3-甲亚基环戊烯 | 930-26-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: 3-甲亚基环戊烯
• 英文名称: 3-methylene-1-cyclopentene
• 英文别名: 3-methylenecyclopent-1-ene；3-Methylen-1-cyclopenten；3-methylene-cyclopentene；3-methylenecyclopentene；3-Methylen-cyclopenten；3-methylidenecyclopentene
• CAS: 930-26-7
• 化学式: C₆H₈
• 分子量: 80.1295
• InChiKey: YWQLRBQGXHZJCF-UHFFFAOYSA-N

物化性质

• 沸点：
  79.5 °C(Press: 750 Torr)
• 密度：
  0.82±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902199090

反应信息

• 作为反应物：
  描述：

  1,1-二氯乙烷 、 3-甲亚基环戊烯 在 正丁基锂 作用下， 以 正己烷 、 正戊烷 为溶剂， 反应 0.5h， 生成 anti-1-Chlor-1-methylspiro<2,4>hept-4-en
  参考文献：
  名称：

  Roth, Wolfgang R.; Winzer, Markus; Korell, Michael, Liebigs Annalen, 1995, # 5, p. 897 - 920

  摘要：

  DOI：
• 作为产物：
  描述：

  月桂烯 在 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以86%的产率得到3-甲亚基环戊烯
  参考文献：
  名称：

  钌催化的β-月桂烯及其衍生物与丙烯酸甲酯的交叉易位

  摘要：

  在第一步Ru催化剂Neolyst M2的存在下，β-月桂烯与丙烯酸甲酯的反应生成3-亚甲基环戊-1-烯。在第二步中，生成的亚甲基单元与丙烯酸甲酯反应，通过交叉复分解反应得到相应的不饱和环状酯。在优化的反应条件下（80°C，Neolyst M2，16当量的丙烯酸甲酯），β-月桂烯，月桂烯醇，乙酸烯丙烯基酯和β-月桂烯的衍生物反应生成官能化的无环酯。

  DOI：

  10.1002/cctc.201500993

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。
• 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。
• One-pot Formation of Functionalized Cyclopentenone Derivatives via Retro-Benzilic Acid Rearrangement of the Proto-Photocycloadducts of Methyl 2,4-Dioxopentanoate to Methylenecycloalkanes
  作者：Toshihide Hatsui、Shin-ya Ikeda、Hitoshi Takeshita

  DOI：10.1246/cl.1992.1891

  日期：1992.10

  The proto-Photocycloadducts of methyl 2,4-dioxopentanoate to several methylenecycloalkanes and -alkenes spontaneously caused retro-benzilic acid rearrangement, exclusively. The reaction proceeded quite cleanly, and a simple work-up without chromatographic separation allowed to isolate the products directly in very good material balance.

  2,4- 二氧代戊酸甲酯与几种亚甲基环烷和-烯的原光环加成物会自发地发生逆二苯乙二酸重排反应。反应进行得非常干净利落，无需色谱分离的简单工作就能直接分离出产物，且物料平衡非常好。
• Photoisomerization of Bicyclopropylidene and 1,2-Dimethylenecyclobutane in Rare-Gas Matrices: Towards the IR-Spectroscopic Identification of Tetramethyleneethane (2,3-Dimethylenebutane-1,4-diyl)
  作者：Günther Maier、Stefan Senger

  DOI：10.1002/(sici)1099-0690(199906)1999:6<1291::aid-ejoc1291>3.0.co;2-m

  日期：1999.6

  2-dimethylenecyclobutane (7) is exposed to the light of a KrF excimer laser (λ = 248 nm), an isomeric species is produced, showing an absorption at 793.1 cm–1 (argon matrix) or 791.2 cm–1 (xenon matrix) in the IR spectrum. The back reaction can be induced with light of λ = 254 nm. This photochemical interconversion, together with the comparison between the experimental and calculated band positions, supports

  双环亚丙基 (3) 和 1,2-二亚甲基环丁烷 (7) 已在稀有气体基质中进行辐照。如果 1,2-二亚甲基环丁烷 (7) 暴露在 KrF 准分子激光 (λ = 248 nm) 的光线下，则会产生同分异构体，在 793.1 cm-1（氩基质）或 791.2 cm-1（红外光谱中的氙气矩阵）。可以用 λ = 254 nm 的光诱导反向反应。这种光化学互变，以及实验和计算带位置之间的比较，支持将 790 cm-1 附近的 IR 吸收分配给四亚甲基甲烷 (5)。
• Central and lateral bicyclo[1.1.0]butane bond cleavage with subsequent Wagner-Meerwein rearrangements or carbene formation in the 185-nm photolysis of tricyclo[3.1.0.02,6]hexane, tricyclo[4.1.0.02,7]heptane, and tricyclo[5.1.0.02,8]octane
  作者：Waldemar Adam、Christine Alt、Max Braun、Uwe Denninger、Gerald Zang

  DOI：10.1021/ja00012a027

  日期：1991.6

  From the deuterium-labeling studies, it is concluded that, in the case of the tricyclooctane, the central bicyclobutane bonds cleave in the primary step to give radical cationic or zwitterionic species that undergo a Wagner-Meerwein rearrangement. Also, in the case of tricycloheptane, this is the dominating pathway but lateral C-C bond cleavage with subsequent carbene and product formation takes place

  从氘标记研究得出的结论是，在三环辛烷的情况下，中心双环丁烷键在初级步骤中裂解，产生自由基阳离子或两性离子物质，这些物质经历 Wagner-Meerwein 重排。此外，在三环庚烷的情况下，这是主要途径，但横向 CC 键断裂以及随后的卡宾和产物形成发生在大约 10 倍的范围内。15%。对于三环己烷，该途径成为主要途径。我们的光机械观察与早期关于双环丁烷 HOMO 的相对能量排序的理论研究非常一致，因为产品组成反映了这一点

表征谱图