4-methyl-3-phenyl-1,3-pentadiene | 74752-51-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-methyl-3-phenyl-1,3-pentadiene
• 英文别名: 2-methyl-3-phenyl-2,4-pentadiene；4-Methylpenta-1,3-dien-3-ylbenzene
• CAS: 74752-51-5
• 化学式: C₁₂H₁₄
• 分子量: 158.243
• InChiKey: AKBYIIIXWCDWAL-UHFFFAOYSA-N

物化性质

• 沸点：
  208.1±7.0 °C(Predicted)
• 密度：
  0.888±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  4-methyl-3-phenyl-1,3-pentadiene 在 过氧乙酸 、 sodium acetate 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 2,2-dimethyl-3-ethenyl-3-phenyloxirane
  参考文献：
  名称：

  Stereochemistry of Carbenic 1,2-Vinyl Shifts

  摘要：

  Various 1-phenylbut-3-enylidenes, (Ph)CCR2CH=CHR', were generated thermally and photolytically from tosylhydrazone (diazo) precursors. 1,2-Vinyl shifts, leading to 1,3-dienes, R'CH=CHC(Ph)=CR2, were found to predominate over gamma-C-H insertion (R = Me) and to compete with 1,2-H shifts (R = H). Intramolecular addition to the double bond was detected in the case of R = R' = Me. The resulting bicyclobutane is thermally stable and does not mediate the vinyl shift. Stereospecific migration of 1-propenyl groups (R' = Me), with retention of configuration, was observed on thermolysis and direct photolysis of appropriate substrates. These data exclude the intervention of a triplet diradical and point, to vinyl migration in the singlet manifold. Benzophenone-sensitized generation of the carbenes led to partial stereomutation but did not provide conclusive evidence for a triplet rearrangement (isomerization of the diene products could not be avoided under these conditions).

  DOI：

  10.1021/jo971691t
• 作为产物：
  描述：

  1,1-二甲基-2-苯基-1-硅杂-2-环丁烯 、 丙酮 以20%的产率得到
  参考文献：
  名称：

  TZENG, D.;FONG, R. H.;DILANJAN, SOYSA, H. S.;WEBER, W. P., J. ORGANOMETAL. CHEM., 1981, 219, N 2, 153-161

  摘要：

  DOI：

文献信息

• A New Highly Efficient Three-Component Domino Heck–Diels–Alder Reaction with Bicyclopropylidene: Rapid Access to Spiro[2.5]oct-4-ene Derivatives Part 77 in the series “Cyclopropyl Building Blocks in Organic Synthesis”. For Part 76 see: S. Wiedemann, I. Marek, A. de Meijere, Synlett 2002, submitted. Part 75: M. W. Nötzel, K. Rauch, T. Labahn, A. de Meijere, Org. Lett. 2002, 4, 839–841.
  作者：Hanno Nüske、Stefan Bräse、Sergei I. Kozhushkov、Mathias Noltemeyer、Mazen Es-Sayed、Armin de Meijere

  DOI：10.1002/1521-3765(20020517)8:10<2350::aid-chem2350>3.0.co;2-e

  日期：2002.5.17

  three-component reaction with a variety of dienophiles to furnish the domino Heck-Diels-Alder products 18 regioselectively in most cases in good to very high yields (49-100 %). The reaction of 1 with iodobenzene (2-Ph) and 17 a gave 18 a-Ph in virtually quantitative yield-also on a gram scale-using only 1 mol % of catalyst, and even bromobenzene (22) gave 18 a-Ph in 59 % yield. Bicyclopropylidene (1), in the

  发现双环亚丙基（1）在用芳基或烯基钯进行碳钯反应的速率上甚至超过丙烯酸甲酯（17a），从而导致取代的亚芳基亚环丙烷5、7和10大部分以高收率（37-78％）形成。这些二烯和交叉共轭三烯以Diels-Alder模式与亲二烯体反应，分别以良好的收率得到螺[2.5]辛烯18 a-Ph，18 b-Ph和18 a-Vin（89％，69％和65％ ）。可以通过与多种亲二烯体的单锅三组分反应来实现整体转化，从而在大多数情况下以良好或非常高的收率（49-100％）选择性地提供多米诺Heck-Diels-Alder产品18。1与碘代苯（2-Ph）和17a的反应可得到几乎定量的收率18a-Ph，也以克为单位，仅使用1 mol％的催化剂，甚至溴苯（22）也能以18％的收率获得18 a-Ph。在乙酸钯/三苯膦存在下的双环亚丙基（1）经过重排反应生成烯丙基亚环丙烷（5-H），后者在没有其他反应伙伴的情况下又二聚（7
• AN INTERPRETATION OF THE SUBSTITUENT EFFECT IN THE BLAISE REARRANGEMENT IN TERMS OF PI-ORBITALS
  作者：Yukio Abe、Tadashi Suehiro

  DOI：10.1246/cl.1983.389

  日期：1983.3.5

  The migratory aptitude of the substituent groups in the Blaise rearrangement can be explained in terms of the pi-electronic properties of the groups in the highest occupied molecular orbitals. The rates of the rearrangement reaction with relation to the substituent groups were also rationally understood based on the energy levels of the molecular orbitals.

  Blaise 重排中取代基的迁移能力可以用最高占据分子轨道中基团的 pi 电子特性来解释。基于分子轨道的能级，也可以合理地理解与取代基相关的重排反应速率。
• Evidence for the intermediacy of 1,1-dimethyl-2-phenyl-1-sila-1,3-butadiene in the photochemistry and pyrolysis of 1,1-dimethyl-2-phenyl-1-sila-2-cyclobutene
  作者：Dongjaw Tzeng、Raymond H Fong、H.S. Dilanjan Soysa、William P. Weber

  DOI：10.1016/s0022-328x(00)83007-7

  日期：1981.10

  Photolysis of 1,1-dimethyl-2-phenyl-1-sila-2-cyclobutene (I) in methanol and methanol-O-d1 yields dimethylmethoxy(1-phenyl-2-propenyl)silane and dimethylmethoxy(1-d1-1-phenyl-2-propenyl)silane, respectively, as major products. These products may be formed by reaction of methanol or methanol-O-d1 with 1,1-dimethyl-2-phenyl-1-sila-1,3-butadiene. Gas phase pyrolysis of I and acetone or formaldehyde have

  1,1-二甲基-2-苯基-1-硅-2-环丁烯（I）在甲醇和甲醇-O- d 1中的光解产生二甲基甲氧基（1-苯基-2-丙烯基）硅烷和二甲基甲氧基（1- d 1）分别是-1-苯基-2-丙烯基）硅烷。这些产物可以通过甲醇或甲醇-O- d 1与1，1-二甲基-2-苯基-1-sila-1，3-丁二烯反应形成。还研究了I和丙酮或甲醛的气相热解。