1-氯-2,2-二甲基-5-己烯 | 76695-77-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 中文名称: 1-氯-2,2-二甲基-5-己烯
• 英文名称: 6-Chloro-5,5-dimethyl-1-hexene
• 英文别名: 1-chloro-2,2-dimethyl-5-hexene；6-Chloro-5,5-dimethylhex-1-ene
• CAS: 76695-77-7
• 化学式: C₈H₁₅Cl
• mdl: MFCD19232258
• 分子量: 146.66
• InChiKey: LHVNNDODVUCCRR-UHFFFAOYSA-N

物化性质

• 沸点：
  168.9±19.0 °C(Predicted)
• 密度：
  0.877±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-氯-2,2-二甲基-5-己烯 在 lithium pyrrolidide 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以5%的产率得到(E)-6-chloro-5,5-dimethylhex-2-ene
  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：

  2,2-二甲基-5-己烯酸 在 四氯化碳 、 lithium aluminium tetrahydride 、 三苯基膦 作用下， 以 乙醚 为溶剂， 反应 72.0h， 生成 1-氯-2,2-二甲基-5-己烯
  参考文献：
  名称：

  Occurrence of electron transfer in the reduction of organic halides by lithium aluminum hydride and aluminum hydride

  摘要：

  DOI：

  10.1021/jo00193a019

文献信息

• Organometallic reaction mechanisms. 17. Nature of alkyl transfer in reactions of Grignard reagents with ketones. Evidence for radical intermediates in the formation of 1,2-addition product involving tertiary and primary Grignard reagents
  作者：E. C. Ashby、Joseph R. Bowers

  DOI：10.1021/ja00399a018

  日期：1981.5
• Investigation of the purity of alkali metal diphenylphosphides and their reactions with organic halides. Evidence for single electron transfer
  作者：E. C. Ashby、R. Gurumurthy、R. W. Ridlehuber

  DOI：10.1021/jo00073a051

  日期：1993.10

  For the first time the purity of lithium, sodium, and potassium diphenylphosphide, prepared by various methods, has been evaluated using P-31 NMR spectroscopy. A method was developed to prepare each of the phosphides in a high state of purity. Highly pure potassium diphenylphosphide was then allowed to react with p-iodotoluene in order to determine the effect of purity on the S(RN)1 nature of this reaction. The results were then compared with literature reports which used less pure KPPh2. The mechanism of reaction of alkyl halides with pure alkali metal diphenylphosphides, using the radical probes 6-halo-5,5-dimethyl-1-hexenes and 1-halo-2,2-dimethylhexanes, was investigated. The results provide the first evidence to support single electron transfer (SET) in the reaction of an alkali metal diphenylphosphide with an alkyl halide. SET was found to be the major reaction pathway in the reaction of hindered alkyl iodides (neopentyl type). On the other hand, SET was found to be a minor pathway in the reaction of the corresponding alkyl bromides and chlorides with PPh2-. There was no evidence found for SET in the reactions of unhindered alkyl halides with PPh2- although SET participation cannot be rigorously excluded.
• 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.
• 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*.