1-methyl-4-(3-phenylpropa-1,2-dienyl)benzene | 32092-99-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 1-methyl-4-(3-phenylpropa-1,2-dienyl)benzene
• 英文别名: 1-phenyl-3-(p-tolyl)-1,2-propadiene；1-Phenyl-3-p-methylphenylallen；1-p-Tolyl-3-phenylallen；Benzene, 1-methyl-4-(3-phenyl-1,2-propadienyl)-
• CAS: 32092-99-2；32093-00-8；61692-95-3
• 化学式: C₁₆H₁₄
• 分子量: 206.287
• InChiKey: AUTYPJYFPZWZDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-甲基-4-((e)-苯乙烯)-苯 在 sodium hydroxide 、 叠氮磷酸二苯酯 、 sodium methylate 、 乙酸酐 、 copper(II) sulfate 、 溶剂黄146 、 三乙胺 、 sodium nitrite 作用下， 以 甲醇 、 甲苯 、 苯 为溶剂， 反应 10.55h， 生成 1-methyl-4-(3-phenylpropa-1,2-dienyl)benzene
  参考文献：
  名称：

  Electron demand in the transition state of the cyclopropylidene to allene ring opening

  摘要：

  The electronic structure of the transition state for the cyclopropylidene to allene conversion has been probed. The methodology involved the relative rates of ring opening vs trapping by MeOH for a series of variously substituted 2,3-diarylcyclopropylidenes. With the assumption that the rate of trapping was unaffected by substituents, a Hammett correlation was constructed. The negative value (-0.72) for rho indicated that the carbenic center attracts electron density in the ring-opening transition state, much like the cyclopropyl cation to allyl cation transition state. Temperature-dependent studies showed that the observed preference for ring opening was driven by entropy factors. Also, using reasonable estimates for the close to diffusion-controlled trapping activation enthalpies, the derived enthalpies for ring opening were in close agreement with the best theoretical values.

  DOI：

  10.1021/jo00049a042

文献信息

• Silver(<scp>i</scp>)-mediated highly enantioselective synthesis of axially chiral allenes under thermal and microwave-assisted conditions
  作者：Vanessa Kar-Yan Lo、Cong-Ying Zhou、Man-Kin Wong、Chi-Ming Che

  DOI：10.1039/b914516h

  日期：——

  Silver(I) salts mediated stereospecific transformation of optically active propargylamines to axially chiral allenes with excellent enantioselectivities (17 examples with 96-99% ee; one substrate with 91% ee) without subsequent racemization.

  银（I）盐介导的光学活性炔丙基胺向具有良好对映选择性的轴向手性烯键的立体定向转化（17个示例，其ee值为96-99％；一个底物的ee为91％），而没有随后的外消旋作用。
• Synthesis of Allenes via Gold-Catalyzed Intermolecular Reaction of Propargylic Alcohols and Aromatic Compounds
  作者：Cheng-Fu Xu、Mei Xu、Liu-Qing Yang、Chuan-Ying Li

  DOI：10.1021/jo300147u

  日期：2012.3.16

  Functionalized allenes are efficiently synthesized in moderate to high yield from gold-catalyzed intermolecular reaction of propargylic alcohols and aromatic compounds. The user-friendly process could be conducted under mild reaction conditions with easily accessible starting materials.

  通过金催化的炔丙醇和芳族化合物的分子间反应，可以中等至高收率有效地合成官能化的烯。用户友好的过程可以在温和的反应条件下用容易获得的原料进行。
• Mechanism of the electrophilic iodination of 1,3-diarylallenes
  作者：Anton J. G. van Rossum、Rutger J. F. Nivard

  DOI：10.1039/p29760001322

  日期：——

  observation that the addition is accompanied by racemisation, and that racemisation and addition rate constants are equal at the same temperature. The ρ value for the iodination of 1-phenyl-3-(p-tolyl)allenes, substituted in the phenyl ring is only –2.3 at 5°. The diminished influence of substituents in this series is ascribed to the alteration of the charge distribution in the transition state by the fixed

  给出了将碘添加到作为溶剂的1,2-二氯乙烷中的12个取代的1,3-二苯基丙二烯中的动力学数据。发现基于σ +值的线性哈米特图对于一个环中被取代的二苯丙二烯而言，在5°时的ρ值为–3.2。这已被证明是过渡态类似于平面的1,3-二苯基烯丙基阳离子的证据。该结论得到以下观察结果的支持，即加成过程伴随着外消旋作用，并且在相同温度下外消旋作用和加成速率常数相等。1-苯基-3-（p的碘化的ρ值在5°时，在苯环中取代的-tolyl）Allenes仅为–2.3。该系列中取代基的影响减小归因于另一环中固定的对甲基取代基改变了过渡态的电荷分布。
• The Polarized Absorption Spectrum of 1,3-Diphenyl-1,2-propadiene: Interaction between Mutually Perpendicular Equivalent<b><i>π</i></b>-Electronic Systems
  作者：Jun Okubo、Takayasu Shimazaki、Shin-ichi Sato、Hiraku Shinozaki

  DOI：10.1246/bcsj.67.1405

  日期：1994.5

  The polarized UV absorption spectrum of 1,3-diphenyl-1,2-propadiene (DPA) was measured in a stretched polymer film at 101 K, and the polarization directions of the electronic absorption bands were determined. Pariser–Parr–Pople (PPP) calculations extended to three dimensions were performed, and the position, intensity, and polarization of each absorption band of DPA were obtained from the calculations. The observed 289.8 and 265.2 nm bands polarized along the longer molecular axis were assigned to the calculated S1←S0 and S3←S0 transitions, respectively, and the 237.1 nm band along the shorter molecular axis was assigned to the S4←S0 transition. The results of configuration analysis indicate that the second transitions (at 260.5 nm) of two styrenes, whose π-electronic systems are perpendicular to each other, contribute equally to the third and fourth transitions observed at 265.2 and 237.1 nm of DPA. In addition, it was clarified that the first absorption band of DPA corresponding to Parity’s forbidden transition was intensified by an increase of the ionization energy of the sp hybridized carbon atom in the allenic moiety.

  在 101 K 下测量拉伸聚合物薄膜中 1,3-二苯基-1,2-丙二烯 (DPA) 的偏振紫外吸收光谱，并确定电子吸收带的偏振方向。进行扩展到三个维度的Pariser-Parr-Pople (PPP)计算，并从计算中获得DPA每个吸收带的位置、强度和偏振。观察到的沿较长分子轴偏振的 289.8 和 265.2 nm 谱带分别分配给计算出的 S1←S0 和 S3←S0 跃迁，而沿较短分子轴偏振的 237.1 nm 谱带则分配给 S4←S0 跃迁。构型分析结果表明，π电子体系相互垂直的两个苯乙烯的第二次跃迁（260.5 nm处）对DPA在265.2和237.1 nm处观察到的第三次和第四次跃迁的贡献相等。此外，还表明，对应于Parity禁戒跃迁的DPA第一吸收带是通过丙二烯部分中sp杂化碳原子的电离能的增加而增强的。
• Chromium–Carbyne Complexes: Intermediates for Organic Synthesis
  作者：Romain Bejot、Anyu He、John R. Falck、Charles Mioskowski

  DOI：10.1002/anie.200604015

  日期：2007.2.26