methyl-2,4,6-tribromophenylnitroxyl | 67384-84-3

• 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: methyl-2,4,6-tribromophenylnitroxyl
• CAS: 67384-84-3
• 化学式: C₇H₅Br₃NO
• 分子量: 358.835
• InChiKey: ZOBVIJXRGOIOBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  4.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1,3,5-三溴-2-亚硝基-苯 、 碘甲烷 在 羰基镁 作用下， 以 二氯甲烷 为溶剂， 生成 methyl-2,4,6-tribromophenylnitroxyl
  参考文献：
  名称：

  Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings

  摘要：

  用可见光光解二锰十羰基化合物 [Mn2(CO)10] 会产生锰五羰基自由基 [·Mn(CO)5]，该自由基与卤代烃反应生成以碳为中心的自由基。与烯丙基或苯甲基卤代物，或具有较弱碳-卤素键的多卤代前驱体，发生高效的卤素原子抽取反应。立体相互作用也很重要，初级卤代物通常比次级或三级卤代物与 ·Mn(CO)5 反应更快。以碳为中心的自由基可以进行高效的二聚反应，或者在存在接受体双键的情况下，环化形成5员环。末端烯烃的环化反应会导致生成初级自由基，随后这些自由基可以通过碘或溴原子转移反应，或者在加入异丙醇的情况下进行氢原子转移反应。当环化反应在TEMPO存在的情况下进行时，还可以形成羟胺。这些高产率的环化-捕捉反应在温和的反应条件下发起，锰卤化物副产物 [类型为 XMn(CO)5] 可以通过简单的DBU后处理程序轻松与产物分离。

  DOI：

  10.1039/b000835o

文献信息

• Tanaseichuk, B. S.; Belozerov, A. I.; Sanaeva, E. P., Journal of Organic Chemistry USSR (English Translation), 1983, vol. 19, p. 494 - 497
  作者：Tanaseichuk, B. S.、Belozerov, A. I.、Sanaeva, E. P.、Butin, K. P.

  DOI：——

  日期：——
• Oxiranylcarbinyl Radicals from Allyloxyl Radical Cyclization:  Characterization and Kinetic Information via ESR Spectroscopy¹
  作者：Loris Grossi、Samantha Strazzari、Bruce C. Gilbert、Adrian C. Whitwood

  DOI：10.1021/jo9812678

  日期：1998.11.1

  An ESR spin-trapping technique has been used for the detection of oxiranylcarbinyl radicals as discrete reaction intermediates, formed via cyclization of allyloxyl radicals. The latter were obtained by photolysis of the corresponding nitrites, which were generated directly via an exchange reaction between the appropriate allylic alcohols and tert-butyl nitrite (which also acts as the spin-trap). Experiments have also been conducted with the spin-trap 2,4,6-tribromonitrosobenzene, which has allowed a study to be made of the competition between ring closure and p-scission of a variety of allyloxyl species.
• Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings
  作者：Bruce C. Gilbert、Wilhelm Kalz、Chris I. Lindsay、P. Terry McGrail、Andrew F. Parsons、David T. E. Whittaker

  DOI：10.1039/b000835o

  日期：——

  Photolysis of dimanganese decacarbonyl [Mn2(CO)10] using visible light produces the manganese pentacarbonyl radical [·Mn(CO)5] which reacts with organohalides to form carbon-centred radicals. Efficient halogen-atom abstraction occurs with allylic or benzylic halides or polyhalogenated precursors bearing a weak carbon–halogen bond. Steric interactions are also important and primary halides generally react much faster with ·Mn(CO)5 than secondary or tertiary halides. The carbon-centred radicals can undergo efficient dimerisation or, in the presence of an acceptor double bond, cyclisation to form 5-membered rings. Cyclisation of terminal alkenes leads to primary radicals, which can then react by iodine- or bromine-atom transfer or, on addition of propan-2-ol, hydrogen-atom transfer. Hydroxylamines can also be formed when cyclisation reactions are carried out in the presence of TEMPO. These high-yielding cyclisation–trapping reactions are initiated under mild reaction conditions and the manganese halide by-products [of type XMn(CO)5] can be easily separated from products by a simple DBU work-up procedure.

  用可见光光解二锰十羰基化合物 [Mn2(CO)10] 会产生锰五羰基自由基 [·Mn(CO)5]，该自由基与卤代烃反应生成以碳为中心的自由基。与烯丙基或苯甲基卤代物，或具有较弱碳-卤素键的多卤代前驱体，发生高效的卤素原子抽取反应。立体相互作用也很重要，初级卤代物通常比次级或三级卤代物与 ·Mn(CO)5 反应更快。以碳为中心的自由基可以进行高效的二聚反应，或者在存在接受体双键的情况下，环化形成5员环。末端烯烃的环化反应会导致生成初级自由基，随后这些自由基可以通过碘或溴原子转移反应，或者在加入异丙醇的情况下进行氢原子转移反应。当环化反应在TEMPO存在的情况下进行时，还可以形成羟胺。这些高产率的环化-捕捉反应在温和的反应条件下发起，锰卤化物副产物 [类型为 XMn(CO)5] 可以通过简单的DBU后处理程序轻松与产物分离。