9-benzyl-9H-purin-2-amine | 226247-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 9-benzyl-9H-purin-2-amine
• 英文别名: 9-Benzylpurin-2-amine
• CAS: 226247-80-9
• 化学式: C₁₂H₁₁N₅
• 分子量: 225.253
• InChiKey: XIVMTDGNMPFFMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  69.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  9-benzyl-9H-purin-2-amine 在 四(三苯基膦)钯 溴 作用下， 以 N-甲基吡咯烷酮 、 二氯甲烷 为溶剂， 生成 2-amino-8-cyano-9-benzylpurine
  参考文献：
  名称：

  Highly fluorescent donor–acceptor purines

  摘要：

  制备出的受体嘌呤在有机溶液中显示出近乎统一的荧光量子产率，这是将简单的生物相关杂环用于光电和光子应用的一个步骤。

  DOI：

  10.1039/b618171f
• 作为产物：
  描述：

  9-苄基-6-氯嘌呤-2-胺 在 水 、 氧气 、 一水合肼 、 copper(II) sulfate 作用下， 以 乙醇 为溶剂， 反应 8.0h， 生成 9-benzyl-9H-purin-2-amine
  参考文献：
  名称：

  Efficient synthesis of nebularine and vidarabine via dehydrazination of (hetero)aromatics catalyzed by CuSO₄in water

  摘要：

  首次在催化量的CuSO4存在下实现了一步简单的脱氢反应。以CuSO4 (2 mol%)为催化剂，水为溶剂，脱氢产物获得了良好的产率（66-95%）。此外，成功合成了药物 nebularine 和 Vidarabine，并且 Vidarabine 可在0.923公斤规模生产，显示出良好的工业应用潜力。

  DOI：

  10.1039/c3gc41658e

文献信息

• A site selective C–H arylation of free-(NH2) adenines with aryl chlorides: Application to the synthesis of 6,8-disubstituted adenines
  作者：Sophian Sahnoun、Samir Messaoudi、Jean-Daniel Brion、Mouâd Alami

  DOI：10.1039/b912033e

  日期：——

  An efficient site selective method for the direct arylation of free-(NH2) adenines 1 to provide a range of C-8 arylated adenines 3 in excellent yields is described. This process based on the use of Pd(OH)2/C as the catalyst and a stoichiometric amount of CuI under ligandless conditions is general. It allows the coupling to proceed with a variety of aryl halides, including for the first time cheaper

  描述了一种用于自由-（NH 2）腺嘌呤1的直接芳基化的有效位点选择方法，以优异的产率提供了一系列C-8芳基化的腺嘌呤3。通常基于在无配体条件下使用Pd（OH）2 / C作为催化剂和化学计量的CuI的方法。它可以使偶联反应与各种芳基卤化物进行，包括第一次更便宜，反应性更低的芳基氯化物。还报道了该方法的扩展用于顺序制备非对称的C8 / N 6-芳基腺嘌呤4。
• Synthesis, Photophysical Behavior, and Electronic Structure of Push−Pull Purines
  作者：Roslyn S. Butler、Pamela Cohn、Phillip Tenzel、Khalil A. Abboud、Ronald K. Castellano

  DOI：10.1021/ja806348z

  日期：2009.1.21

  purines have been synthesized by the introduction of electron-accepting functional groups (A = CN, CO(2)Me, and CONHR) to the heterocyclic C(8) position to complement typical electron-donating substituents at C(2) (D(1)) and C(6) (D(2)). The donor-acceptor purines show significantly altered, and overall improved photophysical properties relative to their acceptor-free precursors (A = H); these include red-shifted

  “推拉”嘌呤是通过将受电子官能团（A = CN、CO(2)Me 和 CONHR）引入杂环 C(8) 位置合成的，以补充 C( 2) (D(1)) 和 C(6) (D(2))。供体-受体嘌呤相对于它们的无受体前体 (A = H) 显示出显着改变和整体改善的光物理性质；这些包括红移 (20-50 nm) 吸收最大值、高溶剂致变色发射曲线（355-466 nm 的 em λ(max)，取决于取代模式和溶剂），在发射能量和溶剂极性之间具有极好的线性相关性 (E(T) )(N))，提高连续照射时的光化学稳定性，并增强（高达 2500%）荧光量子产率。综合结构性质研究表明吸收/发射最大值和量子产率如何取决于供体和受体结构、相对供体位置（C(2) 或 C(6)）和溶剂（1,4-二恶烷、二氯甲烷、乙腈、甲醇，在某些情况下是水）。对电子结构的进一步了解来自对溶剂相关发射数据（提供 1.9 至 3.4 D 的
• The synthesis of nebularine and its analogs <i>via</i> oxidative desulfuration in aqueous nitric acid
  作者：Ran Xia、Li-Ping Sun、Gui-Rong Qu

