1,7-di(3-bromobenzyl)cyclen | 1039510-38-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,7-di(3-bromobenzyl)cyclen
• 英文别名: 1,7-Bis[(3-bromophenyl)methyl]-1,4,7,10-tetrazacyclododecane；1,7-bis[(3-bromophenyl)methyl]-1,4,7,10-tetrazacyclododecane
• CAS: 1039510-38-7
• 化学式: C₂₂H₃₀Br₂N₄
• 分子量: 510.315
• InChiKey: GQJKOTHRSAUXFW-UHFFFAOYSA-N

物化性质

• 熔点：
  145-147 °C
• 沸点：
  574.1±45.0 °C(Predicted)
• 密度：
  1.357±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  30.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,7-di(3-bromobenzyl)cyclen 在 potassium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 1,4-二氧六环 、 乙腈 为溶剂， 反应 8.03h， 生成 32,37-dipyrimidin-2-yl-12,15,18-trioxa-1,8,22,29,32,37-hexaazatetracyclo[27.5.5.1(3,7).1(23,27)]hentetraconta-3(41),4,6,23(40),24,26-hexaene
  参考文献：
  名称：

  Synthesis of Macrobi- and Macrotricyclic Compounds Comprising Pyrimidyl Substituted Cyclen and Cyclam

  摘要：

  The synthesis of novel N-1,N-7-bis(bromobenzyl)cyclens and N-1,N-8-bis(bromobenzyl)cyclens is described. Arylation of these compounds with excess 4,6-dichloropyrimidine and 2-chloropyrimidine gave corresponding tetrasubstituted cyclen and cyclam in good yields. Bis(bromobenzyl)bis(pyrimidyl) substituted cyclens and cyclams were used in the Pd-catalyzed reactions with polyamines to give macrobi- and macrotricycles. The yields of macropolycyclic compounds were shown to be dependent on the nature of starting tetraazamacrocycles and polyamines. In the case of cyclam monopyrimidyl derivatives were also obtained and macropolycyclic compounds were synthesized on their base.

  DOI：

  10.3987/com-10-s(e)98
• 作为产物：
  描述：

  3-溴苄溴 在 sodium hydroxide 作用下， 以 乙腈 为溶剂， 生成 1,7-di(3-bromobenzyl)cyclen
  参考文献：
  名称：

  基于含有 1,3-二取代金刚烷部分的 Cyclen 和 cyclam 的大型自行车

  摘要：

  将根据先前描述的程序获得的环烯和环己烯的双（溴苄基）衍生物引入钯催化的与 1,3-双（氨基甲基）金刚烷和 1,3-双（2-氨基乙基）金刚烷的反应中，以中等产率生产大双环。在许多情况下观察到三环环二聚体的形成。Cyclen 和 cyclam 的四苄基衍生物由相应的二苄基衍生物合成，并与 1,3-双（2-氨基乙基）金刚烷反应，以相似的产率得到大双环产物。

  DOI：

  10.3998/ark.5550190.0013.713

文献信息

• Pd-catalyzed amination in the synthesis of cyclen-based macrotricycles
  作者：Sergei M. Kobelev、Alexei D. Averin、Alexei K. Buryak、Franck Denat、Roger Guilard、Irina P. Beletskaya

  DOI：10.1016/j.tetlet.2011.11.024

  日期：2012.1

  Three approaches to three types of cyclen-based macrotricycles have been elaborated starting from trans-bis(3-bromobenzyl)cyclen. The macrotricycles were synthesized via Pd-catalyzed amination. The first approach employed consecutive macrocyclization and benzylation steps giving a cage-like tricycle. In the second, cyclen amino groups were Boc-protected prior to formation of the second and the third rings. In the third method, macrotricycles were synthesized according to a one-step procedure using diazacrown ethers. (C) 2011 Elsevier Ltd. All rights reserved.
• Macrobicyclic and Macrotricyclic Derivatives of N,N’,N’’,N’’’-Tetrasubstituted Cyclen and Cyclam
  作者：Irina P. Beletskaya、Alexei D. Averin、Sergei M. Kobelev、Alexei K. Buryak、Andrei I. Vovk、Valerii P. Kukhar、Franck Denat、Roger Guilard

