2-金刚烷羧醛 | 39750-93-1

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 中文名称: 2-金刚烷羧醛
• 中文别名: 2-金刚烷甲醛
• 英文名称: adamantane-2-carbaldehyde
• 英文别名: 2-adamantanecarboxaldehyde
• CAS: 39750-93-1
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: VGBBJZYOAOCLLS-UHFFFAOYSA-N

物化性质

• 熔点：
  158-160℃
• 沸点：
  247.5±9.0℃ (760 Torr)
• 密度：
  1.124±0.06 g/cm3 (20 ºC 760 Torr)
• 闪点：
  85.5±11.2℃

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2912299000
• 储存条件：
  2-8℃

反应信息

• 作为反应物：
  描述：

  2-金刚烷羧醛 在 sodium hydride 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 生成 2-(4-fluorobenzoyl)-2-methyladamantane
  参考文献：
  名称：

  Enhanced Enantio- and Diastereoselectivity via Confinement and Cation Binding:  Yang Photocyclization of 2-Benzoyladamantane Derivatives within Zeolites

  摘要：

  Irradiation of 2-benzoyladamantane derivatives in zeolites yields the endo-cyclobutanols as the only photoproduct via a gamma-hydrogen abstraction process. The cyclobutanols readily undergo retro-aldol reaction to give delta-ketoesters. The enantiomeric excess (ee) in the endo-cyclobutanols is measured by monitoring the ee in the ketoesters. Whereas in solution the ee in the product ketoester is zero, within achiral NaY zeolite, in the presence of a chiral inductor such as pseudoephedrine, ee's up to 28% have been obtained. The influence of zeolite on several chiral esters of 2-benzoyladamantane-2-carboxylic acids has also been examined. Whereas in solution the diastereomeric excess is <15%, in zeolite the delta-ketoesters are obtained in 79% de (best examples). Ab initio computations suggest that enhancement of chiral induction within zeolites is likely to be due to cation complexation with the reactant ketone. Alkali ion-organic interaction, a powerful tool, is waiting to be fully exploited in photochemical and thermal reactions. In this context zeolites could be a useful medium as one could view them as a reservoir of "naked" alkali ions that are only partially coordinated to the zeolite walls.

  DOI：

  10.1021/jo0260793
• 作为产物：
  描述：

  金刚烷酮 在 caesium carbonate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 20.0h， 生成 2-金刚烷羧醛
  参考文献：
  名称：

  用于迭代合成的羰基化合物的光诱导同系化

  摘要：

  描述了用于羰基同系化的光致 Büchner-Curtius-Schlotterbeck 型反应。该协议允许通过相应的 N-tosylhydrazone 阴离子的直接光激发，将羰基化合物用作安全且易于获得的重氮前体。以实用和迭代的方式制备功能化脂肪醛和酮。

  DOI：

  10.1002/anie.202211578

文献信息

• Synthesis and SAR of New 5-Phenyl-3-ureido-1,5-benzodiazepines as Cholecystokinin-B Receptor Antagonists
  作者：Antonella Ursini、Anna M. Capelli、Robin A. E. Carr、Paolo Cassarà、Mauro Corsi、Ornella Curcuruto、Giovanni Curotto、Michele Dal Cin、Silvia Davalli、Daniele Donati、Aldo Feriani、Harry Finch、Gabriella Finizia、Giovanni Gaviraghi、Marc Marien、Giorgio Pentassuglia、Stefano Polinelli、Emiliangelo Ratti、Aldo Reggiani、Giorgio Tarzia、Giovanna Tedesco、Maria E. Tranquillini、David G. Trist、Frank T. M. Van Amsterdam

  DOI：10.1021/jm990967h

  日期：2000.10.1

  A series of 5-phenyl-3-ureidobenzodiazepine-2,4-diones was synthesized and evaluated as cholecystokinin-B (CCK-B) receptor antagonists. Structure-activity relationship (SAR) studies revealed the importance of the N-1 substituent for potent and selective CCK-B affinity. Addition of substituents at the urea side chain provided in some cases more potent compounds. Moreover the introduction of bulky substituents

  合成了一系列5-苯基-3-脲基苯并二氮杂-2，4-二酮，并作为胆囊收缩素-B（CCK-B）受体拮抗剂进行了评估。结构活性关系（SAR）研究表明，N-1取代基对于有效和选择性CCK-B亲和力的重要性。在某些情况下，在脲侧链上添加取代基可提供更有效的化合物。此外，在N-1处引入笨重的取代基（如金刚烷基甲基）和拆分外消旋脲导致了我们的铅化合物GV150013。
• Reduction of <i>N</i> ,<i>N</i> -Dimethylcarboxamides to Aldehydes by Sodium Hydride-Iodide Composite
  作者：Guo Hao Chan、Derek Yiren Ong、Zhihao Yen、Shunsuke Chiba