  DOI：10.1080/10426507.2016.1225057

  日期：2017.1.2

  GRAPHICAL ABSTRACT ABSTRACT The synthesis of nebularine and its analogs has been achieved via oxidative desulfuration in H2O for the first time. With 50% HNO3 as an oxidant and solvent, 18 products were obtained in good yields (70%–94%). The oxidative desulfuration system could tolerate different functional groups including fluoro, chloro, amino, alkyl, allyl, ribosyl, deoxyribosyl, and arabinofuranosyl

  图形摘要 摘要 nebularine 及其类似物的合成首次通过在 H2O 中氧化脱硫实现。以 50% HNO3 作为氧化剂和溶剂，以良好的收率 (70%–94%) 获得了 18 种产物。氧化脱硫系统可以耐受不同的官能团，包括氟、氯、氨基、烷基、烯丙基、核糖基、脱氧核糖基和阿拉伯呋喃糖基。更重要的是，药物 nebularine 可以在 20 g 的规模上成功获得，这使得该路线对工业应用更具吸引力。
• Nucleic Acid Related Compounds. 136. Synthesis of 2-Amino- and 2,6-Diaminopurine Derivatives via Inverse-Electron-Demand Diels-Alder Reactions
  作者：Xiaoyu Lin、Morris J. Robins

  DOI：10.1135/cccc20061029

  日期：——

  Thermal inverse-electron-demand Diels-Alder reactions of 5-aminoimidazoles and 2,4,6-tris(ethoxycarbonyl)-1,3,5-triazine (2) with spontaneous retro-Diels-Alder loss of ethyl cyanoformate and elimination of ammonia give 2,6-bis(ethoxycarbonyl)purines. A report that selective alkaline hydrolysis followed by acid-catalyzed decarboxylation gave 6-(ethoxycarbonyl)purine products was not in harmony with known reactions in purine chemistry. Our reinvestigation has shown that the 6-(ethoxycarbonyl) group undergoes preferential base-promoted hydrolysis, as expected, but regioselectivity for attack of hydroxide at the carbonyl group at C6 is not high (relative to hydrolysis of both C2 and C6 esters). The structure of 9-benzyl-2-(ethoxycarbonyl)purine was determined by X-ray crystallography and confirmed by Curtius rearrangement of the azidocarbonyl analogue to give 2-amino-6-benzylpurine. Acid-catalyzed decarboxylation of the 2,6-dicarboxylate formed during hydrolysis gave 9-benzylpurine, and Curtius rearrangement of 2,6-bis(azidocarbonyl)-9-benzylpurine gave 2,6-diamino-9-benzylpurine. Attempted applications of inverse-electron-demand Diels-Alder reactions of 2 with nucleoside derivatives were problematic.

  5-氨基咪唑和2,4,6-三(乙氧羰基)-1,3,5-三嗪的热反向电子需求Diels-Alder反应与乙基氰甲酸乙酯自发性逆Diels-Alder失去和氨的消除反应，形成2,6-双(乙氧羰基)嘌呤。一份报告指出，选择性碱水解后接酸催化脱羧可得到6-(乙氧羰基)嘌呤产物，但与嘌呤化学中已知的反应不一致。我们的再研究表明，6-(乙氧羰基)基团更倾向于碱促水解，但羟基攻击C6羰基的区域选择性并不高（相对于C2和C6酯的水解）。9-苄基-2-(乙氧羰基)嘌呤的结构经X射线晶体学确定，并通过Curtius重排验证了其氮氧羰基类似物的2-氨基-6-苄基嘌呤。在水解过程中形成的2,6-二羧酸酯的酸催化脱羧产生了9-苄基嘌呤，而2,6-双(氮氧羰基)-9-苄基嘌呤的Curtius重排产生了2,6-二氨基-9-苄基嘌呤。尝试使用反向电子需求Diels-Alder反应与核苷衍生物的2进行应用时出现问题。
• Addition and Cycloaddition to 2- and 8-Vinylpurines.
  作者：Fusheng Liu、Bjørn Dalhus、Lise-Lotte Gundersen、Frode Rise、Inger Søtofte、Jørgen Møller、Alexander Senning、Xin-Kan Yao、Hong-Gen Wang、J. -P. Tuchagues、Mattias Ögren

  DOI：10.3891/acta.chem.scand.53-0269

  日期：——

  The reactivity of purines carrying an alkenyl substituent in the 2- or 8-position in nucleophilic addition and cycloaddition reactions has been studied. A vinyl substituent situated at C-8 is highly electrophilic and readily participates as a Michael acceptor in nucleophilic additions and as a dienophile in Diels-Alder reactions. 2-Vinylpurines may also give addition and cycloaddition products. When benzenethiol was added to 9-benzyl-2-vinylpurine, both the simple adduct as well as 9-benzyl-2-(2-phenylthio-1-hydroxyethyl)-9H-purine were formed. The structure of the latter compound was determined by single-crystal X-ray methods.