金刚烷-1-基(吡咯烷-1-基)甲酮 | 22508-51-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 中文名称: 金刚烷-1-基(吡咯烷-1-基)甲酮
• 英文名称: adamantan-1-yl(pyrrolidin-1-yl)methanone
• 英文别名: ((pyrrolidinyl)tricyclo[3.3.1.1^3,7]dec-1-yl)methanone；((3r,5r,7r)-adamantan-1-yl)(pyrrolidin-1-yl)methanone；1-adamantyl(pyrrolidin-1-yl)methanone
• CAS: 22508-51-6
• 化学式: C₁₅H₂₃NO
• mdl: MFCD00154659
• 分子量: 233.354
• InChiKey: RVXVNLMWQYKNHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.933
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  金刚烷-1-基(吡咯烷-1-基)甲酮 在 diborane(6) 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到1-Adamantan-1-ylmethyl-pyrrolidine
  参考文献：
  名称：

  Amines That Transport Protons across Bilayer Membranes:  Synthesis, Lysosomal Neutralization, and Two-Phase pK_a Values by NMR

  摘要：

  It is desirable to be able to control the pH of lysosomes. A collection of lipophilic, nitrogenous bases, designed to act as membrane-active, catalytic proton transfer agents, were prepared and their effective pK(a)s measured in a vigorously stirred, two-phase system. One phase was a phosphate buffer whose pH was varied over the range ca, 1-11. The other was an immiscible, deuterated organic solvent in which the compounds preferentially resided even when protonated. When chemical shift changes versus the pH of the buffer were plotted, clear pK(a) curves were generated that are relevant to transmembrane proton transfer behavior. The two-phase pK(a)s increased with increasing counterion lipophilicity and with increasing organic solvent polarity, The compounds were also tested for their ability to neutralize the acidity of lysosomes, a model for other acidic vesicles involved in drug sorting. The most successful of these, imidazole 6a, has > 100 times the neutralizing power of ammonia, a standard lysosomotropic amine, causing a 1.7 unit rise in lysosomal pH of RAW cells at 0.1 mM, compared to a 0.2 and 1.4 unit rise for ammonium chloride at 0.1 and 10 mM, respectively.

  DOI：

  10.1021/jo960367f
• 作为产物：
  描述：

  1-溴金刚烷 在 aluminum (III) chloride 、 氧气 、 caesium carbonate 作用下， 以 硝基甲烷 、 乙腈 为溶剂， 50.0 ℃ 、101.33 kPa 条件下， 反应 25.0h， 生成 金刚烷-1-基(吡咯烷-1-基)甲酮
  参考文献：
  名称：

  使用O2立体要求α-取代的丙二腈与胺进行氧化酰胺化反应。

  摘要：

  简单地使用分子氧和碳酸盐碱即可实现易于获得的1,1-二氰基烷烃与手性或非手性胺之间的高效酰胺化方法。该氧化方案可以高度化学选择性，实用和快速的方式应用于空间和电子挑战性底物。环丙基和硫醚底物的使用可支持α-过氧丙二腈物种的自由基形成，后者可以环化成二恶英，后者可以单价氧化丙二腈α-碳二酮以提供能够与胺亲核试剂反应的活化的酰基氰化物。

  DOI：

  10.1002/anie.201603399

文献信息

• A Fast and General Route to Ketones from Amides and Organolithium Compounds under Aerobic Conditions: Synthetic and Mechanistic Aspects
  作者：Simone Ghinato、Davide Territo、Andrea Maranzana、Vito Capriati、Marco Blangetti、Cristina Prandi

  DOI：10.1002/chem.202004840

  日期：2021.2.5

  We report that the nucleophilic acyl substitution reaction of aliphatic and (hetero)aromatic amides by organolithium reagents proceeds quickly (20 s reaction time), efficiently, and chemoselectively with a broad substrate scope in the environmentally responsible cyclopentyl methyl ether, at ambient temperature and under air, to provide ketones in up to 93 % yield with an effective suppression of the

