dimethyl-5,5 hexadiene-1,3 cis | 59697-92-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: dimethyl-5,5 hexadiene-1,3 cis
• 英文别名: Z-1-t-butyl-1,3-butadiene；5,5-dimethyl-hexa-1,3c-diene；5,5-Dimethyl-hexa-1,3c-dien；cis-tert.-butyl-butadiene；(3Z)-5,5-dimethylhexa-1,3-diene
• CAS: 59697-92-6
• 化学式: C₈H₁₄
• 分子量: 110.199
• InChiKey: YKCQGTKPNABNLF-SREVYHEPSA-N

物化性质

• 沸点：
  115.7±7.0 °C(Predicted)
• 密度：
  0.737±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  carbon monoxide,cobalt,cyclopenta-1,3-diene 、 dimethyl-5,5 hexadiene-1,3 cis 以 四氢呋喃 为溶剂， 以0%的产率得到(η4-1,2:3,4-(Z-1-t-butyl-1,3-butadiene))(η5-cyclopentadienyl)cobalt
  参考文献：
  名称：

  The thermally-induced prototropic isomerization of η4-1,3-, η4-1,4-, η4-1,5-dialkenes complexed to (η5-cyclopentadienyl)cobalt

  摘要：

  This study reports a series of facile, thermally-induced, prototropic isomerizations of eta4-1,4- and eta4-1,5-dienes of (eta5-cyclopentadienyl)cobalt to their corresponding eta4-1,3-complexes. The data indicate the E-isomers to be thermodynamically favored over the Z-isomers. Furthermore, in the case of eta4-hexadiene complexes, the eta4-2,4-EE-isomer is observed to be thermodynamically preferred relative to either the eta4-2,4-E,Z- or eta4-1,3-E-isomers.

  DOI：

  10.1016/0022-328x(93)80363-g
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 溶剂黄146 作用下， 以 氘代苯 为溶剂， 生成 dimethyl-5,5 hexadiene-1,3 cis
  参考文献：
  名称：

  Rhodium(I)-Assisted Stereoselective Coupling of an Alkyl, Aryl or Vinyl Group with a Vinylidene Ligand: A Novel Synthetic Route to π-Allyl and π-Butadienyl Rhodium Complexes

  摘要：

  AbstractIn the first part of this work, a general method for the preparation of aryl, methyl, vinyl and alkynyl(vinyl‐idene)rhodium(I) complexes trans‐[Rh(R')‐(CCHR)(PiPr3)2] (8–14, 18–22) and trans‐[Rh(R')(CCMe2)(PiPr3)2] (16, 17) from the corresponding chloro(vinyl‐idene) derivatives and Grignard reagents is described. Whilst compounds 8 and 10–13 react with pyridine to give trans‐[Rh(CCR)(py)(PiPr3)2] (23–25) by elimination of R'H, treatment of 8–11, 16, and 18 with carbon monoxide yields the square‐planar η1‐vinyl and η1‐butadienylrhodiumcarbonyl complexes trans‐[Rh{η1‐(Z)‐C(R')CHR}(CO)(PiPr3)2] (27–32). The reaction of 8 or 18 with methyl or tert‐butylisocyanide leads stereoselectively to the isocyaniderhodium(I) compounds trans‐ [Rh{η1‐(Z)‐C(R)CHPh}(CNR') (PiPr3)2] (33–35). Acid‐induced cleavage of the rhodium‐carbon σ bond of 27, 30, or 31 with CH3CO2H gives trans‐[Rh(η1‐O2CCH3)‐(CO)(PiPr3)2] (38) and the corresponding olefin or diene, respectively. In the absence of a Lewis base such as pyridine, CO, or CNR', compounds 18–20 rearrange in benzene at 40–50 °C to afford the isomeric π‐allyl complexes [Rh(η3‐1‐RC3H4)(PiPr3)2] (40–42) almost quantitatively. The vinyl(vinylidene) compounds 11 and 12 also undergo an intramolecular rearrangement that leads to the η3‐2,3,4‐butadienyl‐ or to the alkynyl(ethene)rhodium(I) isomers, depending on the reaction conditions. In an analogous manner to the η1‐vinyl‐and η1‐butadienyl(carbonyl) derivatives 27, 30, and 31, the π‐allyl and π‐butadienyl complexes also react with acetic acid to give [Rh(η1‐O2CCH3)(PiPr3)2] (47) and the respective olefin.

