1-溴-6-甲基环己烯 | 40648-09-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 1-溴-6-甲基环己烯
• 英文名称: 1-bromo-6-methylcyclohexene
• 英文别名: 2-bromo-3-methylcyclohexene；1-bromo-6-methylcyclohex-1-ene；1-Brom-6-methylcyclohexen
• CAS: 40648-09-7
• 化学式: C₇H₁₁Br
• 分子量: 175.068
• InChiKey: JNJOTSRJOBHFBW-UHFFFAOYSA-N

物化性质

• 沸点：
  177.7±19.0 °C(Predicted)
• 密度：
  1.325±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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-溴-6-甲基环己烯 生成 1-碘-6-甲基环己烯
  参考文献：
  名称：

  1-卤代环己烯和甲基取代的1-卤代环己烯与叔丁醇钾的反应

  摘要：

  1-卤代环己烯和1-卤代-4-甲基环己烯与叔丁醇钾（t-BuOK）在二甲亚砜和四氢呋喃中的反应已通过三种竞争的脱卤化氢机理发生。它们是：工作在C脱卤化氢1 C 6键，得到cyclohexyne; 工作在C脱卤化氢1 C 6键合得到1，2-环己二烯：和质子重排成相应的3-卤代环己烯，然后β-消除成1，3-环己二烯。高度应变的环己炔和1,2-环己二烯中间体与t-BuOK反应生成1-叔丁氧基环己烯，在DMSO中的产率为5–20％，在THF中的产率为60％。与取代反应竞争的是1,2-环己二烯二聚为三环[6.4.0.0 2,7 ] -dodeca - 2,12 -diene，以及1,2-和1的1,2-和1,4-环加成，3-环己二烯。

  DOI：

  10.1016/0040-4020(72)88141-9
• 作为产物：
  描述：

  (6-甲基环己烯-1-基)三氟甲磺酸酯 在 三(乙酰丙酮酸)钌(III) 、 1,10-菲罗啉 、 乙基溴化镁 、 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以91%的产率得到1-溴-6-甲基环己烯
  参考文献：
  名称：

  Ruthenium-catalyzed transformation of alkenyl triflates to alkenyl halides

  摘要：

  在钌催化剂的存在下，烯基三氟甲磺酸酯通过与锂卤化物（1.2当量）的处理，被发现可以简单地转化为相应的溴化物、氯化物和碘化物。

  DOI：

  10.1039/b907761h

文献信息

• Stereoselective Benzannulations and Cyclohexadienone Annulations of Fischer Carbene Complexes in the Synthesis of Decala-2,4-dien-1-ones and in the Synthesis of Tetralin Chromium Tricarbonyl Complexes
  作者：Richard P. Hsung、William D. Wulff、Cynthia A. Challener

  DOI：10.1055/s-1996-4292

  日期：1996.6

  The first general study is reported on the stereoselectivity of the benzannulation reaction involving diastereoselection at the planar center of chirality of the newly formed arene ring complexed to chromium that is induced from a chiral carbon center on the carbene complex. The stereochemistry of a number of 5- and 8-substituted tetralin chromium tricarbonyl complexes, which are produced from the benzannulations of cyclohexenyl carbene complexes with chiral centers at the 3- and 6-position, is determined. These results are compared with the stereochemistry of the formation of 5,9- and 8,9-disubstituted decala-2,4-dien-1-ones produced from the reactions of the same carbene complexes bearing an additional substituent in the 2-position of the cyclohexenyl ring. The benzannulation reaction is most selective with 3-substituted cyclohexenyl carbene complexes giving predominately the anti-isomer of the 8-substituted tetralin chromium tricarbonyl complexes. In contrast, the cyclohexadienone annulation is most selective with 6-substituted cyclohexenyl carbene complexes giving predominantly the trans-isomer of the 5,9-disubstituted decala-2,4-dien-1-ones. A mechanistic accounting of the stereochemical results is proposed which is predicated on three assumptions: 1) that the η 1,η 3-vinyl carbene complexed intermediate is in equilibrium, 2) vinyl ketene complex formation is irreversible and occurs with a carbon monoxide migration that is in concert with coordination of the double bond of the cyclohexene ring, and 3) the electrocyclic ring closure of the vinyl ketene complex is stereospecific.

