phenethyl 2-bromo-2-methylpropanoate | 43216-34-8

• 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: phenethyl 2-bromo-2-methylpropanoate
• 英文别名: 2-Phenylethyl 2-bromo-2-methylpropanoate
• CAS: 43216-34-8
• 化学式: C₁₂H₁₅BrO₂
• 分子量: 271.154
• InChiKey: RBJIEZRBKCJGLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  phenethyl 2-bromo-2-methylpropanoate 在 异丙醇 、 反式-二叔丁基连二次硝酸酯 作用下， 反应 5.0h， 生成 异丁酸苯乙酯
  参考文献：
  名称：

  Organic Reducing Agents: Some Radical Chain Reactions of Ketyl and 1,3-Dioxolanyl Radicals with Activated Bromides

  摘要：

  The radical chain reduction of primary and secondary alpha-bromo esters by 2-propanol and 2-methyldioxolane has been shown to be a kinetically viable process with average chain lengths of >10 at temperatures between 30 and 60 degrees C. For electron-deficient bromides, these simple organic reagents may effectively replace the more commonly used (and more expensive) organosilicon or tin hydides. Some mechanistic insights have been obtained from a combination of kinetic and thermodynamic measurements. The rate constants for the reaction of the 2-hydroxy-2-propyl and the 2-methyl-1,3-dioxolan-2-yl radicals with a primary bromo ester have been estimated to be 8 x 10(3) M(-1) s(-1) and 6 x 10(3) M(-1) s(-1), respectively, at 30 degrees C in acetonitrile. The electrochemical oxidation potentials of a number of electron-rich radicals derived from hydrogen atom abstraction from alcohols and dioxolanes, determined using photomodulation voltammetry, provide an assessment of the thermochemisty of the putative outer sphere electron-transfer reaction between the radical and the alpha-bromo ester (the value for 1,3-dioxolane has been redetermined and corrects an erroneous value previously published). From these data, it is shown that the order of reactivity of the organic reducing agents follows the same trend as the oxidation potentials of the corresponding radicals. Rate constants for the outer sphere electron-transfer reduction of the bromo esters by electrochemically generated radical anions were used to establish a Marcus-type relationship between the rate constants and the standard potential of the reducing agent. Comparison of these rate constants with those for the reactions of the electron-rich radicals suggest that the reactions of the methanol; and ethanol-derived radicals do not proceed via outer sphere electron transfer as had been previously suggested but have significant bonding (i.e., atom transfer) character at the transition state. Electron transfer in the reactions of the 2-propanol- and 2-methyl-1,3-dioxolane-derived radicals cannot be ruled out. Nevertheless, the order of reactivity of the organic reducing agents follows the same trend as the oxidation potentials of the corresponding radicals suggesting that these potentials can be used as a predictive tool for the design of new reagents.

  DOI：

  10.1021/jo00095a050
• 作为产物：
  描述：

  2-溴-2-甲基丙酸 、 苯乙醇 在 N,N'-羰基二咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 生成 phenethyl 2-bromo-2-methylpropanoate
  参考文献：
  名称：

  Structure–LCST relationships for end-functionalized water-soluble polymers: an “accelerated” approach to phase behaviour studies

  摘要：

  开发了一种新颖的“高通量”技术，用于测定水溶性聚（2-（二甲基氨基）乙基甲基丙烯酸酯）的LCST，这项技术能够识别端基组成微妙变化对其水相行为的影响。

  DOI：

  10.1039/b702067h

文献信息

• Ruthenium(II)-carboxylate-catalyzed C4/C6–H dual alkylations of indoles
  作者：Isaac Choi、Valentin Müller、Lutz Ackermann

  DOI：10.1016/j.tetlet.2021.153064

  日期：2021.5

  C4/C6–H double alkylations of indoles accomplished by arene-ligand-free ruthenium(II)-carboxylate catalysis. Base-assisted C2–H ruthenation enabled the C4/C6–H dialkylations with ample substrate scope. The robust C4/C6–H alkylations were demonstrated by gram-scale syntheses and late-stage diversifications. Mechanistic studies unraveled the unique features of ruthenium(II)-catalyzed C4/C6–H indole functionalizations

  对特定CH键的位置选择功能化的需求很高。特别是，超越传统C2和C3流形的选择性极具挑战性。在这里，我们公开了通过无芳烃配体的钌（II）-羧酸盐催化完成的吲哚的位点选择性C4 / C6-H双烷基化反应。碱辅助的C2-H钌化使C4 / C6-H二烷基化反应具有足够的底物范围。克级合成和后期分散证明了鲁棒的C4 / C6-H烷基化。机理研究揭示了钌（II）催化的C4 / C6-H吲哚官能化的独特特征。
• Carbon-Centered Radical Addition to OC of Amides or Esters as a Route to CO Bond Formations
  作者：Dong Liu、Shan Tang、Hong Yi、Chao Liu、Xiaotian Qi、Yu Lan、Aiwen Lei

