ap-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid | 104805-30-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: ap-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid
• 英文别名: 3-(1,4-dimethyl-9-triptycyl)butanoic acid rotamers (ap or sc)；(+/-)sc-3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoic acid；ap-3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoic acid；3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoic acid；ap-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid [sc-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid]；3-(3,6-dimethyl-1-pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2,4,6,9,11,13,15,17,19-nonaenyl)-3-methylbutanoic acid
• CAS: 104805-30-3；104872-36-8；188708-90-9；153744-62-8；163378-81-2；163378-82-3
• 化学式: C₂₇H₂₆O₂
• 分子量: 382.502
• InChiKey: LYYXMUIMRIHKGC-UHFFFAOYSA-N

物化性质

• 沸点：
  519.9±19.0 °C(predicted)
• 密度：
  1.206±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.95
• 重原子数：
  29.0
• 可旋转键数：
  3.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  ap-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid 在 4-二甲氨基吡啶 、 草酰氯 作用下， 生成 2-thiono-1-pyridyl 3-(1,4-dimethyl-9-triptycyl)-3-butanoate ester rotamers (ap or sc)
  参考文献：
  名称：

  2-（1-硫代-1-吡啶基）3-（1,4-二甲基-9-三苯甲基）-3-丁酸酯的热解与光解之间产物分布的显着差异以及旋转异构的影响

  摘要：

  发现标题化合物在热解中的产物分布与光解中的产物分布基本上不同。产物的分布也受该化合物的旋转异构性影响。

  DOI：

  10.1016/0040-4039(94)02333-7
• 作为产物：
  描述：

  3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoyl chloride 在 4-二甲氨基吡啶 作用下， 反应 0.08h， 生成 ap-3-Methyl-3-(1,4-dimethyl-9-triptycyl)butanoic acid
  参考文献：
  名称：

  2-（1-硫代-1-吡啶基）3-（1,4-二甲基-9-三苯甲基）-3-丁酸酯的热解与光解之间产物分布的显着差异以及旋转异构的影响

  摘要：

  发现标题化合物在热解中的产物分布与光解中的产物分布基本上不同。产物的分布也受该化合物的旋转异构性影响。

  DOI：

  10.1016/0040-4039(94)02333-7

文献信息

• Reactivities of Stable Rotamers. XXXV. Diazotization of 2-(1,4-Dimethyl-9-triptycyl)-2-methylpropylamine Rotamers
  作者：Michinori Oki、Yasushi Taguchi、Tsutomu Miyasaka、Mika Kitano、Shinji Toyota、Toshimasa Tanaka、Katsumi Yonemoto、Gaku Yamamoto

  DOI：10.1246/bcsj.68.1485

  日期：1995.5

  The title amine rotamers were prepared from the corresponding carboxylic acids and were diazotized with isopentyl nitrite in the presence of acetic acid in benzene. The ap rotamer affords, as main products, olefins that are derived by deprotonation after rearrangement of the intervening carbocation and small amounts each of the corresponding acetate and a cyclized product, both of which are derived

  标题胺旋转异构体由相应的羧酸制备，并在苯中的乙酸存在下用亚硝酸异戊酯重氮化。该适体提供作为主要产物的烯烃，其在中间碳阳离子重排后通过去质子化衍生，以及少量相应乙酸酯和环化产物中的每一种，两者均衍生自未重排的阳离子。相比之下，烯烃是次要产物，环化产物在形式上是通过在重排之前将插入的阳离子插入 1-甲基的 C-H 键而衍生出来的，在 sc 异构体的情况下是主要的。该环状产物是独立合成的。在sc相对于ap的情况下，相应乙酸盐的产率增加到相当大的程度。
• Reactivities of Stable Rotamers. XXXII. Chlorodecarboxylation of 3-(1,4-Dimethyl-9-triptycyl)-3-methylbutanoic Acid Rotamers
  作者：Michinori Oki、Yasushi Taguchi、Toshiyuki Okamoto、Tsutomu Miyasaka、Koji Hamada、Shinji Toyota、Katsumi Yonemoto、Gaku Yamamoto

  DOI：10.1246/bcsj.66.3790

  日期：1993.12

  carboxylic acid were treated with lead(IV) acetate in the presence of lithium chloride or benzyltriethylammonium chloride in benzene. The ap-isomer afforded a chloride, which was expected from normal chlorodecarboxylation, in addition to a cyclized compound, which was produced by radical addition to a near-by benzene ring. By contrast, the sc-isomer afforded no normal chloride, but a benzylic chloride, which

