meso-3,4-diphenylhexa-1,5-diene | 33788-14-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: meso-3,4-diphenylhexa-1,5-diene
• 英文别名: meso-3,4-Diphenyl-1,5-hexadien；3,4-diphenyl-1,5-hexadiene；meso-3,4-diphenyl-hexa-1,5-diene；meso-3,4-Diphenyl-hexa-1,5-dien；meso-3.4-Diphenyl-hexadien-(1.5)；[(3S,4R)-4-phenylhexa-1,5-dien-3-yl]benzene
• CAS: 33788-14-6
• 化学式: C₁₈H₁₈
• 分子量: 234.341
• InChiKey: OOPCIDOIJKFFKD-HDICACEKSA-N

物化性质

• 熔点：
  77.5-86.5 °C(Solv: hexane (110-54-3))
• 沸点：
  308.3±37.0 °C(Predicted)
• 密度：
  0.973±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  meso-3,4-diphenylhexa-1,5-diene 在 氢氧化钾 作用下， 生成 (1E,5E)-1,6-diphenyl-1,5-hexadiene
  参考文献：
  名称：

  221.肉桂基卤化物的偶联反应。内消旋-αβ-二乙烯基二苄基和苯基乙烯基甲基

  摘要：

  DOI：

  10.1039/jr9480001111
• 作为产物：
  描述：

  Cinnamyl bromide 以6%的产率得到
  参考文献：
  名称：

  CLIVE, D. L. J.;ANDERSON, P. C.;MOSS, N.;SINGH, A., J. ORG. CHEM., 1982, 47, N 9, 1641-1647

  摘要：

  DOI：

文献信息

• THE FORMATION OF 1,4-DIPHENYLHEXADIENE-1,5 IN THE REACTION BETWEEN CINNAMYL CHLORIDE AND MAGNESIUM
  作者：Henry Gilman、Stanton A. Harris

  DOI：10.1021/ja01344a059

  日期：1932.5
• Prevost, Bulletin de la Societe Chimique de France, 1931, vol. <4> 49, p. 1372,1376
  作者：Prevost

  DOI：——

  日期：——
• Lund, Torben; Lund, Henning, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1984, vol. 38, # 5, p. 387 - 390
  作者：Lund, Torben、Lund, Henning

  DOI：——

  日期：——
• New method for coupling allylic halides: use of telluride(2-) ion species
  作者：Derrick L. J. Clive、Paul C. Anderson、Neil Moss、Alok Singh

  DOI：10.1021/jo00348a006

  日期：1982.4
• Perturbation of the Degenerate, Concerted Cope Rearrangement by Two Phenyl Groups in Active Positions of (E)-1,4-Diphenylhexa-1,5-diene. Acceleration by High Pressure as Criterion of Cyclic Transition States
  作者：W. von E. Doering、Ludmila Birladeanu、Keshab Sarma、Joaquim Henrique Teles、F.-G. Klaerner、Jan-Stephan Gehrke

  DOI：10.1021/ja00089a018

  日期：1994.5

  Previous examinations of radical-stabilizing substituents in the two distinct types of position in the hypothetical ''aromatic'' transition state of the thermal Cope rearrangement, designated ''a'' or active and ''n'' or nodal after the allyl radical, have concentrated on their effect in the ''n'' positions. In order to provide a quantitatively reliable reference for the ''a'' position, the activation parameters of the degenerate rearrangement of (6-C-13)-1,4-diphenylhexa-1,5-diene have been evaluated: E(a) = 30.8 +/- 0.4 kcal/mol; log A = 10.14 +/- 0.2. The soundly energetically-based proposition that these observations relate to a concerted mechanism is strongly supported by the observation of a 3.0-fold increase in rate of approach to equilibrium on increasing the pressure from 1 bar to 6000 bar (162 degrees C; benzene-d(6)). This rearrangement, like that of cis-1,2-divinylcyclobutane and rac- and meso-3,4-diphenylhexa-1,5-diene, has a negative volume of activation. In contrast, trans-1,2-divinylcyclobutane, which does not rearrange by a cyclic transition state and gives cycloocta-1,5-diene, 4-vinylcyclohexene and butadiene as products, has a positive volume of activation. To place the possibility of reaction by the homolytic/colligative (dissociative/recombinative) mechanism on a ''quantitative'' base, a further sighting on the heat of formation of the cinnamyl radical is provided by activation parameters for thermal syn-anti equilibration between (E)- and (Z)-1,1'-bi-3-phenylcyclohex-2-enylidene: E(a) = 35.8 +/- 0.2 kcal/mol; log A = 12.7 +/- 0.1. After correction for conjugative interaction between phenyl and the double bond in the educts and without regard for any proposed structure for the transition state, the two phenyl groups in ''a'' positions appear to have lowered the enthalpy of activation by 7.7 kcal/mol relative to the paradigm, hexa-1,5-diene, whereas the two phenyl groups in the ''n'' positions of 3,5-diphenylhexa-1,5-diene have lowered the enthalpy of activation by 17.0 kcal/mol.