  DOI：10.1002/hlca.201800049

  日期：2018.5

  established using sodium hydride (NaH) in the presence of sodium iodide (NaI) under mild reaction conditions. The present protocol with the NaH‐NaI composite allows for reduction of not only aromatic and heteroaromatic but also aliphatic N,N‐dimethylamides with wide substituent compatibility. Retention of α‐chirality in the reduction of α‐enantioriched amides was accomplished. Use of sodium deuteride (NaD)

  在温和的反应条件下，在碘化钠（NaI）存在下，使用氢化钠（NaH）建立了一种新的简洁的协议，用于将N，N-二甲基酰胺选择性还原为醛。具有NaH-NaI复合材料的本协议不仅可以还原具有广泛取代基相容性的芳族和杂芳族化合物，而且还可以还原脂肪族N，N-二甲基酰胺。在减少α-对映体酰胺的过程中，保留了α-手性。氘化钠（NaD）的使用为制备氘掺入率高的氘代醛提供了一种新的经济实惠的替代方法。NaH-NaI复合材料具有独特的化学选择性，可减少N，N-二甲基酰胺比酮。
• Methods and compositions for treating amyloid-related diseases
  申请人：Kong Xianqi

  公开号：US20060223855A1

  公开（公告）日：2006-10-05

  Methods, compounds, pharmaceutical compositions and kits are described for treating or preventing amyloid-related disease.

  描述了用于治疗或预防与淀粉样蛋白相关疾病的方法、化合物、药物组合物和试剂盒。
• Cobalt carbonyl catalyzed reactions of esters and lactones with hydrosilane and carbon monoxide. A novel synthetic method for the introduction of the siloxymethylidene group
  作者：Naoto. Chatani、Satoru. Fujii、Yasuhiro. Yamasaki、Shinji. Murai、Noboru. Sonoda

  DOI：10.1021/ja00283a035

  日期：1986.11

  monoxide took place except for bridgehead alkyl acetates. The mechanism of the catalytic reaction has been proposed, and the importance of the silycobalt carbonyl, R/sub 3/SiCO(CO)/sub 4/, as the key catalyst species has been suggested. The high affinity of the silicon in R/sub 3/SiCo(CO)/sub 4/ toward the oxygen atom in the ester is suggested to be the driving force for the formation of alkylcobalt carbonyls

  酯和内酯与氢硅烷和一氧化碳在 Co/sub 2/(CO)/sub 8/ 存在下的催化反应已被详细研究，重点是它们在有机合成中的效用。乙酸仲烷基酯的催化反应经过一氧化碳的完全结合，得到（甲硅烷氧基亚甲基）烷烃（烯醇甲硅烷基醚）。仲烷基酯类型的内酯类似地反应。甲硅烷氧基甲基化产物转化为醛。乙酸伯烷基酯以非选择性方式产生多种产物。在叔烷基酯的情况下，除了桥头烷基乙酸酯外，没有发生一氧化碳的掺入。已经提出了催化反应的机理，以及羰基硅钴的重要性，R/sub 3/SiCO(CO)/sub 4/，作为已提出的关键催化剂种类。R/sub 3/SiCo(CO)/sub 4/ 中的硅对酯中氧原子的高亲和力被认为是形成作为中间体的烷基羰基钴的驱动力。这一步说明了一种形成碳-过渡金属键的新方法。
• A New Synthetic Application of 1,2-Benzodithiolium Cations: Synthesis of Aldehydes by 1-Carbon Homologation of Carbonyl Compounds
  作者：Maurizio Ceruti、Iacopo Degani、Rita Fochi

  DOI：10.1055/s-1987-27857

  日期：——

  Eleven aldehydes (6a-1) were synthesized by 1-carbon homologation of ketones and aldehydes according to the following sequence: Horner-Emmons reaction of 2-(O,O-dimethylphosphonyl)-1,3-benzodithiole (1)and various carbonyl compounds (2) to give benzo-1,4-dithiafulvenes (3); reduction with sodium borohydride and tetrafluoroboric acid-ether complex in dry acetonitrile to 1,3-benzodithioles (5); subsequent hydrolysis of these with mercury(II)oxide and aqueous tetrafluoroboric acid (35%) in tetrahydrofuran. The procedure is simple, of wide application, and afforded pure aldehydes in good overall yields (55-88%).

  通过1-碳同系化合成11种醛（6a-1），其合成路线如下：2-(O,O-二甲基膦酰基)-1,3-苯并二硫酚（1）与各种羰基化合物（2）进行Horner-Emmons反应，得到苯并-1,4-二硫富烯（3）；在无水乙腈中用硼氢化钠和四氟硼酸-醚络合物还原为1,3-苯并二硫酚（5）；接着在四氢呋喃中用氧化汞和35%的四氟硼酸水溶液进行水解。该方法简便、适用广泛，最终以较高总收率（55-88%）得到纯净的醛。