3-methylene-1,6-heptadiene | 16626-48-5

• 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-1,6-heptadiene
• 英文别名: 3-methylene hepta-1,6-diene；3-methylidenehepta-1,6-diene
• CAS: 16626-48-5
• 化学式: C₈H₁₂
• 分子量: 108.183
• InChiKey: DOCZMKSURIPHOA-UHFFFAOYSA-N

物化性质

• 沸点：
  119.7±10.0 °C(Predicted)
• 密度：
  0.742±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 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-1,6-heptadiene 在 ((η5-Me5C5)2SmH)2 作用下， 以 甲苯 为溶剂， 反应 8.0h， 生成 1,2-dimethylene-3-methylcyclopentane
  参考文献：
  名称：

  高亲电性 d0/fn 金属茂催化亚甲基环烷烃的开环齐格勒聚合。功能化聚烯烃的反应性、范围、反应机理和途径

  摘要：

  一系列锆和镧系金属茂催化剂在应变的外亚甲基环烷烃的区域选择性开环聚合反应中具有活性，以产生外亚甲基官能化聚乙烯。MCB(亚甲基环丁烷)在(1,2-Me2Cp)2ZrMe+MeB(C6F5)3-的催化作用下得到聚合物[CH2CH2CH2C(CH2)]n，MCP(亚甲基环丙烷)得到聚合物[CH2CH2C(CH2)]n在[(Me5Cp)2LuH]2的催化作用下。在 MCP 聚合反应中观察到 [(Me5Cp)2LuH]2 催化剂的可逆失活，这归因于基于 D2O 淬灭实验的 Lu-烯丙基物种的形成。相比之下，催化剂 [(Me5Cp)2SmH]2 和 [(Me5Cp)2LaH]2 以高化学选择性从 MCP 产生二聚体 1,2-二亚甲基-3-甲基环戊烷 (DMP)。

  DOI：

  10.1021/ja960811w
• 作为产物：
  描述：

  5-已烯-2-酮 在 potassium hydrogensulfate 作用下， 生成 3-methylene-1,6-heptadiene
  参考文献：
  名称：

  Photosensitized internal addition of dienes to olefins

  摘要：

  DOI：

  10.1021/ja00995a019

文献信息

• 1,4-cycloheptylene and the related allylic diradicals. Thermal nitrogen extrusion from 6,7-diazabicyclo[3.2.2]Non-6-enes
  作者：Tadao Uyehara、Masayuki Takahashi、Tadahiro Kato

  DOI：10.1016/s0040-4039(00)98443-0

  日期：1985.1

  Thermal nitrogen extrusion of 2-methylene-6,7-diazabicyclo[3.2.2]non-6-enes and 6,7- diazabicyclo[3.2.2]nona-2,6-diene,6 proceeded easily to give closure and cleavage products via the corresponding 5-methylene-1,4-cycloheptylenes and 4-cyclohepten-1,3-ylenes, respectively.

  2-亚甲基-6,7-二氮杂双环[3.2.2] non-6-烯和6,7-二氮杂双环[3.2.2] nona-2,6-二烯，6的热氮挤出很容易进行，从而产生闭合和断裂产物分别通过相应的5-亚甲基-1,4-亚环戊烯和4-环庚基-1,3-亚乙基得到。
• Bicyclo[2.2.1]heptan-1-ylcarbene can ring expand
  作者：Rebecca T. Ruck、Maitland Jones

  DOI：10.1016/s0040-4039(98)00840-5

  日期：1998.6

  Generation of bicyclo[2.2.1]heptan-1-ylcarbene from a hydrocarbon precursor avoids the problems that attend generation from nitrogenous molecules and allows the determination that such carbenes can ring expand to bridgehead alkenes.

  由烃前体产生双环[2.2.1]庚基-1-基卡宾避免了伴随含氮分子产生的问题，并使得可以确定此类碳烯可以环膨胀成桥头烯烃。
• Interaction of Acyclic Tetraenes and Trienes with Transition Metals: Organonickel Compounds
  作者：E. Dreher、B. Gabor、P. W. Jolly、C. Kopiske、C. Krueger、A. Limberg、R. Mynott

