3-methylene-cyclohexene | 1888-90-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 3-methylene-cyclohexene
• 英文别名: 3-Methylenecyclohexene；3-methylidenecyclohexene
• CAS: 1888-90-0
• 化学式: C₇H₁₀
• 分子量: 94.1564
• InChiKey: XVKFDCVTYBMNRZ-UHFFFAOYSA-N

物化性质

• 沸点：
  109 °C
• 密度：
  0.82±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  3-methylene-cyclohexene 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (E,Z)-3-<<(bromomethyl)sulfonyl>methylene>cyclohexene
  参考文献：
  名称：

  .alpha.-Haloalkanesulfonyl bromides in organic synthesis. 5. Versatile reagents for the synthesis of conjugated polyenes, enones, and 1,3-oxathiole 1,1-dioxides

  摘要：

  DOI：

  10.1021/ja00275a051
• 作为产物：
  描述：

  2-methylenecyclohexyl acetate 生成 3-methylene-cyclohexene
  参考文献：
  名称：

  Cyclic Dienes. XVII. 3-Methylenecyclohexene^1,2

  摘要：

  DOI：

  10.1021/ja01593a042

文献信息

• Flash vacuum pyrolysis over magnesium. Part 1. Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides
  作者：R. Alan Aitken、Philip K. G. Hodgson、John J. Morrison、Adebayo O. Oyewale

  DOI：10.1039/b108663d

  日期：2002.1.23

  Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E,E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.

  在玻璃棉上覆盖一层新升华的镁,进行闪式真空热解,能有效促使苄基卤化物耦合生成相应的联苄。当有邻位卤素取代基存在时,进一步脱卤生成部分二氢蒽和蒽。卤甲基萘和二苯基甲烷也能高效耦合,而三苯基氯甲烷则生成4,4′-双(二苯甲基)联苯。用α,α′-二卤代邻二甲苯可以获得较高产率的苯并环丁烯,而异构的α,α′-二卤代对二甲苯,通过形成的对二甲苯的聚合,可以得到一系列高热稳定性的聚合物。其他卤代烃苯大体上会脱卤化氢,某些情况下能产生环化反应。同样可以观察到,苯基卤代烷烃脱去羰基生成苯乙炔以及其他产物。简单的烷基卤化物则高效地脱去HCl或HBr生成烯烃。脂肪族二卤化物也会发生这一反应生成二烯,但不发生环化反应生成环烷烃,或在某些情况下发生氢原子转移的脱卤反应生成烯烃。5-溴戊-1-烯的产物符合自由基途径的预期,但6-溴己-1-烯并不符合。2,2-二氯丙烷和1,1-二氯丙烷能脱去HCl,但1,1-二氯丁烷、戊烷和己烷则能部分水解,随后脱去HCl,生成E,E-, E,Z-和Z,Z-异构体二烷-1-烯基醚,并且得到了这些物质的13C NMR全归属数据。6-氯己-1-炔和7-氯庚-1-炔能发生环化反应生成亚甲基环烷烃和环炔烃。本文还考察了1,2-二溴环己烷和1,2-二氯环辛烷在上述条件下的行为。本文给出了众多种证据,表明这些反应过程不涉及气相自由基的形成,而是表面吸附的金属有机物种。
• Thermal Pericyclic Tandem Reactions
  作者：Henning Hopf、Joachim Wolff

  DOI：10.1002/1099-0690(200111)2001:21<4009::aid-ejoc4009>3.0.co;2-4

  日期：2001.11

  Gas phase thermal isomerizations of twelve acetylenic systems, all of which can in principle undergo two successive pericyclic steps, are described. The substrates, the syntheses and spectroscopic properties of which are presented, are formal derivatives of but-2-yne, with different functional groups in the 1- and the 4-positions. The Cope, Claisen, Claisen ester, retro-ene, 1,5-hydrogen shift, and

  描述了十二个炔属体系的气相热异构化，所有这些体系原则上都可以经历两个连续的周环步骤。底物，其合成和光谱特性，是but-2-yne的形式衍生物，在1-和4-位具有不同的官能团。Cope、Claisen、Claisen 酯、逆烯、1,5-氢转移和 1,5-均氢转移过程被用作构成串联过程的周环步骤。获得的热解产物的组成是在很宽的温度范围内确定的，并讨论了产生热解产物的各个步骤的机制。
• Palladium-Catalyzed Regio- and Enantioselective Fluorination of Acyclic Allylic Halides
  作者：Matthew H. Katcher、Allen Sha、Abigail G. Doyle

  DOI：10.1021/ja206960k

  日期：2011.10.12

  This report describes the Pd(0)-catalyzed fluorination of linear allylic chlorides and bromides, yielding branched allylic fluorides in high selectivity. Many of the significant synthetic limitations previously associated with the preparation of these products are overcome by this catalytic method. We also demonstrate that a chiral bisphosphine-ligated palladium catalyst enables highly enantioselective

  本报告描述了 Pd(0) 催化的线性烯丙基氯化物和溴化物的氟化，以高选择性产生支化的烯丙基氟化物。这种催化方法克服了以前与这些产品的制备相关的许多重要的合成限制。我们还证明了手性双膦连接的钯催化剂能够高度对映选择性地获得一类支链烯丙基氟化物，这些氟化物可以很容易地多样化为有价值的氟化产品。
• Synthetic Photochemistry. LX. One-pot Formation of Spirocyclic 3-Acetyl-2-hydroxy-2-cyclopentenone Derivatives from Methylenecycloalkanes and Methyl 2,4-Dioxopentanoate
  作者：Toshihide Hatsui、Shin-ya Ikeda、Hitoshi Takeshita

  DOI：10.1246/bcsj.66.870

  日期：1993.3

  of proto-photocycloadducts of methyl 2,4-dioxopentanoate to methylenecycloalkanes and -alkenes spontaneously caused retro-benzilic acid rearrangement in high yields. The results are utterly different from those of sterically-crowded acyclic alkenes, with which the rearrangement occurred by thermolysis as a minor process.

  2,4-二氧代戊酸甲酯与亚甲基环烷烃和烯烃的一系列原光环加合物自发地以高产率引起逆苯甲酸重排。结果与空间拥挤的无环烯烃的结果完全不同，后者通过热解作为次要过程发生重排。
• Reaction d'elimination-1,3
  作者：H. Blancou、E. Casadevall

  DOI：10.1016/0040-4020(76)80144-5

  日期：——

  The reaction of cis and rans 2-iodomethyl 1-tosyloxycyclohexanes and 4-enes with nBuLi was studied and found to be stereospecific, the products being respectively bicyclo(4.1.0)hexane (ene) cis and methylene cyclohexane (ène). A parallel is drawn between this reaction and alkaline deshydrohalogenation of cyclic 1,2-halohydrins; a reaction pathway is proposed.

  的反应顺式和失败者2-碘甲基-1- tosyloxycyclohexanes和4 -烯用nBuLi进行了研究并发现是立体有择的，产品分别为双环（4.1.0）己烷（烯）顺式和亚甲基环己烷（烯）。该反应与环状1,2-卤代醇的碱性脱氢卤化反应相似。提出了反应途径。

表征谱图