  我们报道，脂肪族和（杂）芳族酰胺通过有机锂试剂的亲核酰基取代反应进行迅速（20 s反应时间），有效地进行，并且在环境温度和环境温度下，在对环境负责的环戊基甲基醚中具有广泛的底物范围进行化学选择性空气，以提供高达93％的产率的酮，并有效抑制臭名昭著的加成反应。详细的DFT计算和NMR研究支持了实验结果。事实证明，所描述的方法适用于规模扩大和可回收性协议。与在惰性气氛下进行的经典程序相反，这项工作为羧酸酰胺与有机锂的反应性发生深刻的范式转变奠定了基础，
• Uncovering the Importance of Proton Donors in TmI ₂ ‐Promoted Electron Transfer: Facile CN Bond Cleavage in Unactivated Amides
  作者：Michal Szostak、Malcolm Spain、David J. Procter

  DOI：10.1002/anie.201303178

  日期：2013.7.8

  for the development of challenging electron‐transfer processes. It was demonstrated that alcohols are critical for the formation of a thermodynamically more powerful reductant from TmI2 (thulium diiodide), the first nonclassical lanthanide(II) iodide in the series (TmI2, DyI2, NdI2). The TmI2(ROH)n reagent promotes an unprecedented cleavage of the σ CN bond in amides.

  非经典镧系 (II) 碘化物是用于开发具有挑战性的电子转移过程的现代试剂。事实证明，醇对于从 TmI 2（二碘化铥）（该系列中的第一种非经典镧系元素 (II) 碘化物（TmI 2、 DyI 2、 NdI 2 ））形成热力学更强大的还原剂至关重要。TmI 2 (ROH) n试剂促进酰胺中 σ C  N 键前所未有的断裂。
• COSMETIC COMPOSITIONS WITH TRICYCLODECANE AMIDES
  申请人：Conopco, Inc., d/b/a UNILEVER

  公开号：US20160008249A1

  公开（公告）日：2016-01-14

  The invention is directed to a cosmetic composition and the precursor thereof. The composition has solid agent and liquid agent, both of which are cosmetic benefit ingredients. The solubility of solid agents in liquid agents in the inventive compositions is enhanced in the presence of a tricyclodecane amide.

  该发明涉及一种化妆品组合物及其前体。该组合物具有固体剂和液体剂，两者均为化妆品益处成分。在创新组合物中，固体剂在液体剂中的溶解性在三环十二碳酰胺的存在下得到增强。
• [EN] PHOTOPROTECTIVE COMPOSITIONS WITH TRICYCLODECANE AMIDES<br/>[FR] COMPOSITIONS DE PHOTOPROTECTION CONTENANT DES TRICYCLODÉCANES AMIDES
  申请人：UNILEVER PLC

  公开号：WO2014139965A1

  公开（公告）日：2014-09-18

  A personal care photoprotective composition is provided having a UV-A and UV-B sunscreen in conjunction with a tricyclodecane amide. The tricyclodecane amide functions to boost UV-A, UV-B and SPF performance when the personal care composition is applied to skin or hair of the human body.

  提供一种个人护理光保护组合物，其中包含UV-A和UV-B防晒剂，以及三环十二烷酰胺。当该个人护理组合物被涂抹在人体皮肤或头发上时，三环十二烷酰胺能够增强UV-A、UV-B和SPF的性能。
• Highly Chemoselective Transamidation of Unactivated Tertiary Amides by Electrophilic N−C(O) Activation by Amide‐to‐Acyl Iodide Re‐routing
  作者：Dongxu Zuo、Qun Wang、Long Liu、Tianzeng Huang、Michal Szostak、Tieqiao Chen

  DOI：10.1002/anie.202202794

  日期：2022.6.13

  The challenging transamidation of unactivated tertiary amides using equivalent amounts of amines has been accomplished via cooperative acid/iodide catalysis. The method provides a novel manifold to re-route the reactivity of unactivated and unreactive N,N-dialkyl amides through reactive acyl iodide intermediates, representing a powerful new activation mode of unactivated amide bonds.

  使用等量的胺对未活化的叔酰胺进行具有挑战性的转酰胺化反应是通过协同酸/碘化物催化完成的。该方法提供了一种新的方法，通过反应性酰碘中间体重新引导未活化和未反应性N,N-二烷基酰胺的反应性，代表了一种强大的未活化酰胺键的新活化模式。