienyl) with magnesium allows these reactions to be performed under mild conditions with high efficiency. In most cases, the catalyst concentrations required are significantly lower than those used

  描述了一种用于原子转移自由基加成（ATRA）和环化（ATRC）反应的新催化程序。钌（III）配合物[RuCl（2）Cp *（PPh3）]（Cp *：五甲基环戊二烯基）与镁的结合使这些反应可以在温和的条件下高效地进行。在大多数情况下，所需的催化剂浓度明显低于先前报道的程序中使用的浓度。建议镁充当还原剂，其产生和再生催化活性的钌（II）物种。通过X射线晶体学分析了前催化剂[RuCl（2）Cp *（PPh3）]。
• Photoinitiated ambient temperature copper-catalyzed atom transfer radical addition (ATRA) and cyclization (ATRC) reactions in the presence of free-radical diazo initiator (AIBN)
  作者：Marielle Nicole C. Balili、Tomislav Pintauer

  DOI：10.1039/c0dt01764g

  日期：——

  monoadduct was obtained in lower yields in the ATRA of less active halogenated compounds, which was mostly due to incomplete alkene conversions. Ambient temperature ATRA of CCl4 to various 1,6-dienes followed by sequential ATRC was also performed in the presence of UV light using [CuII(TPMA)Cl][Cl] complex and AIBN. High yields of the 5-exo-trig cyclic product were obtained for all dienes with preferential

  据报道，在AIBN存在下，紫外线在铜催化的原子转移自由基加成（ATRA）和各种（多）卤代化合物与高活性烯烃的环化（ATRC）反应中的使用。由AIBN的光分解产生的自由基可在环境温度下有效地再生铜（I）配合物，从而实现ATRA的ATRA四氯化碳4催化剂负载量低至0.05 mol％的CBr 4和CBr 4。活性较低的卤代化合物在ATRA中以较低的收率获得了所需的单加合物，这主要是由于烯烃转化不完全所致。的环境温度ATRA四氯化碳4使用[Cu II（TPMA）Cl] [Cl]配合物和AIBN ，在紫外光存在下，先后制得各种1,6-二烯，然后依次进行ATRC 。对于所有二烯，以顺式异构体的优先形成，获得了高产率的5- exo - trig环状产物。
• A half-sandwich 1,2-azaborolyl ruthenium complex: synthesis, characterization, and evaluation of its catalytic activities
  作者：Zicheng Liu、Junjie Xu、Wenqing Ruan、Chen Fu、Hui-Jun Zhang、Ting-Bin Wen

  DOI：10.1039/c3dt51177d

  日期：——

  A half-sandwich 1,2-azaborolyl (Ab) ruthenium complex, (Ab–CCPh)RuCl(PPh3)2 (1), has been synthesized by treating RuCl2(PPh3)3 with lithium 1,2-azaborolide L-1, or by treating either RuCl2(PPh3)3 or RuHCl(PPh3)3 directly with 1,2-azaborole LH-1. It is evaluated as a suitable precatalyst in [2 + 2] cycloadditions of norbornene derivatives with DMAD and in atom transfer radical additions of halogenated compounds with olefins.

  通过将 RuCl2(PPh3)3 与 1,2-氮杂硼酸锂 L-1 一起处理，或将 RuCl2(PPh3)3 或 RuHCl(PPh3)3 直接与 1,2-氮杂硼酸 LH-1 一起处理，合成了一种半夹心 1,2-氮杂硼酸（Ab）钌配合物 (Ab-CCPh)RuCl(PPh3)2 (1)。在降冰片烯衍生物与 DMAD 的[2 + 2]环加成反应中，以及卤代化合物与烯烃的原子转移自由基加成反应中，它被评估为一种合适的前催化剂。
• Controlled homopolymerization of multi-vinyl monomers: dendritic polymers synthesized via an optimized ATRA reaction
  作者：Yu Zheng、Tianyu Zhao、Ben Newland、Julien Poly、Wenxin Wang

  DOI：10.1039/c3cc44898c

  日期：——

  managed to find the optimal ATRA system that can obtain the highest mono-adduct yields with the purpose of minimizing the chain growth of divinyl monomers. The most highly hyperbranched polymers have been synthesized by the homopolymerization of multi-vinyl monomers via ATRA reaction.

  在这项研究中，我们设法找到了最佳的ATRA系统，该系统可以获得最高的单加合物收率，目的是最大程度地减少二乙烯基单体的链增长。最高的超支化聚合物是通过ATRA反应使多乙烯基单体均聚而合成的。
• Atom transfer radical addition and enol-ester synthesis catalyzed by Ru–vinylidene complexes
  作者：Tom Opstal、Francis Verpoort

  DOI：10.1016/s0040-4039(02)02233-5

  日期：2002.12

  L) (L=PCy3 or N-heterocyclic carbenes) reveal themselves as a versatile catalyst for the atom transfer radical addition (ATRA) of polyhalogenated alkanes to olefins, such as methylmethacrylate, styrene and 1-octene. Furthermore, these systems are excellent catalysts for the nucleophilic addition of carboxylic acids to terminal alkynes and yielded exclusively alk-1-en-2-yl esters. These complexes can

  Ru-亚乙烯基络合物，Cl 2 Ru CC（H）t But}（PCy 3）（L）（L = PCy 3或N-杂环卡宾）揭示了它们本身是原子转移自由基加成的通用催化剂（将多卤代烷烃转化为烯烃（例如甲基丙烯酸甲酯，苯乙烯和1-辛烯）。此外，这些系统是将羧酸亲核加成至末端炔烃的极佳催化剂，并且仅产生烷基-1-烯-2-基酯。这些络合物也可以通过用AgBF 4处理中性络合物而转化为它们的阳离子对应物，并研究它们在ATRA和乙烯基化反应中的催化潜力。