cyclohepta-2,4,6-trienecarboxylic acid | 4440-40-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: cyclohepta-2,4,6-trienecarboxylic acid
• 英文别名: 1,3,5-cycloheptatriene-7-carboxylic acid；2,4,6-cycloheptatiene-1-carboxylic acid；Cyclohepta-2,4,6-triencarbonsaeure；cyclohepta-1,3,5-triene-7-carboxylic acid；Cyclohepta-2,4,6-triene-1-carboxylic Acid
• CAS: 4440-40-8
• 化学式: C₈H₈O₂
• mdl: MFCD06208382
• 分子量: 136.15
• InChiKey: MMJMJYGSJNZKBB-UHFFFAOYSA-N

物化性质

• 熔点：
  71-72 °C
• 沸点：
  103-105 °C(Press: 0.4 Torr)
• 密度：
  1.170±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.125
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cyclohepta-2,4,6-trienecarboxylic acid 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 Dilithium-heptafulven-8,8-diolat
  参考文献：
  名称：

  Bestimmung des Aggregations公司将四氢呋喃中的锂有机溶剂Verbindungen durch Kryoskopie分级

  摘要：

  四氢呋喃中有机硅化合物的冰晶凝集度

  DOI：

  10.1002/hlca.19840670736
• 作为产物：
  描述：

  2,4,6-环庚三烯-1-甲腈 在 硫酸 作用下， 生成 cyclohepta-2,4,6-trienecarboxylic acid
  参考文献：
  名称：

  环庚三烯的碱催化 1-3 质子异构化

  摘要：

  在氢氧化钠水溶液或氢氧化钾水溶液介质中研究了带有吸电子基团的环庚三烯的碱催化质子迁移（从 7 位到 2 位）和质子交换（在 7 位）。各种取代基对相对速率的影响顺序约为：CN>CONH2>COO-，Ph。碱催化的质子异构化通过以下方式进行：i) 碱对 7 位质子的提取， ii) 生成的碳负离子迁移到烯丙基位置（速率决定步骤），以及 iii) 从溶剂中回收质子。7-羧基环庚三烯（Ia）异构化的动力学研究公开了异构化速率（k[环庚三烯][碱]）和参数（Ea=22.6 kcal/mol，ΔH\eweq=22.0 kcal/mol，ΔS\eweq=−15.4 eu 在 60°）。讨论了作为中间体形成的环庚三烯基阴离子的结构。

  DOI：

  10.1246/bcsj.43.200

文献信息

• NMR Motional Averaging in the Isotopically Perturbed Cope Rearrangement
  作者：Eric R. Johnston、Jodi S. Barber、Marc Jacomet、James C. Barborak

  DOI：10.1021/ja970281j

  日期：1998.2.1

  The effect of deuterium substitution on the positional equilibrium and rate of the Cope rearrangement in barbaralone-d1 has been investigated by 1H and 13C dynamic NMR spectroscopy. Deuterium favors the allylic position over the cyclopropyl position. Skewing of the equilibrium requires that the Cope rearrangement be considered as a nonmutual exchange process that transports 13C−1H spin pairs between

  已通过 1 H 和 13 C 动态核磁共振光谱研究了氘取代对 barbaralone-d1 中 Cope 重排的位置平衡和速率的影响。与环丙基位置相比，氘更倾向于烯丙基位置。平衡的偏斜要求 Cope 重排被认为是一个非相互交换过程，它在分布不均的分子构型之间传输 13C-1H 自旋对。根据最近提出的替代平均理论（Jones, DH; Kurur, ND; Weitekamp, DP Bull. Magn. Reson. 1992, 14, 214）批判性地解释了核磁共振快速交换结果。我们的实验结果与传统理论一致，但与替代理论的预测不一致。
• 489. The tropylium ion. Part IV. Conversion of cyclohepta-2,4,6-trienecarboxylic acid into tropylium salts
  作者：M. J. S. Dewar、C. R. Ganellin

  DOI：10.1039/jr9590002438

  日期：——
• Synthesis of 3-arylecgonine analogs as inhibitors of cocaine binding and dopamine uptake
  作者：Richard H. Kline、Jeremy Wright、Kristine M. Fox、Mohyee E. Eldefrawi

