2,2-Dimethylhex-5-ene-1-al hydrazone | 155886-66-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,2-Dimethylhex-5-ene-1-al hydrazone
• 英文别名: 2,2-dimethylhex-5-en-1-al hydrazone
• CAS: 155886-66-1
• 化学式: C₈H₁₆N₂
• 分子量: 140.228
• InChiKey: HNJNAMYITORWDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  10.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  38.38
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,2-Dimethylhex-5-ene-1-al hydrazone 在 lithium aluminium tetrahydride 、 碘 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 21.0h， 生成 1,1,3-三甲基环戊烷
  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
• 作为产物：
  描述：

  2,2-二甲基-5-己烯-1-醇 在 一水合肼 、 pyridinium chlorochromate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 2,2-Dimethylhex-5-ene-1-al hydrazone
  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。
• Mechanism of Reaction of Geminal Dihalides with Magnesium. Evidence for the Formation of Carbenes from Radical Precursors. The Similarity in Reactions of Geminal Dihalides with Magnesium and LiAlH4
  作者：E. C. Ashby、Abhay K. Deshpande、Fabio Doctorovich

  DOI：10.1021/jo00100a024

  日期：1994.10

  Two geminal dihalides, 6,6-dichloro-5,5-dimethyl-1-hexene (2a) and 6,6-diiodo-5,5-dimethyl-1-hexene (2b) were allowed to react with Rieke activated magnesium (Mg*) in THF at 25 degrees C. Both radical and carbene intermediates were identified by product analyses, by radical trapping experiments using DCPH and THF-d(8), and by selective experiments in which isolated intermediates were shown to form the predicted products. Although carbene products predominated over radical products when the dichloride was allowed to react with Mg*, radical products predominated when the diiodide was allowed to react with Mg*. Evidence is presented that indicates that the carbene intermediate arises from a radical precursor. A mechanistic scheme (Scheme 5) is presented that is consistent with all of the observed data. A comparison of the reactions of 2b with Mg* and 2b with LiAlH4 shows that most of the products are common in both reactions thereby providing further evidence for LiAlH4 as a one-electron donor, as is the known behavior of Mg*.