1,1-二甲基-5-己烯基氯 | 34986-80-6

• 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: 1,1-二甲基-5-己烯基氯
• 英文名称: 1,1-dimethyl-5-hexenyl chloride
• 英文别名: 1-chloro-1,1-dimethyl-5-hexene；6-chloro-6-methyl-1-heptene；6-chloro-6-methylhept-1-ene
• CAS: 34986-80-6
• 化学式: C₈H₁₅Cl
• 分子量: 146.66
• InChiKey: JAYGDRUWKMRMNV-UHFFFAOYSA-N

物化性质

• 沸点：
  56-60 °C(Press: 22 Torr)
• 密度：
  0.877±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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：

  1,1-二甲基-5-己烯基氯 以5%的产率得到
  参考文献：
  名称：

  Walborsky H. M., Hamdouchi C., J. Org. Chem, 58 (1993) N 5, S 1187-1193

  摘要：

  DOI：
• 作为产物：
  描述：

  5-溴-1-戊烯 在 氯化亚砜 、 magnesium 作用下， 以 吡啶 为溶剂， 生成 1,1-二甲基-5-己烯基氯
  参考文献：
  名称：

  使用9,9-二正丁基-9-硼环[3.3.1]壬酸锂将叔烷基，苄基和烯丙基卤选择性还原为烃

  摘要：

  标题9-borabicyclo [3.3.1]壬烷（9-BBN）配合物（1）可以选择性地除去叔烷基，苄基和烯丙基卤，从而以优异的收率得到相应的烃，而不会伴随着对仲，伯和芳基的攻击衍生品。的还原顺式-和反式- 4 -吨-丁基- 1 -甲基环己基氯化物（2）与1给出4 -吨-丁基- 1 - methylcyclohexanes（3），在环己烷的配置的局部反转，而在苯给出热力学稳定的反式- 3为主。1,1-二甲基-5-己烯基氯化物的反应（4）和1,7,7- -三甲基二环[2.2.1]庚- 2 -基磺酰氯（8）配有1继续进行到碳离子中间特性的重排。要求1所述的还原-乙基- 1 -甲基戊基氯与1如下二阶速率方程。

  DOI：

  10.1016/s0040-4020(01)97982-7

文献信息

• Selective reduction of tertiary alkyl, benzyl, and allyl halides to hydrocarbons using lithium 9,9-di-n-butyl-9-borabicyclo[3.3.1]nonanate
  作者：Hiroo Toi、Yoshinori Yamamoto、Akio Sonoda、Shun-Ichi Murahashi

  DOI：10.1016/s0040-4020(01)97982-7

  日期：——

  The title 9-borabicyclo[3.3.1]nonane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives. The reduction of cis- and trans - 4 - t - butyl - 1 - methylcyclohexyl chlorides (2) with 1 gives 4 - t - butyl - 1 - methylcyclohexanes

  标题9-borabicyclo [3.3.1]壬烷（9-BBN）配合物（1）可以选择性地除去叔烷基，苄基和烯丙基卤，从而以优异的收率得到相应的烃，而不会伴随着对仲，伯和芳基的攻击衍生品。的还原顺式-和反式- 4 -吨-丁基- 1 -甲基环己基氯化物（2）与1给出4 -吨-丁基- 1 - methylcyclohexanes（3），在环己烷的配置的局部反转，而在苯给出热力学稳定的反式- 3为主。1,1-二甲基-5-己烯基氯化物的反应（4）和1,7,7- -三甲基二环[2.2.1]庚- 2 -基磺酰氯（8）配有1继续进行到碳离子中间特性的重排。要求1所述的还原-乙基- 1 -甲基戊基氯与1如下二阶速率方程。
• DTBB-catalysed lithiation of 6-chloro-1-hexene and related systems: synthetically useful temperature-dependent behaviour
  作者：Miguel Yus、Rosa Ortiz、Fernando F Huerta

