1-benzylcyclohexa-2,5-dienyl-1-carboxylic acid | 52457-04-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: 1-benzylcyclohexa-2,5-dienyl-1-carboxylic acid
• 英文别名: 1-benzylcyclohexa-2,5-diene-1-carboxylic acid；1-benzyl-1,4-dihydrobenzoic acid；1-benzyl-cyclohexa-2,5-dienecarboxylic acid；1-Benzyl-cyclohexa-2,5-diencarbonsaeure
• CAS: 52457-04-2
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: AXWSLZGJWRFOOK-UHFFFAOYSA-N

物化性质

• 熔点：
  76-77 °C
• 沸点：
  364.4±31.0 °C(Predicted)
• 密度：
  1.177±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 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：

  1-benzylcyclohexa-2,5-dienyl-1-carboxylic acid 在 吡啶 、 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 24.5h， 生成 (1-benzylcyclohexa-2,5-dienyl)(2,5-dihydropyrrol-1-yl)methanone
  参考文献：
  名称：

  A Convenient One-Pot Procedure to Afford Bicyclic Molecules by Stereospecific Iron Carbonyl Mediated [6 + 2] Ene-Type Cyclization:  A Possible Approach to Gelsemine

  摘要：

  A convenient one-pot procedure to prepare angularly substituted bicyclic and tricyclic molecules with excellent diastereoselectivity in good yield was developed, by Fe(CO)5 promoted cyclization. Three transformations (complexation, isomerization, and cyclization) were realized in a single operation. The product of this reaction may be a precursor for synthesis of the alkaloid gelsemine.

  DOI：

  10.1021/ja030407e
• 作为产物：
  描述：

  methyl 1-benzylcyclohexa-2,5-dienecarboxylate 反应 2.0h， 以94%的产率得到1-benzylcyclohexa-2,5-dienyl-1-carboxylic acid
  参考文献：
  名称：

  Bandara, B. M. Ratnayake; Birch, Arthur J.; Raverty, Warwick D., Journal of the Chemical Society. Perkin transactions I, 1982, # 8, p. 1763 - 1770

  摘要：

  DOI：

文献信息

• Rapid Access to <i>Ortho</i>-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C–H Olefination/Rearomatization
  作者：Hung-Chang Tsai、Yen-Hsiang Huang、Chih-Ming Chou

  DOI：10.1021/acs.orglett.8b00064

  日期：2018.3.2

  A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C–H olefination followed by rearomatization to deliver ortho-alkylated

  描述了一种由两步简单的方法从易得的苯甲酸制备正烷基化乙烯基芳烃的方法。合成途径涉及通过桦木还原使苯甲酸脱芳香化，从而提供烷基化的环己-2,5-二烯基-1-羧酸。随后，二烯经历脱羧CH烯化反应，然后重新芳构化以交付邻烷基化的乙烯基芳烃。机理研究表明，Pd / Ag双金属催化体系在串联脱羧CH-H烯烃化/芳构化步骤中很重要。
• Reductive free-radical alkylations and cyclisations mediated by 1-alkylcyclohexa-2,5-diene-1-carboxylic acids
  作者：Paul A. Baguley、John C. Walton

  DOI：10.1039/a802024h

  日期：——

  1-alkylcyclohexa-2,5-diene-1-carboxylic acids were prepared by Birch reduction–alkylation of benzoic acid and their efficiency as mediators of alkyl radical chain addition and cyclisation processes was investigated. Reductive alkylations were respectably successful, even with only one or two equivalents of alkene, for secondary, tertiary and benzylic radicals. Reaction of 1-[2-(cyclohex-2-enyloxy)ethyl]cyclohexa-2

  通过对苯甲酸进行Birch还原-烷基化反应，制备了一系列1-烷基环六-2,5-二烯-1-羧酸，并研究了它们作为烷基链加成和环化过程的介质的效率。对于仲，叔和苄基，即使仅使用一或两个当量的烯烃，还原烷基化也相当成功。1-反应[2-（环己-2-烯基氧基）乙基]环己-2,5-二烯-1-羧酸，得到的产品外切- TRIG -cyclisation，即7-氧杂二环[4.3.0]壬烷，在产率与氢化三丁基锡诱导的3-（2'-碘乙氧基）环己烯的环化反应相当。这以及exo-和end的隔离1- [2-（6,6-二甲基双环[3.1.1]庚-2-烯-2-基甲氧基）乙基]环六-2,5-二烯-1-羧酸的环化产物确定闭环也可以用这些试剂令人满意地介导。制剂完全不含金属污染物，并且在添加或环化之前完全不存在烷基的直接还原。然而，所需的产物伴随有烷基苯，以及引发剂分解的副产物，并且这种复杂的后处理。在反式的桦木还原烷基化中未能获得1-
• Homolytic dissociation of 1-substituted cyclohexa-2,5-diene-1-carboxylic acids: an EPR spectroscopic study of chain propagation†
  作者：Leon V. Jackson、John C. Walton

