4-methylenecyclohexene | 13407-18-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4-methylenecyclohexene
• 英文别名: 4-Methylencyclohexen；1-Methylen-cyclohexen-(3)；Cyclohexene, 4-methylene-；4-methylidenecyclohexene
• CAS: 13407-18-6
• 化学式: C₇H₁₀
• 分子量: 94.1564
• InChiKey: FASOVRLJMZNZJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 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

• 作为产物：
  描述：

  cyclohex-3-en-1-ylmethyl 4-methylbenzenesulfonate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium bromide 作用下， 以 丙酮 为溶剂， 生成 4-methylenecyclohexene
  参考文献：
  名称：

  Smithson, Tracy L.; Ibrahim, Nan; Wieser, Hal, Canadian Journal of Chemistry, 1983, vol. 61, p. 442 - 453

  摘要：

  DOI：

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。
• Umsetzungen des Cyclohex-3-en-carbaldehyd-p-toluolsulfonylhydrazons
  作者：M. Rey、R. Begrich、W. Kirmse、Andr� S. Dreiding

  DOI：10.1002/hlca.19680510502

  日期：1968.7.10

  The vacuum thermolysis (80–90°) of the sodium salt of cyclohex-3-ene-carbaldehyde p-toluenesulfonylhydrazone (1) in silicone oil gave diazomethyl-cyclohex-3-ene (2). Pyrolytic and photolytic decomposition of this diazo compound 2 lead to methylenecyclohex-3-ene (5) and bicyclo [4.1.0]hept-2-ene (6) (about 3:1), while the CuCl catalyzed cleavage yielded only 5. The postulated carbene mechanism should

  环己-3-烯甲醛的钠盐的真空热解（80-90°）p -toluenesulfonylhydrazone（1在硅油），得到重氮甲基-环己-3-烯（2）。该重氮化合物2的热解和光解分解导致亚甲基环己-3-烯（5）和双环[4.1.0]庚-2-烯（6）（约3：1），而CuCl催化的裂解仅产生5。假定的卡宾机理也应在二甘醇二甲醚中1的钠盐的非质子传递直接分解条件下应用，其中除小分子外还形成亚甲基环己-3-烯和双环[4.1.0]庚-2-烯（约3：1） 1-甲基环己-1，3-二烯（9）和双环[4.1.0]庚-3-烯（8）。在质子条件下（在乙二醇中），亚甲基环己-3-烯，1-甲基环己-1、3-二烯和1-甲基环己-1、4-二烯（14）以1∶1∶1的比例产生。
• The transition metal complex promoted isomerization of trans-bicyclo[4.1.0]hept-3-ene to cis-bicyclo[4.1.0]hept-3-ene
  作者：Paul G. Gassman、Steven M. Bonser

  DOI：10.1016/s0040-4039(00)86005-0

  日期：1983.1

  An unprecedented isomerization of a trans-1,2-disubstituted cyclopropane to a cis-1,2-disubstituted cyclopropane has been achieved with both rhodium(I) and platinum(II) catalysts.

  用铑（I）和铂（II）催化剂都已经实现了反式1,2-二取代的环丙烷前所未有的异构化为顺式1,2-二取代的环丙烷。
• Molecules with twist bent bonds. The synthesis, properties, and reactions of trans-bicyclo[4.1.0]hept-3-ene and certain methylated derivatives
  作者：Paul G. Gassman、Steven M. Bonser、Kata Mlinaric-Majerski

  DOI：10.1021/ja00189a046

  日期：1989.3
• Zefirov, N. S.; Kozhushkov, S. I.; Kuznetsova, T. S., Journal of Organic Chemistry USSR (English Translation), 1987, vol. 23, # 10, p. 1863 - 1873
  作者：Zefirov, N. S.、Kozhushkov, S. I.、Kuznetsova, T. S.、Sosonkin, I. M.、Domarev,A. M.、et al

  DOI：——

  日期：——