  在氯化锂或苄基三乙基氯化铵的苯中，用乙酸铅(IV)处理标题羧酸的旋转异构体。除了通过自由基加成到附近的苯环产生的环化化合物之外，对映异构体还提供氯化物，这是正常的氯代脱羧反应所预期的。相比之下，sc-异构体不提供正常氯化物，但主要产物是苄基氯化物，它是通过氢转移到苄基位置的 9-取代基中的自由基位点形成的。此外，获得原始sc-羧酸的丙酮酯和少量的1-乙酰氧基甲基化合物和烯烃。
• Reactivities of Stable Rotamers. XXXIX. Thermal Decomposition of<b><i>t</i></b>-Butyl 3-Methyl-3-(substituted 9-triptycyl)peroxybutanoate Rotamers
  作者：Michinori Oki、Ichiro Fujino、Daisuke Kawaguchi、Kazumasa Chuda、Yoko Moritaka、Yasunori Yamamoto、Shingo Tsuda、Tadashi Akinaga、Michihiko Aki、Hiroharu Kojima、Nobuhiro Morita、Makoto Sakurai、Shinji Toyota、Yasuhiro Tanaka、Toshihiro Tanuma、Gaku Yamamto

  DOI：10.1246/bcsj.70.457

  日期：1997.2

  The ap and sc rotamers of the title compound, where substituents are 1,4-dimethyl, 1,4-dimethoxy, 1,2,3,4-tetrafluoro, and 1,2,3,4-tetrachloro, were thermolyzed in toluene solutions to examine the effects of interactions between the radical center and the substituent. The rates of thermolyses were affected neither by the substituent nor by the rotameric positions, but the product distributions showed dependence on the substituent. In the ap-forms, the effectively bulkier the substituent at the 1-position, the higher the yields of the 5-membered ring compound. This was attributed to the degree of the tilting of the 9-substituent, which forces the radical center to be pushed into the triptycene skeleton. For the sc-forms, the chloro and the methyl substituents exhibited special effects, the former affording a colligation product between benzyl and 2-(1,2,3,4-tetrachloro-9-triptycyl)-2-methylpropyl radicals and the latter showing a tendency of radical migration to the benzylic position. Comparison of the results of thermolyses of the 1,4-dimethyl peroxyester with those of 2(1H)-thioxo-1-pyridyl 3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoate indicates that, although it is believed that these precursors afford the same 2-(1,4-dimethyl-9-triptycyl)-2-methylpropyl radicals, the product distributions were significantly different from each other. These results were attributed to the stabilizing effects of the sulfur compound on the radical in the solvent cage in the latter.

  在甲苯溶液中对取代基为 1,4-二甲基、1,4-二甲氧基、1,2,3,4-四氟和 1,2,3,4-四氯的标题化合物的 ap 和 sc 转聚体进行热解，以考察自由基中心与取代基之间相互作用的影响。热解速率既不受取代基的影响，也不受转子位置的影响，但产物分布却与取代基有关。在 ap 型化合物中，1 位上的取代基越大，5 元环化合物的产量就越高。这是因为 9-取代基的倾斜程度迫使自由基中心挤入三庚烯骨架。对于 sc 形式，氯和甲基取代基显示出特殊效果，前者在苄基和 2-（1,2,3,4-四氯-9-三辛基）-2-甲基丙基自由基之间产生碰撞产物，后者则显示出自由基向苄基位置迁移的趋势。将 1,4-二甲基过氧化酯的热解结果与 2(1H)-硫酮-1-吡啶基 3-(1,4-二甲基-9-三甲苯基)-3-甲基丁酸酯的热解结果进行比较后发现，虽然认为这些前体产生的 2-(1,4-二甲基-9-三甲苯基)-2-甲基丙基自由基相同，但产物分布却明显不同。这些结果归因于硫化合物对后者溶剂笼中自由基的稳定作用。
• Absolute Conformation of Methyl 3-(1,4-Dimethoxy- and 1,4-dimethyl-9-triptycyl)-3-methylbutanoate Rotamers
  作者：Shinji Toyota、Tsutomu Miyasaka、Michinori Oki

  DOI：10.1246/cl.1993.1571

  日期：1993.9

  title compounds were resolved via their camphor sultam amides and their absolute conformation was determined by X-ray crystallography. The chiroptical properties of the methyl esters are correlated with the absolute conformations. Both of these compounds are shown to possess dextrorotatory property at Na D line, if their stereochemistry is Psc.

  标题化合物母酸的旋转异构体的外消旋体通过樟脑磺胺酰胺拆分，其绝对构象由 X 射线晶体学确定。甲酯的手性特性与绝对构象相关。如果这些化合物的立体化学为 Psc，则这两种化合物都显示出在 Na D 线上具有右旋特性。
• Ooki, Michinori; Taguchi, Yasushi; Toyota, Shinji, Chemistry Letters, 1990, # 12, p. 2209 - 2212
  作者：Ooki, Michinori、Taguchi, Yasushi、Toyota, Shinji、Yonemoto, Katsumi、Yamamoto, Gaku

  DOI：——

  日期：——