1,2,4,5-tetrakis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl] benzene-1,2,4,5-tetracarboxylate | 122874-72-0

• 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: 1,2,4,5-tetrakis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl] benzene-1,2,4,5-tetracarboxylate
• 英文别名: (-)-tetramenthyl 1,2,4,5-benzenetetracarboxylate；tetra(L-menthyl) pyromellitate；tetrakis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] benzene-1,2,4,5-tetracarboxylate
• CAS: 122874-72-0
• 化学式: C₅₀H₇₈O₈
• 分子量: 807.165
• InChiKey: HRFYYYNUAJFDEC-OPXRAZQMSA-N

物化性质

• 熔点：
  120-123.5 °C(Solv: ethanol (64-17-5))
• 沸点：
  757.9±55.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  15.2
• 重原子数：
  58
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  L-薄荷醇 、 1,2,4,5-苯四(甲酰氯) 在 吡啶 作用下， 反应 12.0h， 以73%的产率得到1,2,4,5-tetrakis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl] benzene-1,2,4,5-tetracarboxylate
  参考文献：
  名称：

  Steric hindrance-induced dual fluorescence of congested benzenehexacarboxylates

  摘要：

  Alkyl benzenetetra- and benzenehexacarboxylates were shown to fluoresce weakly in fluid solutions, in sharp contrast to entirely nonfluorescent mono-, di-, or tricarboxylates. Interestingly, benzenehexacarboxylates with bulky alkyl groups provide a novel dual-fluorescing molecular system involving a mechanism differing from the well-documented excimer formation, protonation/deprotonation, or twisted intramolecular charge transfer. Thus hexacarboxylates of isopropyl, tert-butyl, (-)-bornyl, (-)-menthyl, and 1-adamantyl alcohols show unambiguous, bulkiness-dependent dual fluorescence peaks with both small and substantially large Stokes shifts at room and/or low temperatures, whereas the hexamethyl ester and the corresponding tetracarboxylates with bulky alkyl groups never show such unusual fluorescence behavior. This dual fluorescence phenomenon is attributed to the decelerated conformational relaxation in the excited state owing to steric hindrance between adjacent bulky alkyl groups.

  DOI：

  10.1021/ja00006a011
• 作为试剂：
  描述：

  (顺式)-1,1'-(1,2-环丙烷二基)二苯 在 1,2,4,5-tetrakis[(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl] benzene-1,2,4,5-tetracarboxylate 作用下， 以 正戊烷 为溶剂， 反应 80.0h， 生成 (反式)-1,1'-(1,2-环丙烷二基)二苯
  参考文献：
  名称：

  Enantiodifferentiating cis-trans photoisomerizations of 1,2-diarylcyclopropanes and 2,3-diphenyloxirane sensitized by chiral aromatic esters

  摘要：

  Photosensitized enantiodifferentiating cis-trans isomerizations of 1,2-diphenylcyclopropane (1), 1,2-bis(4-methoxyphenyl)cyclopropane (2), and 2,3-diphenyloxirane (3) were performed in the presence of optically active alkyl arenecarboxylates as electron-accepting photosensitizers. Several photosensitizers possessing different chromophores and chiral groups were examined in polar and nonpolar solvents, and optical purities (op) up to 10% for It and 1% for 2t and 3t were obtained. The product's op varied drastically with solvent polarity and, in an extreme case, typical polar and nonpolar solvents gave antipodal products. Mechanistic investigations revealed that the enantiodifferentiation occurs in the quenching of the excited chiral sensitizer by racemic substrates and that full equilibrium is not established between the enantiomeric ambident intermediates, probably owing to their short lifetimes.

  DOI：

  10.1021/jo00059a032

文献信息

• Esters of Pyromellitic Acid. Part II. Esters of Chiral Alcohols: Para Pyromellitate Diesters as a Novel Class of Resolving Agents and Use of Pyromellitates as Duplicands for Chiral Purification
  作者：John B. Paine

  DOI：10.1021/jo8005446

  日期：2008.7.1

  advantage of the easily separated benzyl diesters and their derived acid chlorides (19, 21), with the benzyl esters serving as temporary blocking groups removable by catalytic hydrogenolysis. Pyromellitate tetraesters (26) were prepared by base-catalyzed transesterification of the tetraethyl ester (25). Tri-l-menthyl pyromellitate (27b) was obtained by catalytic hydrogenolysis of benzyl tri-l-menthyl pyromellitate

  提出了制备手性萜烯醇的均苯四酸酯的方法，包括d-（3）或l-薄荷醇（4），d-异薄荷醇（7），l-冰片（8）或d-（5）或l -异opinocampheol（6）。PMDA在CH的醇解2氯2 / ET 3 n个LED以单酯（例如，形成18）或二酯（11，12），视需要而定，取决于两个酸酐基团的差异反应性。容易分离的对位二酯（11）在HOAc的间位二酯（12）之前结晶。尼古丁（1，14）中的有效的解决为1：1克的盐与薄荷基（11A，11B）或冰片（11F）的对二酯，的什么承诺，是一大类新颖的拆分剂的原型。对-二-薄荷基均苯四酸酯（11a）的重结晶大大提高了所含d-薄荷醇的手性纯度（3），这是通过“复制”进行纯化的示例。特定的二酯的替代性合成接过容易分离苄酯和它们的衍生酰氯（的优点19，21），与作为临时保护基团苄基酯可移除地通过催化氢解。通过对四乙酯（25）进行碱催化的酯交换反应来制备均苯四