2,2-Dimethylbicyclo<3.1.0>hexane | 128885-83-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: 2,2-Dimethylbicyclo<3.1.0>hexane
• 英文别名: 2,2-Dimethylbicyclo[3.1.0]hexane
• CAS: 128885-83-6
• 化学式: C₈H₁₄
• 分子量: 110.199
• InChiKey: TXCZYRHNBULEQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  112.7±7.0 °C(Predicted)
• 密度：
  0.875±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• 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 吡啶 、 碘 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 24.0h， 生成 2,2-Dimethylbicyclo<3.1.0>hexane
  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

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.
• Mechanism of Reaction of Geminal Dihalides with Lithium Aluminum Hydride. Evidence for Single Electron Transfer as the Major Reaction Pathway
  作者：E. C. Ashby、Abhay K. Deshpande

  DOI：10.1021/jo00093a011

  日期：1994.7

  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.
• 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.
• Mechanism of Reaction of Geminal Dihalides with Lithium Naphthalenide (LiNp.bul.-): Evidence for an Electron Transfer Mechanism. Similarities to the Mechanism of Reaction of Geminal Dihalides with Certain Nucleophiles and Other One-Electron Donors
  作者：E. C. Ashby、Abhay K. Deshpande

  DOI：10.1021/jo00119a034

  日期：1995.7

  The reactions of the sterically hindered geminal dihalides 6,6-dichloro-5,5-dimethyl-1-hexene (1a) and 6,6-diiodo-5,5-dimethyl-1-hexene (1b) with lithium naphthalenide (LiNp.-) in THF were investigated in an attempt to compare the results of reactions involving a known one-electron donor (LiN.- -) with those involving nucleophiles believed to be one-electron donors. On the basis of radical-trapping studies, deuterium tracer studies, and product studies using cyclizable radical probes, it can be concluded that the reactions studied are very similar to those reported by us earlier involving magnesium metal, LiAlH4, and other nucleophiles. In addition to radical-derived products, the reaction of 1a with LiNp.- afforded hydrocarbons, in high yields, that were derived from a carbene intermediate. On the other hand, 1b, on reaction with LiNp.-, did not yield any carbene-derived hydrocarbons. These results show that the formation of a carbene intermediate, derived from a radical, depends on the nature of the halogen present. It was also found that naphthalene can behave as a hydrogen atom donor toward a radical in the presence of known hydrogen atom donors, such as THF.