cis-2-Iodo-1,1,3-trimethylcyclopentane

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 英文名称: cis-2-Iodo-1,1,3-trimethylcyclopentane
• 英文别名: (2R,3R)-2-iodo-1,1,3-trimethylcyclopentane
• 化学式: C₈H₁₅I
• 分子量: 238.112
• InChiKey: DEHARFISXSFFTL-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2,2-二甲基-5-己烯-1-醇 在 lithium aluminium tetrahydride 、 碘 、 一水合肼 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 cis-2-Iodo-1,1,3-trimethylcyclopentane
  参考文献：
  名称：

  Mechanism of Reaction of Geminal Dihalides with Lithium Aluminum Hydride. Evidence for Single Electron Transfer as the Major Reaction Pathway

  摘要：

  The reactions of a sterically hindered geminal dichloride 4a and the corresponding diiodide 4b with LiAlH4 (LAH) were found to involve an electron-transfer mechanism. Whereas the monochloro analog of 4a (8) is inert toward LAH, 4a was more reactive. Observation of radical-derived products in the reaction of 4a with LAH indicates that the presence of two chlorine atoms on the same carbon atom results in a favorable reduction potential for 4a, as compared to 8. These results show that LAH can function as a one-electron donor toward geminal dichlorides. It was found that the diiodo analog 4b is more reactive toward LAH than 4a due to the inherent favorable reduction potentials of alkyl iodides compared to chlorides. The reactivity of 4b toward LAH was also found to be greater than that of the monoiodo analog (Ib) in keeping with the more favorable reduction potential of the diiodide (4b) compared to the monoiodide (Ib). The rates of cyclization of the corresponding haloalkyl radicals generated from 4a and 4b were also determined and were found to be 7.4 x 10(5)/s for the chloroalkyl and 5.5 x 10(5)/s for the iodoalkyl radical at 25 degrees C. The formation of small amounts of the carbene-derived product, 5, in the reactions of both 4a and 4b with LAH appeared to be preceded by a radical intermediate.

  DOI：

  10.1021/jo00093a011

文献信息

• 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。
• Electron Transfer in the Reactions of Geminal Dihalides with Ph2P-. Evidence for the Formation of a Carbene Intermediate from a Radical Precursor
  作者：E. C. Ashby、Abhay K. Deshpande

  DOI：10.1021/jo00127a014

  日期：1995.11

  The reactions of two sterically hindered geminal dihalides, 6,6-dichloro-5,5-dimethyl-1-hexene (5a) and 6,6-diiodo-5,5-dimethyl-1-hexene (5b), with Ph(2)P(-) have been found to involve a single electron transfer (SET) pathway. Since the corresponding monochloride reacts with Ph(2)P(-) by a S(N)2 pathway, it is clear that adding a second chlorine atom on a carbon atom produces a more favorable reduction potential resulting in a change in mechanism from S(N)2 to SET. Evidence is also presented that shows that the geminal dihalides produce carbene-derived products and that the carbene was derived from a haloalkyl radical precursor.
• A Mechanistic Study of the Reactions of Geminal Dihalides with LDA. Evidence for a Single Electron Transfer Pathway in the Reaction of Geminal Diiodides
  作者：E. C. Ashby、Abhay K. Deshpande、Girish S. Patil

  DOI：10.1021/jo00108a032

  日期：1995.2

  While the reaction of the geminal dichloride, 6,6-dichloro-5,5-dimethyl-1-hexene (8a) with LDA afforded only one product, wh:ich was derived from a chlorocarbene intermediate, the reaction of the corresponding geminal diiodide 8b resulted in the formation of a number of products that were accounted for by a single electron transfer (SET) initiated reaction. This difference in the reactivity patterns of the two substrates shows that the reduction potential of 8b is more favorable than that of 8a and that LDA can function as a one-electron donor. Additionally, 8a was more reactive toward LDA than the already studied monochloro substrate (1a) with the same carbon skeleton. This enhanced reactivity is attributed to the increased acidity of the hydrogen atom attached to the carbon bearing the two chlorine atoms in 8a. The observation that 8b reacted with LDA at a faster rate, not only relative to 8a but also to the corresponding monoiodo compound 1c, indicates that the reduction potential of 8b is more favorable than that of 1c for SET reduction by LDA. Based on the nature of the products formed in the reactions of 8a and 8b with LDA, evidence is presented that supports the notion that, in addition to funtioning as a strong base, LDA can also function as a one-electron donor toward the geminal diiodide 8b.