  DOI：10.1016/s0040-4039(02)00415-x

  日期：2002.4

  The reaction of 6-chloro-1-hexene 1 with lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 5% molar) in THF at −78°C gives the corresponding organolithium intermediate 2, which by reaction with different electrophiles [ButCHO, PhCHO, Et2CO, (CH2)5CO, PhCOMe] affords, after hydrolysis with water, the expected products 3. The same reaction performed at −30°C gives cyclopentyl

  6-氯-1-己烯的反应1与锂粉末和4,4'-二-催化量叔在THF -butylbiphenyl（DTBB，5％摩尔）在-78℃下，得到相应的有机锂中间体2，通过与不同的亲电子[卜反应吨CHO，苯甲醛，等2 CO，（CH 2）5 CO，PhCOMe]得到，用水水解后，预期的产品3。在-30℃下进行的相同反应可能通过将开链中间体2环化而得到环状有机锂化合物4，从而得到环戊基衍生物5。对于三阶导数6，由于相应的叔有机锂中间体7的极大的不稳定性，在-30℃下仅环状化合物10可以被分离，该叔有机锂中间体7甚至在-78℃下也经历了质子提取。在-78℃或-30℃下从烯丙基2-氯-苯基醚11中仅分离出相应的环状化合物14。在所有情况下，都假定发生了比自由基更好的碳负离子环化。
• Organolithiums by reductive lithiation: the catalytic aromatic method versus the use of preformed aromatic radical-anions. Naphthalene can behave as a catalyst or an inhibitor
  作者：Ao Yang、Heather Butela、Kai Deng、Mary Dosch Doubleday、Theodore Cohen

  DOI：10.1016/j.tet.2006.03.056

  日期：2006.7

  using aromatic radical-anions for reductive lithiation, the replacement of a C–heteroatom bond with a C–Li bond, have been compared with regard to yield and the mildness of reaction conditions required. It was found that the use of preformed radical-anions generally resulted in higher yields and milder reaction conditions than the ‘catalytic’ method in which catalytic amounts of the aromatic compound

  在收率和所需反应条件的温和性方面，已经比较了两种常见的模式，即使用芳族自由基阴离子进行还原锂化，以及将C-杂原子键替换为C-Li键。已经发现，与“催化”方法相比，使用预制的自由基阴离子通常可产生更高的产率和更温和的反应条件，在“催化”方法中，催化量的芳族化合物被使用，自由基阴离子被生成并就地使用。一个明显的例外是N-苯基氮丙啶，但事实表明，在这种情况下，芳族化合物萘实际上是抑制剂而不是催化剂。给出了合理的机械解释。
• 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
• Reactions of Saturated and Unsaturated Tertiary Alkyl Halides and Saturated Secondary Alkyl Iodides with Lithium Aluminum Deuteride. Convincing Evidence for a Single-Electron-Transfer Pathway
  作者：E. C. Ashby、Catherine O. Welder

  DOI：10.1021/jo9807058

  日期：1998.10.1

  Reactions of saturated secondary and tertiary alkyl halides with LiAlH4 (LAH) and LiAlD4 (LAD) have been carried out, and convincing evidence for a single-electron-transfer (SET) pathway has been obtained. Reactions involving saturated alkyl halides with LAD provide a model system in which a halogen-atom radical chain process is not possible, and therefore, the observation of large quantities tin some cases >90%) of protium in the reduction product provides strong evidence for a radical intermediate and a SET pathway. Specifically, the reaction of 2-iodooctane (10) with LAD produced octane with a deuterium content as low as 21%. Also, the reaction of the tertiary halide 2-iodo-2-methylheptane (15) with LAD produced 2-methylheptane (16) with a deuterium content as low as 8%. The effect of stoichiometry, halogen type, and reaction vessel surface on these reactions was studied. Reaction of the unsaturated tertiary halide 6-iodo-6-methyl-1-heptene (25) with LAD was also studied and was found to proceed predominantly by a SET process involving a halogen-atom radical chain process. The possibility of a carbocation intermediate in all of these reactions is discussed.