  首次报道了关于苯并化反应立体选择性的综合研究，该反应涉及在新形成的手性芳环平面中心处的立体选择性，该芳环与铬络合，其手性源自卡宾络合物的手性碳中心。确定了从3-和6-位具有手性的环己烯基卡宾络合物苯并化反应生成的若干5-和8-取代的四氢萘铬三羰基络合物的立体化学。这些结果与从相同卡宾络合物（环己烯环的2-位具有额外取代基）反应生成的5,9-和8,9-二取代的癸-2,4-二烯-1-酮的立体化学形成进行了比较。苯并化反应在3-取代的环己烯基卡宾络合物中显示出最高的立体选择性，主要生成8-取代的四氢萘铬三羰基络合物的反式异构体。相比之下，环己二烯酮并环反应在6-取代的环己烯基卡宾络合物中最具选择性，主要生成5,9-二取代的癸-2,4-二烯-1-酮的顺式异构体。提出了一个基于三个假设的机理性解释来解释立体化学结果：1) η1, η3-乙烯基卡宾络合物中间体处于平衡状态，2) 乙烯基烯酮络合物形成是不可逆的，并且伴随着一氧化碳迁移，这与环己烯环双键的配位同时发生，3) 乙烯基烯酮络合物的电环闭环反应是立体专一性的。
• Copper‐Catalyzed C−P Cross‐Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with <i>in</i>   <i>situ</i> Halogen Exchange
  作者：Paweł Woźnicki、Marek Stankevič

  DOI：10.1002/ejoc.202100456

  日期：2021.6.25

  A protocol for copper-catalyzed halogen exchange/C−P cross-coupling between (cyclo)alkenyl/aryl bromides and secondary phosphine oxides has been developed. The addition of sodium iodide increases the yield of the cross-coupling by promoting in situ halogen exchange of organic bromides to the corresponding iodides.

  已经开发了用于（环）烯基/芳基溴化物和二级氧化膦之间的铜催化卤素交换/CP 交叉偶联的协议。碘化钠的添加通过促进有机溴化物与相应碘化物的原位卤素交换来增加交叉偶联的产率。
• A Mild Synthesis of Vinyl Halides and <i>gem</i>-Dihalides Using Triphenyl Phosphite−Halogen-Based Reagents
  作者：Alberto Spaggiari、Daniele Vaccari、Paolo Davoli、Giovanni Torre、Fabio Prati

  DOI：10.1021/jo061346g

  日期：2007.3.1

  A new application of (PhO)(3)P-halogen-based reagents to the synthesis of vinyl halides and gem-dihalides is described. Vinyl halides were prepared in good to excellent yields from enolizable ketones, whereas aldehydes afforded the corresponding gem-dihalides. The halogenation proceeded smoothly under mild conditions.
• A regioselective entry to vinyl lithiums from unsymmetrical ketones via enol triflates
  作者：William D. Wulff、Glen A. Peterson、William E. Bauta、Kin-Shing Chan、Katherine L. Faron、Scott R. Gilbertson、Ralph W. Kaesler、Dominic C. Yang、Christopher K. Murray

  DOI：10.1021/jo00352a039

  日期：1986.1
• Catalytic Formal Homo-Nazarov Cyclization
  作者：Filippo De Simone、Julien Andrès、Riccardo Torosantucci、Jérôme Waser

  DOI：10.1021/ol802970g

  日期：2009.2.19

  The first catalytic method for the cyclization of vinyl-cyclopropyl ketones (formal homo-Nazarov reaction) is reported. Starting from activated cyclopropanes, heterocyclic, and carbocyclic compounds were obtained under mild conditions using Bronsted acid catalysts. Preliminary investigation of the reaction mechanism indicated a stepwise process.