6-碘-5,5-二甲基己-1-烯 | 77400-57-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 中文名称: 6-碘-5,5-二甲基己-1-烯
• 英文名称: 6-Iodo-5,5-dimethyl-1-hexene
• 英文别名: 2,2-dimethyl-1-iodo-5-hexene；5,5-dimethyl-6-iodo-1-hexene；6-Iodo-5,5-dimethylhex-1-ene
• CAS: 77400-57-8
• 化学式: C₈H₁₅I
• 分子量: 238.112
• InChiKey: RQVHXKDIEMPANY-UHFFFAOYSA-N

物化性质

• 沸点：
  200.3±19.0 °C(Predicted)
• 密度：
  1.364±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  6-碘-5,5-二甲基己-1-烯 在 六苯基二锡 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 63.0h， 生成 1,1,3-三甲基环戊烷
  参考文献：
  名称：

  Competing radical, carbanion, and carbene pathways in the reactions of hindered primary alkyl halides with lithium dialkylamides

  摘要：

  A variety of methods were utilized to study the mechanism of reaction of 6-iodo-5,5-dimethyl-1-hexene and its bromo, chloro, and tosylate derivatives with LDA and several other lithium dialkylamides. In the reaction of 6-iodo-5,5-dimethyl-1-hexene with LDA in THF, radical, carbanion, and carbene pathways occurred simultaneously. However, when the corresponding bromide was allowed to react with LDA, the radical pathway was minor and when the corresponding chloride or tosylate was allowed to react with LDA, no evidence for radical products was observed. This is the first time that competing radical, carbanion, and carbene pathways have been detected in the reaction of a primary alkyl halide with any nucleophile.

  DOI：

  10.1021/jo00054a028
• 作为产物：
  描述：

  5-氯-5-甲基己-1-烯 在 吡啶 、 lithium aluminium tetrahydride 、 碘 、 magnesium 、 三苯基膦 作用下， 以 乙醚 、 苯 为溶剂， 反应 24.0h， 生成 6-碘-5,5-二甲基己-1-烯
  参考文献：
  名称：

  Occurrence of electron transfer in the reduction of organic halides by lithium aluminum hydride and aluminum hydride

  摘要：

  DOI：

  10.1021/jo00193a019
• 作为试剂：
  描述：

  苯丙酮 、 二环己基膦 在 6-碘-5,5-二甲基己-1-烯 、 lithium diisopropyl amide 作用下， 生成 2-(dicyclohexylphosphino)-1-phenyl-1-propanone
  参考文献：
  名称：

  Single electron transfer in the reaction of enolates with alkyl halides

  摘要：

  DOI：

  10.1021/jo00218a007

文献信息

• Electron transfer in the reduction of primary halides by metal hydrides
  作者：Eugene C. Ashby、Robert N. DePriest、Anil B. Goel

  DOI：10.1016/s0040-4039(01)90433-2

  日期：1981.1

  hydrides with 1-halo-5-hexenes and with 1-halo-2,2-dlmethyl-5-hexenes produce both straight chain and cyclized reduction products. The formation of cyclic hydrocarbons clearly indicates the presence of radical intermediates during the course of these reactions.

  各种主族金属氢化物与1-卤代5-己烯和1-卤代2,2-二甲基5-己烯的反应可生成直链和环化还原产物。环状烃的形成清楚地表明在这些反应过程中存在自由基中间体。
• Evidence for single electron transfer in the reaction of alkoxides with alkyl halides
  作者：E.C. Ashby、Dong-Hak Bae、Won-Suh Park、Robert N. Depriest、Wei-Yang Su

  DOI：10.1016/s0040-4039(01)81536-7

  日期：1984.1

  Evidence for a radical process in the reaction of lithium alkoxides with alkyl iodides was obtained by the observation of cyclization of appropriate radical probes, by the trapping of radicals, and by EPR spectroscopic observations relating to the one electron donor properties of alkoxides.

  通过观察合适的自由基探针的环化，自由基的捕获以及与醇盐的单电子给体性质有关的EPR光谱观察，获得了锂醇盐与烷基碘化物反应中自由基过程的证据。
• Concerning the preparation of geminal digrignard reagents.
  作者：Fabio Doctorovich、Abhay K. Deshpande、E.C. Ashby

  DOI：10.1016/s0040-4020(01)90449-1

  日期：1994.1

  Mechanistic studies of the reactions of geminal dihalides with magnesium and sodium have been carried out and the possibility of preparing geminal DiGrignard Reagents for use in situ has been explored.

  已经进行了双金属卤化物与镁和钠反应的机理研究，并探索了制备双基吉尼亚试剂原位使用的可能性。
• Transition-Metal-Free Radical C(sp³)–C(sp²) and C(sp³)–C(sp³) Coupling Enabled by 2-Azaallyls as Super-Electron-Donors and Coupling-Partners
  作者：Minyan Li、Simon Berritt、Lucas Matuszewski、Guogang Deng、Ana Pascual-Escudero、Grace B. Panetti、Michal Poznik、Xiaodong Yang、Jason J. Chruma、Patrick J. Walsh

  DOI：10.1021/jacs.7b09394

  日期：2017.11.15

  and alkyl radicals. The SET process converts the 2-azaallyl anions into persistent 2-azaallyl radicals, which capture the aryl and alkyl radicals to form C-C bonds. The radical coupling of aryl and alkyl radicals with 2-azaallyl radicals makes possible the synthesis of functionalized amine derivatives without the use of exogenous radical initiators or transition metal catalysts. Radical clock studies

  过去十年见证了自由基生成策略及其在CC成键反应中的应用的快速发展。大多数这些过程需要引发剂、过渡金属催化剂或有机金属试剂。在此，我们报告了一种简单的有机系统（2-氮杂烯丙基阴离子）的发现，该系统可以在无过渡金属的条件下实现自由基偶联反应。N-苄基酮亚胺的去质子化产生半稳定的 2-氮杂烯丙基阴离子，其充当“超级电子给体”(SED)，并将芳基碘和烷基卤还原为芳基和烷基。SET 过程将 2-氮杂烯丙基阴离子转化为持久的 2-氮杂烯丙基自由基，捕获芳基和烷基自由基形成 CC 键。芳基和烷基与2-氮杂烯丙基的自由基偶联使得在不使用外源自由基引发剂或过渡金属催化剂的情况下合成官能化胺衍生物成为可能。自由基时钟研究和 2-氮杂烯丙基阴离子偶联研究为这种独特的反应性提供了机制见解。
• Evidence for single electron transfer in the reaction of a lithium enolate with a primary alkyl iodide
  作者：E.C. Ashby、J.N. Argyropoulos

  DOI：10.1016/s0040-4039(01)91134-7

  日期：1984.1

  Evidence for a radical process in the reaction of the lithium enolate of propiophenone with a primary alkyl iodide was obtained by the observation of cyclization of an appropriate radical probe, by the trapping of the radical intermediate and by the comparison of the relative rates of reactions of the probe alkyl iodide with the corresponding bromide and tosylate.

  通过观察合适的自由基探针的环化，捕获自由基中间体并比较三乙胺的相对反应速率，获得了苯乙酮的烯醇锂与伯烷基碘的反应中发生自由基过程的证据。探针烷基碘与相应的溴化物和甲苯磺酸酯。