9-benzyl-6-(phenylethynyl)-9H-purine | 292036-87-4

• 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-6-(phenylethynyl)-9H-purine
• 英文别名: 9-benzyl-6-(phenylethynyl)purine；9-Benzyl-6-(2-phenylethynyl)purine
• CAS: 292036-87-4
• 化学式: C₂₀H₁₄N₄
• 分子量: 310.358
• InChiKey: WRIGMYJLOIMKSY-UHFFFAOYSA-N

物化性质

• 熔点：
  116-118 °C(Solv: toluene (108-88-3))
• 沸点：
  548.3±60.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  43.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  9-benzyl-6-(phenylethynyl)-9H-purine 在 bis-triphenylphosphine-palladium(II) chloride 、 三正丁基氢锡 、 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以82%的产率得到9-Benzyl-6-[(E)-styryl]purine
  参考文献：
  名称：

  Synthesis of (E)-6-alkenylpurines via Pd-catalyzed stannation/protodestannation tandem process of alkynylpurines

  摘要：

  介绍了一种从6-碘嘌呤出发，基于Pd催化的锡化/脱锡化协议，合成（E）-6-烯基嘌呤的方法。炔基化反应在乙腈中由Pd（OAc）2 / PPh3催化。 Pd催化的锡化本身提供了混合的Z-异构体，但是使用TFA进行脱锡化后，引发了Z到E的异构化，从而得到（E）-6-烯基嘌呤。还研究了其他2-和8-炔基嘌呤的反应性。

  DOI：

  10.1135/cccc2009563
• 作为产物：
  描述：

  9-苄基-6-碘嘌呤 、 苯乙炔 在 palladium diacetate 、 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以92%的产率得到9-benzyl-6-(phenylethynyl)-9H-purine
  参考文献：
  名称：

  Synthesis of (E)-6-alkenylpurines via Pd-catalyzed stannation/protodestannation tandem process of alkynylpurines

  摘要：

  介绍了一种从6-碘嘌呤出发，基于Pd催化的锡化/脱锡化协议，合成（E）-6-烯基嘌呤的方法。炔基化反应在乙腈中由Pd（OAc）2 / PPh3催化。 Pd催化的锡化本身提供了混合的Z-异构体，但是使用TFA进行脱锡化后，引发了Z到E的异构化，从而得到（E）-6-烯基嘌呤。还研究了其他2-和8-炔基嘌呤的反应性。

  DOI：

  10.1135/cccc2009563

文献信息

• 9-Benzylpurines with inhibitory activity against Mycobacterium tuberculosis
  作者：Anne Kristin Bakkestuen、Lise-Lotte Gundersen、Geir Langli、Fusheng Liu、Jens M.J Nolsøe

  DOI：10.1016/s0960-894x(00)00188-8

  日期：2000.6

  the 2-, 6- and/or 8-position have been prepared and screened for antimycobacterial effects. High inhibitory activity against Mycobacterium tuberculosis was found for 9-benzylpurines carrying a phenylethynyl-, trans-styryl or aryl substituents in the 6-position and generally chlorine in the 2-position tends to increase activity.

  已经制备了在2-，6-和/或8-位具有多种取代基的9-苄嘌呤，并对其抗分枝杆菌作用进行了筛选。发现对于在6-位带有苯基乙炔基，反式-苯乙烯基或芳基取代基的9-苄基嘌呤具有高的抗结核分枝杆菌活性，并且通常在2-位带有氯趋于增加活性。
• 6-Alkynylpurines bearing electronacceptor substituents: Preparation, reactivity in cycloaddition reactions and cytostatic activity
  作者：Martin Křováček、Hana Dvořáková、Ivan Votruba、Ivana Císařová、Dalimil Dvořák

  DOI：10.1135/cccc2011176

  日期：——

  While direct Sonogashira coupling of 6-halopurines with methyl propiolate and with propargyl aldehyde was not successful, the corresponding orthoester and propargyl aldehyde diethylacetal reacted smoothly. Such prepared orthoester was then converted to the desired methylester by methanolysis, the acetal was too stable to be hydrolyzed. The obtained 6-ethynylpurines, bearing orthoester, acetal, methoxycarbonyl and for comparison also the phenyl substituent on the ethynyl group, were subjected to the cycloaddition reaction with cyclopentadiene, diazomethane and phenylazide. Electron deficient alkynylpurines were considerably more reactive in this reaction compared to the not activated phenylethynyl derivative. The prepared alkynylpurines exhibited medium cytostatic activity (IC₅₀ = 2.6–15 μM), while the cycloadducts were inactive.

