2,2-Dimethyl-1,1-dideuterohex-5-en-1-ol | 172035-76-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2,2-Dimethyl-1,1-dideuterohex-5-en-1-ol
• 英文别名: 2,2-Dimethyl-1,1-dideuteriohex-5-en-1-ol；1,1-Dideuterio-2,2-dimethylhex-5-en-1-ol
• CAS: 172035-76-6
• 化学式: C₈H₁₆O
• 分子量: 130.199
• InChiKey: WIYYDFSDWKBPIX-RJSZUWSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-1,1-dideuterohex-5-en-1-ol 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 48.0h， 生成 2-Deuterio-1,1-dimethyl-3-prop-2-enylcyclopropane
  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：

  ethyl 2,2-dimethylhex-5-enoate 在 lithium aluminium deuteride 作用下， 生成 2,2-Dimethyl-1,1-dideuterohex-5-en-1-ol
  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

• 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.
• Competing radical, carbanion, and carbene pathways in the reactions of hindered primary alkyl halides with lithium dialkylamides
  作者：E. C. Ashby、B. Park、G. S. Patil、K. Gadru、R. Gurumurthy

  DOI：10.1021/jo00054a028

  日期：1993.1

  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.
• 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.