cis-3,6-dibromocyclohexene | 42086-54-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: cis-3,6-dibromocyclohexene
• 英文别名: (3S,6R)-3,6-dibromocyclohexene
• CAS: 42086-54-4
• 化学式: C₆H₈Br₂
• 分子量: 239.938
• InChiKey: ZZLDYZLPDLYQAC-OLQVQODUSA-N

物化性质

• 沸点：
  201.2±40.0 °C(Predicted)
• 密度：
  1.867±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  cis-3,6-dibromocyclohexene 在 lithium chloride 作用下， 以 二甲基亚砜 为溶剂， 生成 cis-Dichloro-3,6-cyclohexen
  参考文献：
  名称：

  Ionic addition of chlorine to conjugated dienes

  摘要：

  DOI：

  10.1021/jo00864a033
• 作为产物：
  描述：

  1,3-环己二烯 在 溴 作用下， 以 正戊烷 为溶剂， 以61%的产率得到cis-3,6-dibromocyclohexene
  参考文献：
  名称：

  Gilchrist, Thomas L.; Wood, Jane E., Journal of the Chemical Society. Perkin transactions I, 1992, # 1, p. 9 - 16

  摘要：

  DOI：

文献信息

• Desymmetrization of <i>meso</i>-Dibromocycloalkenes through Copper(I)-Catalyzed Asymmetric Allylic Substitution with Organolithium Reagents
  作者：Shermin S. Goh、Sureshbabu Guduguntla、Takashi Kikuchi、Martin Lutz、Edwin Otten、Makoto Fujita、Ben L. Feringa

  DOI：10.1021/jacs.8b02992

  日期：2018.6.13

  The highly regio- and enantioselective (up to >99:1 dr, up to 99:1 er) desymmetrization of meso-1,4-dibromocycloalk-2-enes using asymmetric allylic substitution with organolithium reagents to afford enantioenriched bromocycloalkenes (ring size of 5 to 7) has been achieved. The cycloheptene products undergo an unusual ring contraction. The synthetic versatility of this Cu(I)-catalyzed reaction is demonstrated

  高度区域选择性和对映选择性（高达 >99:1 dr，高达 99:1 er）使用有机锂试剂的不对称烯丙基取代对内消旋-1,4-二溴环烷-2-烯进行去对称化，以提供对映体富集的溴环烯烃（环大小为5 至 7) 已实现。环庚烯产物经历不寻常的环收缩。这种 Cu(I) 催化反应的合成多功能性通过环状氨基醇的简洁立体控制制备得到证明，环状氨基醇是天然产物和药物中的特权手性结构，广泛用于合成和催化。
• Stereoselective Halogenations of Alkenes and Alkynes in Ionic Liquids
  作者：Cinzia Chiappe、Dario Capraro、Valeria Conte、Daniela Pieraccini

  DOI：10.1021/ol015631s

  日期：2001.4.1

  [GRAPHICS]Room-temperature ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, and 1-butyl-3-methylimidazolium chloride, are used as "green" recyclable alternative to chlorinated solvents for the stereoselective halogenation of alkenes and alkynes.
• Bromination of Cyclohexa-1,3-diene and (<i>R</i>,<i>S</i>)-Cyclohexa-3,5-diene-1,2-diol
  作者：Xinghua Han、Rajashree N. Khedekar、John Masnovi、Ronald J. Baker

  DOI：10.1021/jo990473s

  日期：1999.7.1

  The configuration of 1,2,3,4-tetrabromocyclohexane (mp 90 degrees C), 5a, has been established as 1,2t,3t,4c by an X-ray crystallographic determination. The structures of two of three dibromocyclohexenes (3a, 3b, and 3c) have been reassigned on the basis of NMR evidence and an X-ray crystallographic determination of the structure of 3b (trans-3,6-dibromocyclohexene). The structures of the two major isomers of 3,4,5,6-tetrabromocyclohexane-1,2-diol obtained by bromination of cis-cyclohexa-3,5-diene-1,2-diol also were established by X-ray crystallographic determinations of their monobenzoate esters. Studies of their formation indicate that the mechanism of bromination of 1,3-cyclohexadiene and cis-cyclohexa-3,5-diene-1,2-diol are similar. Addition of 1 equiv of bromine occurs rapidly by anti 1,a-addition, which is followed by rearrangements to form products of conjugation addition. A second equivalent of bromine adds to afford mostly the 1,2t,3t,4c-tetrabromo compounds at -70 degrees C and, with cyclohexadiene, the 1,2t,3c,4t-tetrabromo compound at higher temperature.
• Radical Bromination of Cyclohexene in CCl4 by Bromine: Addition versus Substitution
  作者：D. W. McMillen、John B. Grutzner

  DOI：10.1021/jo00095a029

  日期：1994.8

  The radical reaction of bromine (10(-2)-10(-5) M)with cyclohexene in CCl4 in the light has been investigated. The reactions have been found to be highly reversible and controlled by both thermodynamics and the availability of Br-2 and HBr as equilibrating agents. The selectivity of substitution over addition is controlled by [Br-2]. Bromine addition to the double bond and allylic substitution occur at comparable rates at room temperature. The limiting substitution/addition ratio was found to be 4.0 +/- 0.2 for [Br-2] less than 10(-3) M. While the beta-bromocyclohexyl radical is generated very rapidly, its steady-state concentration is kept low by its rapid reversion to cyclohexene. Substitution via the allyl radical, while relatively slow, is irreversible and fast enough to maintain the concentration of bromine at sufficiently low level to prevent significant addition. The equilibrium constant for the reaction 1 + Br reversible arrow 2a is estimated to be 500 M(-1), and the rate constant for substitution k(2s) as 2000 M(-1) s(-1). The ratio of removal of hydrogen from cyclohexene, 3-bromocyclohexene, and 3,6-dibromocyclohexene by bromine radical was found to be 2.2:1.0:0.1. The ratio for addition of bromine to the double bond was 5.5:1.0:<0.1. A series of polybromo derivatives have been obtained and characterized by NMR spectroscopy as stable intermediates in the exhaustive bromination of cyclohexene. m-Dibromobenzene is the major aromatic product.
• McMillen D. W., Grutzner John B., J. Org. Chem, 59 (1994) N 16, S 4516-4528
  作者：McMillen D. W., Grutzner John B.

  DOI：——

  日期：——