2-(tert-butoxycarbonyl)propan-2-yl radical | 85598-45-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(tert-butoxycarbonyl)propan-2-yl radical
• 英文别名: tert-butyl isobutyrate-2-yl；2-(tert-butoxy)-1,1-dimethyl-2-oxoethyl
• CAS: 85598-45-4
• 化学式: C₈H₁₅O₂
• 分子量: 143.206
• InChiKey: IZIYQBLAZONYCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  2,2,4,5,5-pentamethyl-2,5-dihydro-1H-imidazol-1-yloxy 、 2-(tert-butoxycarbonyl)propan-2-yl radical 以 苯 为溶剂， 生成 2-Methyl-2-(2,2,4,5,5-pentamethyl-2,5-dihydro-imidazol-1-yloxy)-propionic acid tert-butyl ester
  参考文献：
  名称：

  2,5-二氢-1 H-咪唑基一氧化氮在自由基聚合中的预期作用

  摘要：

  应用了许多光谱方法来获得模拟2,5-二氢-1 H-咪唑1-氧化物介导的丙烯酸酯活性聚合反应的动力学参数。通过EPR光谱法在不同温度下测量基于五种氮氧化物的烷氧基胺的均解速率常数。重组率常数k c借助于激光闪光光解法测量相应的烷基和氮氧化物之间的比值。时间分辨的化学诱导的动态核极化（TR-CIDNP）实验表明歧化在重组反应中的贡献可忽略不计。另外，在NMR探针中烷氧基胺的热分解显示出没有从相应的烷氧基胺分子内消除羟胺。动力学参数分析表明，2,5-二氢-1 H-咪唑1-氧化物型自由基是丙烯酸和甲基丙烯酸酯活性聚合的有前途的介质。

  DOI：

  10.1002/hlca.200690218
• 作为产物：
  描述：

  叔-丁基异丁酸酯 在 二叔丁基过氧化物 作用下， 生成 2-(tert-butoxycarbonyl)propan-2-yl radical
  参考文献：
  名称：

  摘要：

  Absolute rate constants and some of their Arrhenius parameters were obtained by time-resolved electron spin resonance (ESR) spectroscopy for the addition of the 2-(alkoxycarbonyl)propan-2-yl and 3,3,3-trifluoroacetonyl (= 3,3,3-trifluoro-2-oxopropyl) radicals to a variety of mono- and 1,1-disubstituted alkenes. Their analysis shows that the addition of 2-(alkoxycarbonyl)propan-2-yl is mainly governed by the exothermicity of the reaction with slight modifications by nucleophilic and electrophilic effects giving rise to an overall ambiphilic behavior. In contrast, large electrophilic polar effects dominate the addition of the 3,3,3-trifluoroacetonyl (= 3,3,3-frifluoro-2-oxopropan-2-yl) radical, as it is expected from its large electron affinity. For both radicals, the activation energies are well-predicted by analytic equations for the enthalpic and polar terms. A comparison of the rate data of 2-(alkoxycarbonyl)propan-2-yl with the homo- and copolymerization rate constants of the propagating radical of methyl methacrylate shows that the additions of these structurally related low- and high-molecular-weight radicals to alkenes are governed by very similar effects.

  DOI：

  10.1002/(sici)1522-2675(20000315)83:3<658::aid-hlca658>3.0.co;2-z

文献信息

• Absolute Rate Constants for the Addition of the 1-(tert-Butoxy)carbonylethyl Radical to Alkenes in Solution
  作者：Bernhard Knühl、Sylvain Marque、Hanns Fischer

  DOI：10.1002/1522-2675(20010815)84:8<2290::aid-hlca2290>3.0.co;2-o

  日期：2001.8.15

  log (A/M−1 s−1)=7.9±0.5. The rate constants of the secondary 1-[(tert-butoxy)carbonyl]ethyl radical are close to the geometric mean of those of the related primary [(tert-butoxy)carbonyl]methyl and the tertiary 2-(methoxycarbonyl)propan-2-yl radicals. The activation energies for addition of these three carboxy-substituted alkyl radicals are mainly governed by the addition enthalpy but are also substantially

