(Z)-2-(m-Methoxymesityl)-1,2-dimesitylvinyl isopropyl ether

• 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: (Z)-2-(m-Methoxymesityl)-1,2-dimesitylvinyl isopropyl ether
• 英文别名: 2-methoxy-1,3,5-trimethyl-4-[(Z)-2-propan-2-yloxy-1,2-bis(2,4,6-trimethylphenyl)ethenyl]benzene
• 化学式: C₃₃H₄₂O₂
• 分子量: 470.695
• InChiKey: XSJUUJHITPQLPA-FPODKLOTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,4,6-三甲酚 在 苄基三乙基氯化铵 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 (Z)-2-(m-Methoxymesityl)-1,2-dimesitylvinyl isopropyl ether
  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

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

  DOI：——

  日期：——
• 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
  作者：Elimelech Rochlin、Zvi Rappoport

  DOI：10.1021/jo00093a018

  日期：1994.7

  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.