4-Methyl-1-phenyl-1,2,4-pentatriene | 31771-12-7

• 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-1-phenyl-1,2,4-pentatriene
• 英文别名: 1-Phenyl-4-methyl-pentatrien(1,2,4)
• CAS: 31771-12-7
• 化学式: C₁₂H₁₂
• 分子量: 156.227
• InChiKey: MSKPABNMXWGCLL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  (4-methylpent-4-en-1-yn-1-yl)benzene 在 二甲基亚砜 作用下， 生成 4-Methyl-1-phenyl-1,2,4-pentatriene
  参考文献：
  名称：

  金属化反应—VIII：1,4-炔的金属化及其阴离子的质子化

  摘要：

  制备了一系列的1，4-烯炔，并用丁基锂在乙醚中将化合物金属化。通过PMR和UV研究了单和二硫代衍生物的形成。二硫代化合物的质子化得到乙烯基丙二烯，1，3-和1，4-烯炔。使用二甲基钠在DMSO中将1,4-烯炔异构化，从含有末端双键的化合物得到乙烯基乙炔，从具有内部双键的化合物得到乙烯基丙二烯。还研究了各种质子的H-D交换的顺序。

  DOI：

  10.1016/0040-4020(70)80019-9

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。
• Electronic and Conformational Effects in the Photochemistry of .alpha.-Alkenyl-Substituted Vinyl Halides
  作者：Erik S. Krijnen、Han Zuilhof、Gerrit Lodder

  DOI：10.1021/jo00105a035

  日期：1994.12

  The photochemical reactions in methanol of the vinylic halides 2-halo-1-phenyl-1,3-butadienes 1-3Z-X (beta-halo-beta-alkenylstyrenes) and 1-halo-1,2-diphenylethenes 4Z-X (alpha-halostilbenes), with X = Cl or Br, have been studied quantitatively. E/Z isomerization, dehydrohalogenation, nucleophilic substitution, a [1,3]-halogen shift, a [1,3]-hydrogen shift, and oxidation are observed as the primary reactions. No reductive dehalogenation products are formed. The efficiencies of product formation are dependent on the halogen used, the electron-donating capacity of the a-substituent, the ground state conformation of the starting material, and the wavelength of excitation. Apart from the photoinduced E/Z isomerization and the oxidation reaction typical for alkenes, product formation occurs exclusively via vinyl-cationic intermediates, which are formed upon photolytic cleavage of the carbon-halogen bond. These ionic species, or part of them, are present as vinyl cation/halide anion-pairs.
• Mild-Condition Synthesis of Allenes from Alkynes and Aldehydes Mediated by Tetrahydroisoquinoline (THIQ)
  作者：Guo-Jie Jiang、Qin-Heng Zheng、Meng Dou、Lian-Gang Zhuo、Wei Meng、Zhi-Xiang Yu

  DOI：10.1021/jo4018183

  日期：2013.12.6

  A practical 1,2,3,4-tetrahydroisoquinoline (THIQ)-mediated synthesis of 1,3-disubstituted allenes from terminal alkynes and aldehydes under mild conditions in the presence of CuBr first and then ZnI2 was reported. This telescoped allene synthesis reaction includes three consecutive steps and two reactions: first, a room-temperature CuBr-catalyzed synthesis of propargylamines, exo-yne-THIQs, from terminal alkynes, aldehydes, and THIQ then filtration of the CuBr catalyst, and finally the ZnI2-mediated allene synthesis from the generated exo-yne-THIQs under mild conditions (either at room temperature or heating at 50 or 75 degrees C). A wide range of aliphatic or aromatic aldehydes and terminal alkynes are tolerated, affording the allene products in up to 92% yield. Especially, temperature-sensitive aldehydes can be used in the reaction system. Preliminary exploration of the asymmetric allene synthesis has also been conducted, and a moderate enantioselectivity has been achieved. Finally, the relative reactivities of several secondary amines were compared with THIQ, showing that THIQ is the best of these amines in the synthesis of allenes under mild reaction conditions.