  报告了将 1-[(叔丁氧基)羰基]乙基自由基 (MeC.HCO2Me3) 加成到乙腈中的几种单或 1,1-二取代烯烃的绝对速率常数和它们的一些 Arrhenius 参数，按时间计算-分辨电子自旋共振光谱。在 295 K 时，速率常数范围从 470 M-1 s-1（丁-1-烯）到 2.4⋅105 M-1 s-1（1,1-二苯基乙烯），实验活化能范围从 26.8 kJ/ mol（丁-1-烯）至14.7 kJ/mol（苯乙烯），频率因子服从平均log（A/M-1 s-1）=7.9±0.5。仲 1-[(叔丁氧基)羰基]乙基自由基的速率常数接近相关伯 [(叔丁氧基)羰基]甲基和叔 2-(甲氧基羰基)丙烷-2 的几何平均值-yl 自由基。加成这三个羧基取代的烷基自由基的活化能主要受加成焓控制，但也因两亲极性效应而显着降低。结果支持先前推导的预测分析，并讨论了与丙烯酸酯聚合速率常数的关系。
• A novel method of alkoxyamine homolysis activation <i>via</i> photochemical rearrangement
  作者：Sergey Cherkasov、Dmitriy Parkhomenko、Denis Morozov、Elena Bagryanskaya

  DOI：10.1039/d3cp05815h

  日期：——

  We proposed the nitrone–oxaziridine rearrangement as a novel method for photochemical activation for the homolysis of alkoxyamine in nitroxide-mediated polymerization. The photoisomerization of the aldo-/ketonitrone-group into the oxaziridine one in 2,5-dihydroimidazole 3-oxide-based alkoxyamines was studied; the products of photolysis have been identified, and quantum yields were measured. Conversion

  我们提出硝酮-氧氮丙啶重排作为一种新的光化学活化方法，用于硝基氧介导的聚合中烷氧基胺的均裂。研究了2,5-二氢咪唑3-氧化物烷氧基胺中醛基/酮硝酮基团光异构化为氧氮丙啶基团的情况；光解产物已被鉴定，并测量了量子产率。发现硝酮基团转化为氧氮杂环丙烷基团可将烷氧基胺均裂的活化能降低约 10%。 10 kJ mol -1 。
• ——
  作者：Torsten Zytowski、Bernhard Knühl、Hanns Fischer

  DOI：10.1002/(sici)1522-2675(20000315)83:3<658::aid-hlca658>3.0.co;2-z

  日期：2000.3.15

  Absolute rate constants and some of their Arrhenius parameters were obtained by time-resolved electron spin resonance (ESR) spectroscopy for the addition of the 2-(alkoxycarbonyl)propan-2-yl and 3,3,3-trifluoroacetonyl (= 3,3,3-trifluoro-2-oxopropyl) radicals to a variety of mono- and 1,1-disubstituted alkenes. Their analysis shows that the addition of 2-(alkoxycarbonyl)propan-2-yl is mainly governed by the exothermicity of the reaction with slight modifications by nucleophilic and electrophilic effects giving rise to an overall ambiphilic behavior. In contrast, large electrophilic polar effects dominate the addition of the 3,3,3-trifluoroacetonyl (= 3,3,3-frifluoro-2-oxopropan-2-yl) radical, as it is expected from its large electron affinity. For both radicals, the activation energies are well-predicted by analytic equations for the enthalpic and polar terms. A comparison of the rate data of 2-(alkoxycarbonyl)propan-2-yl with the homo- and copolymerization rate constants of the propagating radical of methyl methacrylate shows that the additions of these structurally related low- and high-molecular-weight radicals to alkenes are governed by very similar effects.
• 2,5-Dihydro-1H-imidazole-Based Nitroxides as Prospective Mediators in Living Radical Polymerization
  作者：Dmitry Zubenko、Igor Kirilyuk、Galina Roshchupkina、Irina Zhurko、Vladimir Reznikov、Sylvain R. A. Marque、Elena Bagryanskaya

  DOI：10.1002/hlca.200690218

  日期：2006.10

  parameters of reactions modelling the 2,5-dihydro-1H-imidazole 1-oxide mediated living polymerization of acrylates. The homolysis rate constants of alkoxyamines based on five nitroxides were measured by EPR spectroscopy at different temperatures. The recombination rate constants kc between the corresponding alkyl radicals and the nitroxides were measured by means of laser flash photolysis. The time-resolved

  应用了许多光谱方法来获得模拟2,5-二氢-1 H-咪唑1-氧化物介导的丙烯酸酯活性聚合反应的动力学参数。通过EPR光谱法在不同温度下测量基于五种氮氧化物的烷氧基胺的均解速率常数。重组率常数k c借助于激光闪光光解法测量相应的烷基和氮氧化物之间的比值。时间分辨的化学诱导的动态核极化（TR-CIDNP）实验表明歧化在重组反应中的贡献可忽略不计。另外，在NMR探针中烷氧基胺的热分解显示出没有从相应的烷氧基胺分子内消除羟胺。动力学参数分析表明，2,5-二氢-1 H-咪唑1-氧化物型自由基是丙烯酸和甲基丙烯酸酯活性聚合的有前途的介质。