1-(氰基甲基)环己-2,5-二烯-1-羧酸 | 380883-30-7

• 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
• 中文名称: 1-(氰基甲基)环己-2,5-二烯-1-羧酸
• 英文名称: 1-(cyanomethyl)cyclohexa-2,5-diene-1-carboxylic acid
• CAS: 380883-30-7
• 化学式: C₉H₉NO₂
• 分子量: 163.176
• InChiKey: NVOFCWOVBBCTRB-UHFFFAOYSA-N

物化性质

• 沸点：
  365.2±42.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(氰基甲基)环己-2,5-二烯-1-羧酸 在 sodium tetrahydroborate 、 氯甲酸乙酯 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 甲苯 为溶剂， 反应 7.0h， 生成 (1-Benzyloxymethyl-cyclohexa-2,5-dienyl)-acetaldehyde
  参考文献：
  名称：

  Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade

  摘要：

  Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting 1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.

  DOI：

  10.1021/ol0618353
• 作为产物：
  描述：

  lithium benzoate 、 氯乙腈 在 lithium 作用下， 以 氨 、 四氢呋喃 为溶剂， 反应 1.08h， 生成 1-(氰基甲基)环己-2,5-二烯-1-羧酸
  参考文献：
  名称：

  2,5-环己二烯基-1-碳醇的非对映选择性加氢甲酰基化与可逆结合导向基团的催化量

  摘要：

  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。

  DOI：

  10.1021/ol1028546

文献信息

• 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。
• Catalytic Enantioselective Birch–Heck Sequence for the Synthesis of Phenanthridinone Derivatives with an All-Carbon Quaternary Stereocenter
  作者：Mary Sexton、William P. Malachowski、Glenn P. A. Yap、Diana Rachii、Greg Feldman、Andrew T. Krasley、Zhilin Chen、My Anh Tran、Kalyn Wiley、Alexandra Matei、Samantha Petersen、Sabrina Tran Tien

  DOI：10.1021/acs.joc.1c02523

  日期：2022.1.21

  pathway to such derivatives exists. Herein we report a four-step process that transforms inexpensive benzoic acid into 22 different quaternary carbon-containing phenanthridinone analogues with a variety of substituents on all three rings: alkyl groups at the quaternary center; methyl, methoxymethyl, or para-methoxybenzyl on the amide nitrogen; and halogen and methyl substituents on the aryl ring. Good to

  使用 Birch-Heck 序列对映选择性合成了具有全碳四元立构中心的新型菲啶酮类似物。扁平菲啶酮结构具有广泛的生物活性，但因此也存在治疗选择性差的问题。在菲啶酮骨架上添加四元中心有可能产生更复杂的类似物，并提高选择性。不幸的是，不存在此类衍生物的通用合成途径。在此，我们报道了一种四步法，将廉价的苯甲酸转化为 22 种不同的含季碳菲啶酮类似物，所有三个环上都有各种取代基：季中心的烷基；酰胺氮上的甲基、甲氧基甲基或对甲氧基苄基；以及芳环上的卤素和甲基取代基。在关键的分子内去对称 Mizoroki-Heck 反应中证明了良好到非常好的对映选择性。还完成了赫克反应产物向具有潜在更大治疗相关性的分子的转化。
• Synthesis of γ‐Spirolactams by Birch Reduction of Arenes
  作者：Tobias Krüger、Torsten Linker

  DOI：10.1002/ejoc.202100056

  日期：2021.3.12

  Birch reduction of arene carboxylic acids in the presence of chloroacetonitrile affords nitriles and their subsequent catalytic hydrogenation γ‐spirolactams in only 3 steps with excellent stereoselectivities. It is possible to control the degree of saturation by variation of the catalyst at different pressures. Thus, more than 15 new γ‐spirolactams have been synthesized from inexpensive starting materials

  在氯乙腈存在下将芳烃羧酸进行桦木还原，仅需3个步骤，即可得到腈及其随后的催化加氢γ-螺内酰胺，具有出色的立体选择性。可以通过在不同压力下改变催化剂来控制饱和度。因此，已经用廉价的起始原料合成了15种以上的新型γ-螺内酰胺。
• Simple Synthesis of γ-Spirolactams by Birch Reduction of Benzoic Acids
  作者：Tobias Krüger、Alexandra Kelling、Uwe Schilde、Torsten Linker

  DOI：10.1002/ejoc.201601650

  日期：2017.2.10

  Reduction + reduction: This simple sequence allows the synthesis of γ‐spirolactams 3 from commercially available benzoic acids 1 via cyclohexadienes 2 in only two steps. The method is characterized by cheap reagents, good to high yields, and excellent diastereoselectivities, and the products can be isolated by crystallization on a large scale.

  还原+还原：该简单序列允许的合成γ-spirolactams 3从市售的苯甲酸1通过环己二烯2中仅两个步骤。该方法的特点是试剂便宜，收率高至高，非对映选择性好，可以通过结晶大规模分离出产物。
• Process for the preparation of polycarbonates
  申请人：Stichting Dutch Polymer Institute

  公开号：EP2112187A1

  公开（公告）日：2009-10-28

  The invention relates to a process for the preparation of polycarbonates from oxiranes and CO2 characterized in that the polymerization is carried out in a single step in the presence of a chain transfer agent. Preferred chain transfer agents are polyols. The invention also relates to branched polycarbonates that have functional hydroxyl endgroups.

  本发明涉及一种以环氧乙烷和二氧化碳为原料制备聚碳酸酯的工艺，其特征在于聚合反应是在链转移剂存在下一步完成的。首选的链转移剂是多元醇。本发明还涉及具有官能羟基端基的支化聚碳酸酯。