(Z)-1,3,5-hexatriene | 2612-46-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (Z)-1,3,5-hexatriene
• 英文别名: cis-1,3,5-hexatriene；1,3,5-Hexatriene, (Z)-；(3Z)-hexa-1,3,5-triene
• CAS: 2612-46-6
• 化学式: C₆H₈
• 分子量: 80.1295
• InChiKey: AFVDZBIIBXWASR-WAYWQWQTSA-N

物化性质

• 熔点：
  -12°C
• 沸点：
  78.05°C
• 密度：
  0.7175

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  (Z)-1,3,5-hexatriene 生成 1,3-环己二烯
  参考文献：
  名称：

  Evidence for inhomogeneous broadening in vibrational overtone transitions: Formation of 1, 3‐cyclohexadiene from cis‐1, 3, 5‐hexatriene

  摘要：

  By pumping the 4–0 and 5–0 C–H overtones of cis-1, 3, 5-hexatriene, the rates of 1, 3-cyclohexadiene formation are measured using a Stern–Volmer analysis. While the rate for 5–0 C–H excitation is faster than 4–0 C–H excitation, the latter is about one order of magnitude larger than that calculated from an RRKM treatment. Moreover, nonmonotonic variation in rates are found as a function of excitation wavelength within each overtone region. These observations cannot be explained by assuming pure homogeneous broadening of each overtone transition, but can be rationalized by including inhomogeneous contributions, which may originate from hot bonds in the initial state and/or from a rotational dependence of this electrocyclic reaction rate near threshold.

  DOI：

  10.1063/1.448697
• 作为产物：
  描述：

  1,3,5-己三烯 以 gas 为溶剂， 生成 (Z)-1,3,5-hexatriene
  参考文献：
  名称：

  1,5-己二烯的气相热解：连续波二氧化碳激光诱导反应及环化途径研究

  摘要：

  L'irradiation (40 torr et 100 u/cm 2 ) de l'hexadiene-1,5 导管辅助甲烷、乙烯、乙炔、丙烯、丙二烯-1,2、丁烯-1、丁二烯-1,3、环戊二烯-1 ,3 et苯。Le Radical hexadienyl est vraisemblablement un intermediaire de cyclisation。Il est prepare en solution et en phasegazeuse; 儿子举止 chimique est etudie

  DOI：

  10.1021/ja00297a002

文献信息

• Thermally and photochemically induced vinyl-hydrogen activation of [η4-1,2:3,4-(trans-1,3,5-hexatriene)](η5-cyclopentadienyl)cobalt: Regio- and stereospecific hydrogen migrations
  作者：Joseph A. King、K.Peter C. Vollhardt

  DOI：10.1016/0022-328x(94)80169-x

  日期：1994.5

  [η4-1,2:3,4-(trans-1,3,5-hexatriene)](η5-cyclopentadienyl)cobalt (3) undergoes dimerization to form a flyover carbene, 5, with concomitant elimination of one equivalent of trans-1,3,5-hexatriene. Structure 5 thermally rearranges via a metal-mediated [1,5]-H shift to carbene 6: Ea = 29.1 ± 0.4 kcal mol−1, log A = 11.6 ± 0.6. The structures of 5 and 6 were confirmed by single crystal X-ray determination

  [η 4 -1,2-：3,4-（反式-1,3,5-己三烯）]（η 5 -环戊二烯基）钴（3）经历二聚化以形成天桥卡宾，5，伴随消去一个当量的的反式-1,3,5-三烯。结构5通过金属介导的[1,5] -H转变为卡宾6而热重排：E a = 29.1±0.4 kcal mol -1，log A = 11.6±0.6。通过单晶X射线测定确认5和6的结构。低温辐照6产生13其经历热诱导的回复至6：E a＝ 19.4±0.9kcal mol -1，log A＝ 10.0±1.3。氘标记研究表明，这些CH转化所涉及的机制是分子内，区域和立体特异性的。该系统的化学研究扩展到包括各种同源的CpCo（三烯）配合物。描述了形成这些天桥戊二烯基卡宾的三烯方法与直接卡宾加成之间的比较。
• A rapidly reversible degenerate cope rearrangement
  作者：W. von E. Doering、W.R. Roth