  DOI：

  10.1002/chem.19970030120

文献信息

• The thermally-induced prototropic isomerization of η4-1,3-, η4-1,4-, η4-1,5-dialkenes complexed to (η5-cyclopentadienyl)cobalt
  作者：Joseph A. King、K. Peter、C. Vollhardt

  DOI：10.1016/0022-328x(93)80363-g

  日期：1993.11

  This study reports a series of facile, thermally-induced, prototropic isomerizations of eta4-1,4- and eta4-1,5-dienes of (eta5-cyclopentadienyl)cobalt to their corresponding eta4-1,3-complexes. The data indicate the E-isomers to be thermodynamically favored over the Z-isomers. Furthermore, in the case of eta4-hexadiene complexes, the eta4-2,4-EE-isomer is observed to be thermodynamically preferred relative to either the eta4-2,4-E,Z- or eta4-1,3-E-isomers.
• Rhodium(I)-Assisted Stereoselective Coupling of an Alkyl, Aryl or Vinyl Group with a Vinylidene Ligand: A Novel Synthetic Route to π-Allyl and π-Butadienyl Rhodium Complexes
  作者：Helmut Werner、Ralf Wiedemann、Paul Steinert、Justin Wolf

  DOI：10.1002/chem.19970030120

  日期：1997.1

  AbstractIn the first part of this work, a general method for the preparation of aryl, methyl, vinyl and alkynyl(vinyl‐idene)rhodium(I) complexes trans‐[Rh(R')‐(CCHR)(PiPr3)2] (8–14, 18–22) and trans‐[Rh(R')(CCMe2)(PiPr3)2] (16, 17) from the corresponding chloro(vinyl‐idene) derivatives and Grignard reagents is described. Whilst compounds 8 and 10–13 react with pyridine to give trans‐[Rh(CCR)(py)(PiPr3)2] (23–25) by elimination of R'H, treatment of 8–11, 16, and 18 with carbon monoxide yields the square‐planar η1‐vinyl and η1‐butadienylrhodiumcarbonyl complexes trans‐[Rhη1‐(Z)‐C(R')CHR}(CO)(PiPr3)2] (27–32). The reaction of 8 or 18 with methyl or tert‐butylisocyanide leads stereoselectively to the isocyaniderhodium(I) compounds trans‐ [Rhη1‐(Z)‐C(R)CHPh}(CNR') (PiPr3)2] (33–35). Acid‐induced cleavage of the rhodium‐carbon σ bond of 27, 30, or 31 with CH3CO2H gives trans‐[Rh(η1‐O2CCH3)‐(CO)(PiPr3)2] (38) and the corresponding olefin or diene, respectively. In the absence of a Lewis base such as pyridine, CO, or CNR', compounds 18–20 rearrange in benzene at 40–50 °C to afford the isomeric π‐allyl complexes [Rh(η3‐1‐RC3H4)(PiPr3)2] (40–42) almost quantitatively. The vinyl(vinylidene) compounds 11 and 12 also undergo an intramolecular rearrangement that leads to the η3‐2,3,4‐butadienyl‐ or to the alkynyl(ethene)rhodium(I) isomers, depending on the reaction conditions. In an analogous manner to the η1‐vinyl‐and η1‐butadienyl(carbonyl) derivatives 27, 30, and 31, the π‐allyl and π‐butadienyl complexes also react with acetic acid to give [Rh(η1‐O2CCH3)(PiPr3)2] (47) and the respective olefin.