  DOI：10.3987/com-14-s(k)71

  日期：——

  N,N',N '',N'''-Tetrabenzyl derivatives of cyclen and cyclam possessing two bromine atoms in trans-positioned phenyl rings were introduced in the Pd-catalyzed amination reactions with oxadiamines and polyamines to provide a wide series of macrobicyclic compounds with tetrabenzyl substituted cyclen and cyclam central moieties in yields up to 31%. Macrocycles based on 1,7-dibenzylcyclen were modified with two 3-bromobenzyl substituents and introduced in the Pd-catalyzed macrocyclization with di- and trioxadiamines to afford spherically shaped macrotricyclic cryptands in yields up to 33%. An alternative approach to isomeric macrotricyclic cryptands employed Pd-catalyzed amination of di(Boc)-di(3-bromobenzyl)cyclen followed by the dialkylation of the resulting bicycle with two bromobenzyl groups and final catalytic macrocyclization step (yields up to 24%).
• Synthesis of a new family of bi- and polycyclic compounds via Pd-catalyzed amination of 1,7-di(3-bromobenzyl)cyclen
  作者：Alexei D. Averin、Anton V. Shukhaev、Alexei K. Buryak、Franck Denat、Roger Guilard、Irina P. Beletskaya

  DOI：10.1016/j.tetlet.2008.04.045

  日期：2008.6

  New bicyclic cryptand type compounds are synthesized by reacting 1,7-di(3-bromobenzyl)cyclen with 1 equiv of linear polyamines under dilute conditions using Pd-catalyzed amination. Bis(cyclen) and tris(cyclen) compounds containing linear polyamine linkers between benzylated cyclens are obtained by a similar procedure using different reaction conditions. Cyclization of these species via intramolecular catalytic diamination led to tri- and tetracyclic polyaza compounds. (c) 2008 Elsevier Ltd. All rights reserved.
• Synthesis of Macrobi- and Macrotricyclic Compounds Comprising Pyrimidyl Substituted Cyclen and Cyclam
  作者：Irina P. Beletskaya、Roger Guilard、Sergei M. Kobelev、Alexei D. Averin、Alexei K. Buryak、Franck Denat

  DOI：10.3987/com-10-s(e)98

  日期：——

  The synthesis of novel N-1,N-7-bis(bromobenzyl)cyclens and N-1,N-8-bis(bromobenzyl)cyclens is described. Arylation of these compounds with excess 4,6-dichloropyrimidine and 2-chloropyrimidine gave corresponding tetrasubstituted cyclen and cyclam in good yields. Bis(bromobenzyl)bis(pyrimidyl) substituted cyclens and cyclams were used in the Pd-catalyzed reactions with polyamines to give macrobi- and macrotricycles. The yields of macropolycyclic compounds were shown to be dependent on the nature of starting tetraazamacrocycles and polyamines. In the case of cyclam monopyrimidyl derivatives were also obtained and macropolycyclic compounds were synthesized on their base.
• Macrobicycles based on cyclen and cyclam containing 1,3-disubstituted adamantane moiety
  作者：Sergei M. Kobelev、Alexei D. Averin、Alexei K. Buryak、Evgenii N. Savelyev、Boris S. Orlinson、Gennadii M. Butov、Ivan A. Novakov、Franck Denat、Roger Guilard、Irina P. Beletskaya

  DOI：10.3998/ark.5550190.0013.713

  日期：——

  Bis(bromobenzyl)derivatives of cyclen and cyclam obtained according to previously described procedures were introduced in a palladium-catalyzed reaction with 1,3bis(aminomethyl)adamantane and 1,3-bis(2-aminoethyl)adamantane to produce macrobicycles in moderate yields. The formation of tricyclic cyclodimers was observed in many cases. Tetrabenzyl derivatives of cyclen and cyclam were synthesized from the

  将根据先前描述的程序获得的环烯和环己烯的双（溴苄基）衍生物引入钯催化的与 1,3-双（氨基甲基）金刚烷和 1,3-双（2-氨基乙基）金刚烷的反应中，以中等产率生产大双环。在许多情况下观察到三环环二聚体的形成。Cyclen 和 cyclam 的四苄基衍生物由相应的二苄基衍生物合成，并与 1,3-双（2-氨基乙基）金刚烷反应，以相似的产率得到大双环产物。