  DOI：10.1002/chem.201404607

  日期：2014.11.17

  typical applied unsaturated substrates include alkenes, alkynes and imines. Carbonyl is perhaps the most common unsaturated group in nature. This work demonstrates a novel CO bond formation through carbon‐centered radical addition to the carbonyl oxygen of amide or ester, in which amide and ester groups are easily activated through the radical process. EPR spectroscopy and radical clock experiments

  在各种类型的自由基反应中，将碳自由基加至不饱和键是构建新化学键的有力工具，其中典型的不饱和底物包括烯烃，炔烃和亚胺。羰基也许是自然界中最常见的不饱和基团。这项工作证明了通过将以碳为中心的自由基加到酰胺或酯的羰基氧上形成一种新颖的CO键，其中酰胺和酯基很容易通过自由基过程被活化。EPR光谱学和自由基钟实验支持这种转化的自由基过程，而密度泛函理论（DFT）计算则支持将以碳为中心的自由基加到酰胺或酯的羰基氧中的可能性。
• Organic Reducing Agents: Some Radical Chain Reactions of Ketyl and 1,3-Dioxolanyl Radicals with Activated Bromides
  作者：Francesca Fontana、Ralph J. Kolt、Youqin Huang、Danial D. M. Wayner

  DOI：10.1021/jo00095a050

  日期：1994.8

  The radical chain reduction of primary and secondary alpha-bromo esters by 2-propanol and 2-methyldioxolane has been shown to be a kinetically viable process with average chain lengths of >10 at temperatures between 30 and 60 degrees C. For electron-deficient bromides, these simple organic reagents may effectively replace the more commonly used (and more expensive) organosilicon or tin hydides. Some mechanistic insights have been obtained from a combination of kinetic and thermodynamic measurements. The rate constants for the reaction of the 2-hydroxy-2-propyl and the 2-methyl-1,3-dioxolan-2-yl radicals with a primary bromo ester have been estimated to be 8 x 10(3) M(-1) s(-1) and 6 x 10(3) M(-1) s(-1), respectively, at 30 degrees C in acetonitrile. The electrochemical oxidation potentials of a number of electron-rich radicals derived from hydrogen atom abstraction from alcohols and dioxolanes, determined using photomodulation voltammetry, provide an assessment of the thermochemisty of the putative outer sphere electron-transfer reaction between the radical and the alpha-bromo ester (the value for 1,3-dioxolane has been redetermined and corrects an erroneous value previously published). From these data, it is shown that the order of reactivity of the organic reducing agents follows the same trend as the oxidation potentials of the corresponding radicals. Rate constants for the outer sphere electron-transfer reduction of the bromo esters by electrochemically generated radical anions were used to establish a Marcus-type relationship between the rate constants and the standard potential of the reducing agent. Comparison of these rate constants with those for the reactions of the electron-rich radicals suggest that the reactions of the methanol; and ethanol-derived radicals do not proceed via outer sphere electron transfer as had been previously suggested but have significant bonding (i.e., atom transfer) character at the transition state. Electron transfer in the reactions of the 2-propanol- and 2-methyl-1,3-dioxolane-derived radicals cannot be ruled out. Nevertheless, the order of reactivity of the organic reducing agents follows the same trend as the oxidation potentials of the corresponding radicals suggesting that these potentials can be used as a predictive tool for the design of new reagents.
• Structure–LCST relationships for end-functionalized water-soluble polymers: an “accelerated” approach to phase behaviour studies
  作者：Satyasankar Jana、Steven P. Rannard、Andrew I. Cooper

  DOI：10.1039/b702067h

  日期：——

  A novel “high throughput” technique for LCST measurement was developed which is able to identify the effect of subtle changes in end group composition on the aqueous phase behaviour of water-soluble poly(2-(dimethylamino)ethyl methacrylate).

  开发了一种新颖的“高通量”技术，用于测定水溶性聚（2-（二甲基氨基）乙基甲基丙烯酸酯）的LCST，这项技术能够识别端基组成微妙变化对其水相行为的影响。
• Organic reducing agents. Reduction of electron deficient bromides by 1,2,2,6,6-pentamethylpiperidine (PMP)/mercaptoethanol
  作者：Maryam Amoli、Mark S. Workentin、Danial D.M. Wayner

  DOI：10.1016/0040-4039(95)00697-b

  日期：1995.6

  1,2,2,6,6-pentamethylpiperidine (PMP) is shown to be an effective reducing agent for the radical chain conversion of primary bromoesters to the corresponding esters. The problem of inefficient reduction of tertiary bromoesters in these reactions has been overcome by the addition of an alkyl thiol which mediates the hydrogen atom transfer between the two hindered alkyl centers.