  DOI：10.1039/b104859g

  日期：——

  Hydrogen abstraction from 1-substituted cyclohexa-2,5-diene-1-carboxylic acids containing linear, branched and cyclic alkyl substituents, as well as allyl, propargyl (prop-2-ynyl), cyanomethyl and benzyl substituents, has been studied by EPR spectroscopy. For each carboxylic acid, EPR spectra of the corresponding cyclohexadienyl radicals were observed at lower temperatures, followed by spectra due to ejected carbon-centred radicals at higher temperatures. Rate constants, for release of the carbon-centred radicals from the cyclohexadienyl radicals, were determined from radical concentration measurements for the above range of substituents. The rate of cyclohexadienyl radical dissociation increased with branching in the 1-alkyl substituent and with electron delocalisation in the ejected carbon-centred radical; 3,5- and 2,6-dimethyl-substitution of the cyclohexadienyl ring led to reductions in the dissociation rate constants. Rate data for abstraction of bisallylic hydrogens from the cyclohexadienyl acids were also obtained for ethyl, n-propyl and isopropyl radicals. These results indicated a sharp drop in the rate of hydrogen abstraction as the degree of branching in the attacking radical increased. Small decreases in the hydrogen abstraction rate constants were observed for cyclohexadienes containing CO2R substituents.

  通过电子顺磁共振（EPR）光谱研究了从含有线性、支化、环状烷基取代基以及烯丙基、炔丙基（丙-2-炔基）、氰基甲基和苄基取代基的1-取代环己-2,5-二烯-1-羧酸中提取氢的反应。对于每种羧酸，在较低温度下观察到相应的环己二烯基自由基的EPR谱，随后在较高温度下观察到由喷出的碳中心自由基引起的谱。通过对于上述范围的取代基的自由基浓度测量，确定了从环己二烯基自由基释放碳中心自由基的速率常数。环己二烯基自由基解离速率随着1-烷基取代基的分支增加和喷出的碳中心自由基的电子离域程度增加而加快；环己二烯环的3,5-和2,6-二甲基取代导致解离速率常数降低。还获得了从环己二烯羧酸中提取双烯丙基氢的速率数据，涉及乙基、正丙基和异丙基自由基。这些结果表明，随着攻击自由基的分支程度增加，氢提取速率急剧下降。环己二烯中含有CO2R取代基时，氢提取速率常数略有下降。
• Stereospecific Palladium-Catalyzed Decarboxylative C(sp³)C(sp²) Coupling of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Aryl Iodides
  作者：Chih-Ming Chou、Indranil Chatterjee、Armido Studer

  DOI：10.1002/anie.201103450

  日期：2011.9.5

  Walk on the same side! The title reaction occurs by means of highly stereospecific 1,3‐metal migration. The starting carboxylic acids are readily prepared by Birch reduction, and the developed protocol provides an efficient route to enantiomerically pure 5‐arylated‐1,3‐cyclohexadiene derivatives (see scheme).

  走在同一边！标题反应是通过高度立体定向的1,3-金属迁移发生的。可以通过Birch还原轻松制备起始羧酸，并且开发的方案为对映体纯的5芳基化1,3-环己二烯衍生物提供了一条有效途径（参见方案）。
• Diastereoselective Hydroformylation of 2,5-Cyclohexadienyl-1-carbinols with Catalytic Amounts of a Reversibly Bound Directing Group
  作者：Ippei Usui、Kenichi Nomura、Bernhard Breit

  DOI：10.1021/ol1028546

  日期：2011.2.18

  A phosphinite plays a role as a reversibly bound directing group for the regio- and diastereoselective hydroformylation of 2,5-cyclohexadienyl-1-carbinols. Of the two alkene functions only one was functionalized through hydroformylation to form a synthetically attractive quaternary carbon center leaving the second alkene function for potential further functionalization.

  次膦酸酯起2,5-环己二烯基-1-羰基的区域和非对映选择性加氢甲酰基化的可逆结合的导向基团的作用。在两个烯烃官能团中，只有一个通过加氢甲酰化功能化以形成合成上有吸引力的季碳中心，而留下第二个烯烃官能团用于潜在的进一步官能化。