  直接的Sonogashira偶联反应无法成功地将6-卤代嘌呤与丙烯酸甲酯和丙炔醛偶联，但相应的orthoester和丙炔醛二乙醇缩醛却能顺利反应。制备的orthoester随后通过甲醇解反应转化为所需的甲酯，而缩醛却过于稳定而无法水解。所得的6-乙炔基嘌呤，带有orthoester、缩醛、甲氧羰基和为了比较而添加的苯基取代基，被用于与环戊二烯、重氮甲烷和苯基叠氮化物进行环加成反应。与未活化的苯基乙炔衍生物相比，电子不足的炔基嘌呤在这个反应中表现出更高的反应性。制备的炔基嘌呤表现出中等的细胞毒素活性（IC50=2.6-15μM），而环加成产物则无活性。
• Novel Method for Preparation of Highly Substituted 6-Arylpurines by Reactions of 6-Alkynylpurines with Zirconacyclopentadienes
  作者：Pavel Turek、Martin Kotora、Michal Hocek、Ivan Votruba

  DOI：10.1135/cccc20050339

  日期：——

  Reactions of various zirconacyclopentadienes bearing alkyl and aryl groups with 6-alkynylpurines in the presence of NiBr₂(PPh₃)₂ afforded the corresponding 6-arylpurines with highly hydrophobic aryl moieties in low to moderate yields. Some of the title purines showed interesting cytostatic activity.

  在NiBr₂(PPh₃)₂的存在下，带有烷基和芳基的各种锆茂环戊二烯与6-炔基嘌呤反应，得到了相应的6-芳基嘌呤，其芳基部分具有高度疏水性，收率低至中等。其中一些嘌呤表现出有趣的细胞毒抑制活性。
• Covalent Analogues of DNA Base-Pairs and Triplets IV. Synthesis of Trisubstituted Benzenes Bearing Purine and/or Pyrimidine Rings by Cyclotrimerization of 6-Ethynylpurines and/or 5-Ethynyl-1,3-dimethyluracil
  作者：Michal Hocek、Irena G. Stará、Ivo Starý、Hana Dvořáková

  DOI：10.1135/cccc20021223

  日期：——

  Ni-Catalyzed cyclotrimerizations of 6-ethynylpurines 3 or 5-ethynyl-1,3-dimethyluracil (4) afforded the 1,2,4-tris(purin-6-yl)benzenes 7 or 1,2,4-tris(1,3-dimetyhyluracil-5-yl)benzene (9), respectively. The symmetrical 1,3,5-tris(purin-6-yl)benzenes 8 were also formed as minor products in very low yields. Co-cyclotrimerization of 9-benzyl-6-ethynylpurine (3a) with 4 afforded the tris(purinyl)benzene 7a as a major product along with 1,2-bis(9-benzylpurin-6-yl)-4-(1,3-dimethyluracil-5-yl)benzene (10) and a complex mixture of other derivatives and isomers. Compounds 7-10 are analogues of Hoogsteen base-triplets.

  Ni催化的6-乙炔基嘌呤（3）或5-乙炔基-1,3-二甲基尿嘧啶（4）的环三聚反应生成了1,2,4-三（嘌呤-6-基）苯（7）或1,2,4-三（1,3-二甲基尿嘧啶-5-基）苯（9）。对称的1,3,5-三（嘌呤-6-基）苯（8）作为副产物以极低的收率形式存在。9-苄基-6-乙炔基嘌呤（3a）与4的共环三聚反应生成了三（嘌呤基）苯（7a）作为主要产物，还伴随着1,2-双（9-苄基嘌呤-6-基）-4-（1,3-二甲基尿嘧啶-5-基）苯（10）和其他衍生物和异构体的复杂混合物。化合物7-10是Hoogsteen碱基三联体的类似物。
• [2+2+2]-Co-cyclotrimerization 6-alkynylpurines with diynes: a method for preparation of 6-arylpurines
  作者：Pavel Turek、Martin Kotora、Michal Hocek、Ivana Cı́sařová

  DOI：10.1016/s0040-4039(02)02643-6

  日期：2003.1

  A novel approach to 6-arylpurines based on [2+2+2]-co-cyclotrimerization of 6-alkynylpurines with various alpha,omega-diynes is described. Co-cyclotrimerization is catalyzed by Ni- and Co-phosphine catalysts and their choice depends on the substitution pattern of the both reactants. (C) 2003 Elsevier Science Ltd. All rights reserved.