1,3-bis(p-chlorophenyl)allene | 143959-14-2

• 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: 1,3-bis(p-chlorophenyl)allene
• 英文别名: 1,3-bis(4-chlorophenyl)propa-1,2-diene
• CAS: 143959-14-2
• 化学式: C₁₅H₁₀Cl₂
• 分子量: 261.15
• InChiKey: XIGBTDVLJVUOJS-UHFFFAOYSA-N

物化性质

• 沸点：
  436.6±30.0 °C(Predicted)
• 密度：
  1.233±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• 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：

  5-苯基四氮唑 、 1,3-bis(p-chlorophenyl)allene 在 Selectfluor 作用下， 以 硝基甲烷 为溶剂， 反应 15.0h， 以90 mg的产率得到(Z)-2-(1,3-bis(4-chlorophenyl)-2-fluoroallyl)-5-phenyl-2H-tetrazole
  参考文献：
  名称：

  丙二烯对取代乙烯基氟化物的分子间氟胺化

  摘要：

  报道了一种使用丙二烯前体合成氟化烯丙胺的方法。在 Selectfluor 促进的分子间氟胺化反应中，多种杂环胺被用作亲核试剂。该策略提供了一种新的合成途径来获得具有连位胺部分的乙烯基氟化物。

  DOI：

  10.1039/d0ob01697g
• 作为产物：
  描述：

  1-氯-4-[2-(4-氯苯基)乙烯基]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 1,3-bis(p-chlorophenyl)allene
  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

• Ligand‐Controlled Regiodivergent Cyanoboration of Internal Allenes by Copper Catalysis
  作者：Hui Hu、Guo‐Cui Ji、Linjuan Jiang、Siwei Bi、Yuan‐Ye Jiang、Yuanhong Liu

  DOI：10.1002/anie.202210338

  日期：2022.12.19

  The first copper-catalyzed regiodivergent cyanoboration of internal allenes with B2pin2 and NCTS derivatives has been developed. MeOH was identified as the necessary additive for the regeneration of LCu-Bpin species. Computational studies revealed that the copper-mediated allylic cyanation is the regio- and stereo-determining step, while the MeOH-assisted transmetalation with B2pin2 is the rate-determining

  已经开发出第一个铜催化的具有 B 2引脚2和 NCTS 衍生物的内部丙二烯区域发散氰基硼化反应。MeOH 被确定为 LCu-Bpin 物种再生的必要添加剂。计算研究表明，铜介导的烯丙基氰化作用是区域和立体决定步骤，而甲醇辅助的 B 2 pin 2金属转移是速率决定步骤。
• 10.1021/acscatal.4c04038
  作者：Yan, Ru-Jie、Hu, Yuan、Zhu, Lei、Zhang, Jian、Wang, Qi、Huang, Jin-Yu、Chen, Zhi-Chao、Ouyang, Qin、Du, Wei、Chen, Ying-Chun

  DOI：10.1021/acscatal.4c04038

  日期：——

  from racemic allenes, and high levels of enantioselectivity are generally obtained for the tetrahydropyridine products with an E-exo-double bond in a (4 + 2) annulation pattern. Moreover, switchable regiodivergent (4 + 1) or (4 + 2) annulations with different types of racemic allenes can be accomplished via ligand control. In addition, similar oxapalladacycles of Pd(0) and activated enones can be generated

  在这里，我们证明Pd(0)可以在没有路易斯酸或布朗斯台德酸的额外帮助下直接氧化加成到缺电子的1-氮杂二烯上，并且所得的氮杂环化合物可以以独特的C2区域选择性迁移插入到丙二烯中。在随后由外消旋丙二烯原位形成的π-烯丙基钯中间体的N-烯丙基烷基化中实现了精细的动态动力学转化，并且对于在(4 + 2）环行模式。此外，可以通过配体控制来实现与不同类型的外消旋丙二烯的可切换区域发散(4 + 1)或(4 + 2)环化。此外，可以生成类似的Pd(0)和活化烯酮的奥沙帕拉达环，并与外消旋丙二烯组装，以对映选择性地获得二氢吡喃衍生物，进一步丰富了面向多样性的合成。进行了一系列对照实验和光谱分析来确认这些不寻常的杂环中间体的形成，并进一步进行密度泛函理论（DFT）计算以阐明催化途径。
• Dimerization of substituted 1,3-diarylallenes
  作者：Alan J. Brattesani、Emily Maverick、Oliver J. Muscio、Thomas L. Jacobs

  DOI：10.1021/jo00052a063

  日期：1992.12
• Intermolecular fluoroamination of allenes towards substituted vinyl fluorides
  作者：Vibha Tiwari、Jacob T. Bingham、Shubham Vyas、Anand Singh

  DOI：10.1039/d0ob01697g

  日期：——

  synthetic method towards fluorinated allylamines using allene precursors is reported. A variety of heterocyclic amines were employed as nucleophiles in a Selectfluor promoted intermolecular fluoroamination reaction. This strategy provides a novel synthetic route to access vinyl fluorides with a vicinal amine moiety.

  报道了一种使用丙二烯前体合成氟化烯丙胺的方法。在 Selectfluor 促进的分子间氟胺化反应中，多种杂环胺被用作亲核试剂。该策略提供了一种新的合成途径来获得具有连位胺部分的乙烯基氟化物。
• Electron demand in the transition state of the cyclopropylidene to allene ring opening
  作者：Philip Warner、Robert Sutherland

  DOI：10.1021/jo00049a042

  日期：1992.11

  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.