1-Methallyl radical | 903583-91-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-Methallyl radical
• 英文别名: Butenyl；(E)-but-1->3-enyl；but-1->3-enyl；2-butenyl radical；but-2-enyl radical
• CAS: 903583-91-5
• 化学式: C₄H₇
• 分子量: 55.0996
• InChiKey: CRPTXKKKIGGDBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  4
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-Methallyl radical 生成 1,2-丁二烯
  参考文献：
  名称：

  Homolytic Bond Dissociation Enthalpies of the C−H Bonds Adjacent to Radical Centers

  摘要：

  Homolytic bond dissociation enthalpies (BDEs) at 0 and 298 K of the C-H bonds adjacent to various radical centers have been obtained from ab initio CBS-4 (complete basis set) model calculations and experimental data available in the literature. The BDEs of the C-H bonds adjacent to the radical centers derived from 11 saturated hydrocarbons were found to be 33.5 +/- 3 kcal/mol at 298 K. The BDEs of the C-H bonds adjacent to nine allylic and benzylic radical centers were found to be 48 +/- 3 kcal/mol at 298 K, but the benzylic C-H BDE of the PhCH2CH2. radical was found to be only 29.7 and 30.5 kcal/mol at 0 and 298 K, respectively. The BDEs of the vinylic C-H bonds adjacent to four vinylic radical centers were found to be 35.5 +/- 3.5 kcal/mol at 298 K. The BDEs of the vinylic C-H bonds adjacent to three allylic radical centers were found to be 56.5 +/- 3 kcal/mol at 298 K. These results suggest that the radical centers weaken the adjacent C-H bond strengths by about 50-70 kcal/mol. The calculated BDEs agree within +/-2 kcal/mol with most of the available experimental results. Isomerization enthalpies of butenes and pentenes have been obtained. Substituent effects on BDEs have also been examined.

  DOI：

  10.1021/jo971768d
• 作为产物：
  描述：

  丁烯 在 氧气 、 bismuth(III) oxide 作用下， 450.0 ℃ 、133.32 Pa 条件下， 生成 1-Methallyl radical
  参考文献：
  名称：

  1-氧化丁烯和异丁烯在氧化铋上氧化过程中气相甲基烯丙基自由基的形成

  摘要：

  DOI：

  10.1021/j100297a024

文献信息

• Decomposition of 4,4-dimethylpent-1-ene in the presence of oxygen between 400 and 500 °C: oxidation chemistry of allyl radicals
  作者：Zulfiqar H. Lodhi、Raymond W. Walker

  DOI：10.1039/ft9918700681

  日期：——

  as a source of allyl radicals over the temperature range 400–500 °C. The reaction has been studied in both KCl-coated (peroxy species destroyed at the surface) and aged boric-acid-coated vessels (peroxy species preserved), and the basic mechanism shown to be: DMP → t-butyl + [graphic omitted] (1), t-butyl + O2→ i-C4H8+ HO2(2). Previous studies have shown that 99% of the t-butyl radicals undergo reaction

  在O 2存在下4,4-二甲基戊-1-烯（DMP）的分解已被用作在400–500°C温度范围内的烯丙基自由基的来源。已在涂有KCl的表面（过氧化物破坏了表面）和老化的硼酸涂过的容器（保留了过氧化物）中研究了该反应，其基本机理为：DMP→叔丁基+ [省略了图示] （1），叔丁基+ O 2 →iC 4 H 8 + HO 2（2）。先前的研究表明，99％的叔丁基自由基会发生反应（2），因此该体系是烯丙基和HO 2自由基的极好来源。
• Dissociation of 3-methylpenta-1, 4-diene and the resonance energy of the pentadienyl radical
  作者：Antony B. Trenwith

  DOI：10.1039/f19827803131

  日期：——

  = 4.18 J) and this leads to D[H—CH(C2H3)2]= 76.4 kcal mol–1, which by comparison with the value of 95.0 for the secondary C—H bond dissociation energy in alkanes leads to a figure of 18.6 ± 1.5 kcal mol–1 for the resonance stabilisation energy of the pentadienyl radical.

  通过测量在653–716 K范围内的温度和15至200 Torr的压力下3-甲基戊-1、4-二烯热解过程中甲烷的初始形成速率，已证明甲烷是由均相形成的，一阶过程。对其他热解产物的检查表明，形成伯甲烷的最合理方式是[省略图示]，然后是[省略图示]。反应（i）的速率表达式为log（k i / s –1）=（15.36±0.1）–（65040±300）/ θ，其中θ = 2.303 R T / cal mol –1（1 cal = 4.18 J）这导致D [H-CH（C 2 H 3）2 ] = 76.4 kcal mol –1，与烷烃中二级CH键离解能的95.0相比，戊二烯基的共振稳定能为18.6±1.5 kcal mol –1。
• Roth, Wolfgang R.; Staemmler, Volker; Neumann, Martin, Liebigs Annalen, 1995, # 6, p. 1061 - 1118
  作者：Roth, Wolfgang R.、Staemmler, Volker、Neumann, Martin、Schmuck, Carsten

  DOI：——

  日期：——
• Scherzer, K.; Lohse, K.; Loeser, U., Zeitschrift fur Physikalische Chemie (Leipzig), 1983, vol. 264, # 2, p. 196 - 204
  作者：Scherzer, K.、Lohse, K.、Loeser, U.

  DOI：——

  日期：——
• Cuthbertson, Matthew J.; Rizzardo, Ezio; Solomon, David H., Australian Journal of Chemistry, 1983, vol. 36, # 10, p. 1957 - 1973
  作者：Cuthbertson, Matthew J.、Rizzardo, Ezio、Solomon, David H.

  DOI：——

  日期：——