1,2-bis(3,3-dimethylcyclopentyl)ethane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 英文名称: 1,2-bis(3,3-dimethylcyclopentyl)ethane
• 化学式: C₁₆H₃₀
• 分子量: 222.414
• InChiKey: MVWBXGVBNKWOFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.42
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  6,6-二碘-5,5-二甲基-1-己烯 在 naphthalen-1-yl-lithium 作用下， 以 四氢呋喃 为溶剂， 以15%的产率得到1,1,3-三甲基环戊烷
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00119a034

文献信息

• A Photochemical Probe for Single Electron Transfer in Nucleophilic Aliphatic Substitution: Evidence for Geminate Radical Coupling in the Solvent Cage
  作者：Laren M. Tolbert、Xiao-Jing Sun、E. C. Ashby

  DOI：10.1021/ja00115a001

  日期：1995.3

  A major effort to establish single electron transfer (SET) as an important pathway in nucleophilic aliphatic subsitution reactions has involved the use of cyclizable probes, e.g., 6-iodo-5,5-dimethyl-1-hexene. In order to examine the partition between cyclization and direct radical-radical recombination, we have investigated the ground-state and excited-state chemistry of the 9-phenylfluorenyl anion (9PF(-)) with neopentyl-type iodides. It has been shown that 9PF(-) does not react with Me(3)CCH(2)I, but it does undergo efficient reaction upon irradiation (Phi = 1.0) to yield nucleophilic aliphatic substitution products, With the sterically analogous cyclizable probe 6-iodo-5,5-dimethyl-1-hexene, no ground-state reaction is observed, However, both cyclized and uncyclized products of substitution, 9PFR(c) and 9PFR(u), are produced upon irradiation. Thus photoproducts clearly involving electron-transfer-induced radical intermediates can result without acommpanying free-radical cyclization. These results suggest that, although the observation of cyclized products in the reaction of a cyclizable radical probe with a nucleophile is evidence of a radical intermediate, the absence of such cyclized products does not require the absence of radical intermediates.
• 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.