  DOI：10.1021/jm00169a036

  日期：1990.7

  3-Arylecgonine analogues were synthesized and characterized by 1H and 13C NMR, IR, and MS. The compounds were synthesized as racemates from cycloheptatriene-7-carboxylic acid or enantiomerically from (-)-cocaine. These analogues were tested for their ability to inhibit [3H]cocaine binding to bovine striatal tissue and to inhibit [3H]dopamine uptake into striatal synaptosomes. Methyl (1RS-2-exo-3-exo)-8-methyl-3-phenyl-8-azabicyclo[3.2.1]octane-2-ca rboxylate was the most potent analogue. IC50 values for inhibition of cocaine binding and dopamine uptake were 20 and 100 nM, respectively. The racemates and the 1R isomers were equally potent inhibitors of binding and uptake. Methyl (1RS-2-endo-3-exo)-3-(2,4-dinitrophenyl)-8-methyl-8-azabicyclo[3.2 .1]octane- 2-carboxylate was the least potent. IC50 for inhibition of both binding and uptake was 40 microM.
• Heptafulvenone, Vinylketene, Butadienylketene, and Allenylketene − Facile Generation, Observation, and Radical Reaction with TEMPO
  作者：Thomas T. Tidwell、Michael H. Fenwick

  DOI：10.1002/1099-0690(200109)2001:18<3415::aid-ejoc3415>3.0.co;2-w

  日期：2001.9

  Heptafulvenone (1), vinylketene (11), 1,3-butadienylketene [(E)-15], and allenylketene (21) have been prepared by reaction of the corresponding acyl chlorides with 1,8-bis(dimethylamino)naphthalene as long-lived species in solution at room temperature, and their ketenyl IR bands observed under these conditions for the first time, at 2101, 2118, 2111, 2117 cm(-1), respectively. These unsaturated ketenes react with tetramethylpiperidinyloxyl (TEMPO, TO.) with initial attack at the carbonyl carbon giving delocalized radicals which give from 1 a mixture of the ring contracted o-, m-, and p-formylbenzoates O=CHC6H4CO2T (6) and the bis(cycloheptatrienyl) dimer 7. The products from 11, (E)-15, and 21 are the bis(TEMPO) adducts. (E,Z)-TOCH2CH= CHCO2T (12), (E,E)-TOCH2CH=CHCH=CHCO2T (17), and (E,Z)-CH2=C(OT)CH=CHCO2T (22), respectively.
• Ion Pair Acidities and Aggregation of Some Amide and Oxazoline Enolates in THF^,
  作者：Antonio Facchetti、Andrew Streitwieser

  DOI：10.1021/jo981846c

  日期：1999.4.1

  Equilibrium lithium ion pair acidities at 25 degrees C have been determined in THF for the following acetamides: N,N-dimethyl-(4-biphenylyl)acetamide (1) (19.69), N,N-diethyl-(4-biphenylyl)acetamide (2) (20.30), N,N-dimethyl-diphenylacetamide (3) (20.76), N,N-diethyl-diphenylacetamide (4) (21.99), and 1-(diphenylmethylcarbonyl)pyrrolidine (5) (21.08). These acidity data compare well with those previously reported for the corresponding cesium enolates. Lithium and cesium ion pair acidities in THF are reported for two oxazolines: 2-(4-biphenylylmethyl)oxazoline (6) (Li, 21.53; Cs, 25.49) and (E)-(4S,5R)-2-(4-biphenylylmethyl)-4-methyl-5-phenyloxazoline (7) (Li, 20.10; Cs 24.21). Studies of their acidities over a wide range of concentrations indicate that all of the lithium and cesium enolates of 1-7 are essentially monomeric at concentrations ranging from 10(-8) to 10(-4) M. Traces of dimer were detected for the lithium enolates of amides 1 and 2 and for the cesium enolate of oxazoline 6. Their dimerization constants (M-1) were found to be about 450, 200, and 150, respectively. All of the other lithium and cesium enolate probably form small amounts of dimer, but the dimerization constant of < 100 M-1 is below the limit of precision of our spectroscopic method.