  DOI：10.1021/om00004a049

  日期：1995.4

  The tetraene 3,6-dimethylene-1,7-octadiene (DMOD) reacts with zerovalent [NiPR(3)] species to give (eta(2),eta(2)-DMOD)NiPR(3) in which the methylene group of one 1,3-diene fragment and the vinyl group of the second interact with the metal atom. This unsymmetrical complexation of the tetraene has been confirmed by X-ray diffraction for the P(OC6H4-o-Ph)(3)-stabilized derivative (space group P2(1)/c, a = 10.057(1) Angstrom, b = 36.196(1) Angstrom, c = 10.944(1) Angstrom, a = y = 90 degrees, beta = 105.76(1)degrees, Z = 4, R = 0.056, R(W) = 0.071) and is the result of the preferred coordination of a 1,6-heptadiene chain to the metal atom. The NMR spectra indicate that the molecule is fluxional with a pairwise exchange of the methylene groups and of the vinyl groups. The structure of the product formed in the presence of the bidentate ligands (Pr2P)-P-i(CH2)(n)PPr2i (n = 1, 2, 3) is dependent upon the length of the chain bridging the two P-atoms, and compounds have been isolated having the composition (eta(2),eta(2),eta(2),eta(2)-DMOD)Ni-2(Pr-2(i)- PCH2PPr2i), (eta(4),eta(4)-DMOD)[Ni((Pr2PC2H4PPr2i)-P-i)](2), and (eta(2),eta(2)-DMOD)[Ni((Pr2PC3H6PPr)-P-i(2)(i))](2). The molecular structure of the bis(diisopropylphosphino)ethane-containing compound has been established by X-ray diffraction (space group C2/c, a = 17.535(2) Angstrom, b = 24.152(1) Angstrom, c = 11.767(1) Angstrom, a = y = 90 degrees, beta = 120.65(1)degrees, Z = 4, R = 0.034, R(W) = 0.035) and confirms that the two 1,3-diene fragments of the tetraene interact with [Ni((Pr2PC2H4PPr2i)-P-i)] moieties. The trienes 3-methylene-1,6-heptadiene and 3-methylene-1,7-octadiene react with [NiPPr3i] species to give (eta(2),eta(2)-triene)NiPPr3i compounds in which a 1,6-heptadiene chain is complexed to the metal atom.
• Decomposition and isomerization of bridgehead cis 1,2-diazenes (azoalkanes)
  作者：Woo-Ki Chae、Sharon A. Baughman、Paul S. Engel、Manfred Bruch、Cenan Ozmeral、Sandor Szilagyi、Jack W. Timberlake

  DOI：10.1021/ja00406a026

  日期：1981.8
• Interaction of Acyclic Tetraenes and Trienes with Transition Metals: Organoiron Compounds
  作者：P. W. Jolly、C. Kopiske、C. Krueger、A. Limberg

  DOI：10.1021/om00004a048

  日期：1995.4

  The tetraene 3,6-dimethylene-1,7-octadiene (DMOD) reacts with zerovalent [FePR(3)] species (prepared by reduction of FeCl2 . nTHF with active Mg in the presence of the donor ligand) to give (eta(4),eta(4) -DMOD)FePR(3) compounds. The crystal structure of the PPh(3)-stabilized derivative (space group R ($) over bar 3, a = b = c = 20.290(9) Angstrom, alpha = beta = gamma = 117.47(3)degrees, Z = 6, R = 0.048, R(W) = 0.052) confirms that the iron atom lies at the center of a square pyramid with the P atom at the apex and the two 1,3-diene fragments forming the base. That the products of the reaction of the trienes 3-methylene-1,6-heptadiene (MHD) and 3-methylene-1,7-octadiene (MOD) with zerovalent [Fe((Pr2P)-P-i(CH2)(n)PPr2i)] species (n = 1, 2, 3) contain a triene molecule bonded in an eta(2),eta(4)-manner to the metal atom has been confirmed by X-ray diffraction for (eta(2),eta(4)-MHD)Fe((Pr2PC2H4PPr2i)-P-i) (space group P2(1)/c, a = 11.831(1) Angstrom, b = 9.744(1) Angstrom, c = 20.917(2) Angstrom, beta = 104.87(1)degrees, Z = 4, R 0.042, R(W) = 0.039). Warming a red ethereal solution of (eta(2),eta(4)-MOD)Fe((Pr2PC3H6PPr2i)-P-i) to room temperature causes dissociation of the nonconjugated double bond of the triene to give the green, paramagnetic compound (eta(4)-MOD)Fe(Pr-2(i)-PC3H6PPr2i) which reacts with CO to give the yellow, diamagnetic compound (eta(4)-MOD)Fe(CO)((Pr2PC3H6PPr2i)-P-i).