  DOI：10.1016/s0040-4020(01)99207-5

  日期：1963.1

  The occurrence of a structurally degenerate Cope rearrangement which proceeds rapidly at room temperature is revealed by the examination, at varying temperatures, of the N.M.R. spectrum of bicyclo[5.1.0]octa-2,5-diene (I). This molecule is made by the cyclopropanation of cycloheptatriene in the 3, 4 position according to Gaspar-Roth. Its structure is assigned by virtue of its conversion to bicyclo[5

  通过在不同温度下检查双环[5.1.0] octa-2,5-二烯（I）的NMR光谱可知，发生了在室温下迅速进行的结构简并的Cope重排。根据Gaspar-Roth，该分子是由环庚三烯在3、4位的环丙烷化反应制得的。其结构是由于其在催化氢化作用下转化为双环[5.1.0]辛烷和未能吸收λ> 210mμ的紫外光而被指定的。
• Preparation of (<i>E</i>)-1,3,5-Hexatriene and (3<i>E</i>, 5<i>E</i>)-1,3,5,7-Octatetraene by the Palladium Catalyzed Elimination of Acetic Acid from Allylic Acetates
  作者：Keiji Yamamoto、Shigeaki Suzuki、Jiro Tsuji

  DOI：10.1246/bcsj.54.2541

  日期：1981.8

  Palladium complex-catalyzed elimination of acetic acid from (2E,4E)-2,4-hexadienyl acetate and (2E, 4E, 6E)-2,4,6-octatrienyl acetate afforded, respectively, the title conjugated polyenes stereoselectively.

  钯配合物催化从乙酸（2E，4E）-2，4-己二烯基乙酸酯和（2E，4E，6E）-2，4，6-辛三烯基乙酸酯中消除乙酸，分别立体选择性地提供了标题共轭多烯。
• 3-Thiabicyclo[3.2.0]hept-6-ene 3,3-dioxide: a novel synthon for cis-1,2-divinyl intermediates and derived seven-membered ring systems
  作者：R. Alan Aitken、J. I. G. Cadogan、Ian Gosney、Brendan J. Hamill、Leo M. McLaughlin

  DOI：10.1039/c39820001164

  日期：——

  Functionalisation of the 6,7-double bond in the novel bicyclic sulphone, 3-thiabicyclo[3.2.0]hept-6-ene 3,3-dioxide, followed by thermal extrusion of SO2, allows direct entry into seven-membered ring systems via a Cope rearrangement of the resulting cis-1,2-divinyl intermediates.

  在新型双环砜3-噻二环[3.2.0]庚-6-烯3,3-二氧化物中进行6,7-双键的功能化，然后热挤出SO 2，可以直接进入七元环通过产生的顺式-1,2-二乙烯基中间体的Cope重排来合成系统。
• The thermodynamic effect of fluorine as a substituent
  作者：William R. Dolbier、Karl S. Medinger、Arthur Greenberg、Joel F. Liebman

  DOI：10.1016/0040-4020(82)87020-8

  日期：1982.1

  I2-catalyzed isomerizations of 3-fluoropropene and 3,3 - difluoropropene, and a Cope rearrangement of 1,1 - difluoro - 1,5 - hexadiene provide thermodynamic data which allow the determination of a number of important group values for contributions to ΔHof which when combined with those determined in the preceding paper allow the calculations of ΔHof's of most simple F-substituted hydrocarbons: [Cd(F)(H)]

  I 2催化的3-氟丙烯和3,3-二氟丙烯的异构化以及1,1-二氟-1,5-己二烯的Cope重排提供了热力学数据，这些数据可以确定许多重要的基团值对ΔH的贡献ø ˚F当与那些前述纸中测定合并的允许的ΔH计算ø ˚F “最简单F-取代的烃的S：[C d （F）（H）] = - 38.4，[C d （F ）2 ] = − 88.0，[C（F）2（C）（C d）] = − 103.9，[C（F）2（C）2] ＝-104.9kcal /摩尔。从1,1-二氟转化为3,3-二氟-1,5-己二烯的动力学研究为该工艺提供了活化参数：Log A = 10.8，E a = 33.0 kcal / mole和ΔS ≠ =-12.2 eu讨论并对比了F和其他取代基的渐进式宝石稳定。

表征谱图