(E)-2-(m-Methoxymesityl)-1,2-dimesitylethenol | 156571-23-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (E)-2-(m-Methoxymesityl)-1,2-dimesitylethenol
• 英文别名: (E)-2-(3-methoxy-2,4,6-trimethylphenyl)-1,2-bis(2,4,6-trimethylphenyl)ethenol
• CAS: 156571-23-2
• 化学式: C₃₀H₃₆O₂
• 分子量: 428.615
• InChiKey: PVYVNICPYOKTIA-ZQHSETAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-2-(m-Methoxymesityl)-1,2-dimesitylethenol 以27%的产率得到
  参考文献：
  名称：

  Rochlin Elimelech, Rappoport Zvi, J. Org. Chem, 59 (1994) N 14, S 3857-3870

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4,6-三甲酚 在 吡啶 、 sodium hydroxide 、 氯化亚砜 、 硫酸 作用下， 以 四氢呋喃 、 溶剂黄146 、 甲苯 为溶剂， 反应 220.5h， 生成 (E)-2-(m-Methoxymesityl)-1,2-dimesitylethenol
  参考文献：
  名称：

  Mapping the Enantiomerization Routes of Triarylvinyl Propellers. Barriers to the Three-Ring Flip and the Three Different Two-Ring Flips of m-Methoxy-Substituted Trimesitylvinyl Isopropyl Ethers

  摘要：

  E- and Z-(m-methoxymesityl)-1,2-dimesitylethenols (3a and 4a), their isopropyl ethers 3c and 4c, and 1-(m-methoxymesityl)-2,2-dimesitylvinyl isopropyl ether (2c) were prepared. X-ray structures of 3a and 3c were determined. The rotational barriers for the 3-ring flips are 18.8 (3a) and 18.3 (4a) kcal mol(-1). Each of 2c-4c display two MeO singlets and four i-Pr doublets and exist as a mixture of two pairs of enantiomers differing in helicity and in the ''up'' and ''down'' disposition of the OMe in relation to the C=C bond. The threshold process for correlated rotation around the Ar-C bonds of 2c-4c is a three-ring flip which leads to diastereomerization with helicity reversal, with barriers of 15.8-16.1 kcal mol(-1) resembling that for the three-ring flip enantiomerization of trimesitylvinyl isopropyl ether. The DNMR at the i-Pr region showed two coalescence processes. The lower barrier is for a three-ring flip diastereomerization, and the higher barrier is for the two-ring flip enantiomerization of the residual isomers where the MeO-labeled ring passes via the C=C plane. The barriers for the beta,beta'-, alpha,beta-, and alpha,beta' two-ring flips are 25.2 (2c), 23.1 (4c), and 21.1 (3c) kcal mol(-1). RIM calculations on the ground-state conformation are in reasonable agreement with the X-ray data, but in the calculated transition states the rings are distorted and the barriers differ from the observed ones. When ring planarity and o-Me group constraints are imposed, an agreement of the calculated and observed barriers is achieved. The conformation of the i-Pr group significantly affects the calculated barrier. The order of the barriers for the isomeric two-ring nip processes is ascribed mainly to different steric interactions between neighboring rings in the isomeric transition states.

  DOI：

  10.1021/jo00093a018

文献信息

• Stable Simple Enols. Self-Catalyzed <i>E</i>/<i>Z</i>-Isomerization of the Sterically Crowded 2-(<i>m</i>-Methoxymesityl)-1,2-dimesitylethenol¹
  作者：Elimelech Rochlin、Zvi Rappoport

  DOI：10.1021/jo020665e

  日期：2003.3.1

  2-dimesitylethenol (3a) isomerizes in the absence of a catalyst in solution to a 1.0:0.9 E/Z (3a/3b) equilibrium mixture. In CDCl3 the isomerization is first order in 3a within a run, but the plot of the rate constant k(obs) vs the changing [3a]0 in different runs is a half-parabola, indicating self-catalysis by more than one enol molecule. At 0.09 M enol, the isotope effect k(3a)/k(3a)-OD = 2.1. In the presence

  在溶液中不存在催化剂的情况下，（E）-2-（间甲氧基甲磺酰基）-1,2-二甲基间苯三酚（3a）异构化为1.0：0.9 E / Z（3a / 3b）平衡混合物。在CDCl3中，一次运行中3a的异构化为一阶，但速率常数k（obs）与不同运行中变化的[3a] 0的关系曲线为半抛物线，表明由多个烯醇分子进行自我催化。烯醇为0.09 M时，同位素效应k（3a）/ k（3a）-OD = 2.1。在存在0.025-0.25 M吡啶-d5的情况下，k（obs）与[吡啶-d5]的关系图呈钟形。在D6NO2中，在295-430 K下3a / 3b混合物的OH信号形状发生变化。由于乙烯基推进剂的非对映异构作用，在330 K处在330 K处观察到的非对映异构体3a / 3b混合物的四个信号在18.3和18.4 kcal x mol（-1）的势垒下合并。在> 360 K处观察到的结果两个信号在425 K处进一步合并，由于氧至氧质子交换或E