6-(2,2':6',2''-terpyridin-4'-yloxy)hexanoic acid | 359858-14-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-(2,2':6',2''-terpyridin-4'-yloxy)hexanoic acid
• 英文别名: 6-(2,6-Dipyridin-2-ylpyridin-4-yl)oxyhexanoic acid
• CAS: 359858-14-3
• 化学式: C₂₁H₂₁N₃O₃
• 分子量: 363.416
• InChiKey: SWUABMPHXQCDEO-UHFFFAOYSA-N

物化性质

• 熔点：
  187 °C(Solv: tetrahydrofuran (109-99-9))
• 沸点：
  577.3±50.0 °C(Predicted)
• 密度：
  1.208±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  85.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-(2,2':6',2''-terpyridin-4'-yloxy)hexanoic acid 在 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 生成 2'-amino-3'-O-(2-cyanoethoxy(diisopropylamino)phosphino)-2'-deoxy-5'-O-(4,4'-dimethoxytrityl)-2'-N-(6-(2,2':6',2''-terpyridin-4'-yloxy)hexanoyl)uridine
  参考文献：
  名称：

  Effective Modulation of DNA Duplex Stability by Reversible Transition Metal Complex Formation in the Minor Groove

  摘要：

  Herein we describe the reversible changing of DNA duplex thermal stability by exploiting transition metal complexation phenomena. A terpyridine ligand was conjugated to the N2'-atoms of 2'-amino-2'-deoxyuridine and its locked counterpart 2'-amino-LNA, and these metal-complexing monomers were incorporated into oligodeoxyribonucleotides. Upon addition of varying amounts of transition metal ions, the thermal stability of DNA duplexes containing these terpyridine-functionalized units in different constitutions was affected to different degrees (Delta T-m values = -15.5 to +49.0 degrees C, relative to the unmodified duplex). The most pronounced effects were observed when two complexing monomers were positioned in opposite strands. Addition of 1 equiv of Ni2+ to such a system induced extraordinary duplex stabilization. Molecular modeling studies suggest, as an explanation for this phenomenon, formation of nickel-mediated interstrand linkages in the minor groove. Addition of an excess of metal ions resulted in largely decreased T-m values. Alternating addition of metal ions and EDTA demonstrated reversibility of metal ion-induced changes in hybridization strength, proving that the described approach provides an efficient method for duplex stability modulation.

  DOI：

  10.1021/ja071076z
• 作为产物：
  描述：

  6-己内酯 、 4'-氯-2,2':6',2''-三联吡啶 在 氢氧化钾 作用下， 以 二甲基亚砜 为溶剂， 反应 48.5h， 以83%的产率得到6-(2,2':6',2''-terpyridin-4'-yloxy)hexanoic acid
  参考文献：
  名称：

  用于高分子化学和纳米科学的新型 4'-功能化 2,2':6',2''-三联吡啶

  摘要：

  众所周知的 4'-氯-2,2':6',2''-三联吡啶与醇盐亲核试剂反应生成 4'-官能化的 2,2':6',2''-三联吡啶。该反应允许在一个反应​​步骤中容易地将不同的官能团引入三联吡啶的4'-位，即与金属结合位点相反。在此处报道的官能化 2,2':6',2''-三联吡啶中包括胺（包括手性实例）、羧酸、具有不同链长的简单烷氧基链三联吡啶和二苯乙烯官能化三联吡啶。此外，两种重要的已知物质的合成得到了显着改善。还报道了（氨基戊氧基）三联吡啶与二硫杂环戊烷官能团顺序官能化的一个例子。对于两个烷基链官能化的三联吡啶，获得了单晶 X 射线晶体学数据。最后，使用 STM 观察 HOPG 上烷基取代的三联吡啶的有序单层。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300327

文献信息

• New 4′-Functionalized 2,2′:6′,2′′-Terpyridines for Applications in Macromolecular Chemistry and Nanoscience
  作者：Philip R. Andres、Ralph Lunkwitz、Gunther R. Pabst、Karlheinz Böhn、Daan Wouters、Stefan Schmatloch、Ulrich S. Schubert

  DOI：10.1002/ejoc.200300327

  日期：2003.10

  The well-known reaction of 4′-chloro-2,2′:6′,2′′-terpyridine with alkoxide nucleophiles leads to 4′-functionalized 2,2′:6′,2′′-terpyridines. This reaction allows the easy introduction of different functional groups onto the terpyridine at the 4′-position, i.e. opposite to the metal binding site, in one reaction step. Among the functionalized 2,2′:6′,2′′-terpyridines reported here are amines (including

  众所周知的 4'-氯-2,2':6',2''-三联吡啶与醇盐亲核试剂反应生成 4'-官能化的 2,2':6',2''-三联吡啶。该反应允许在一个反应​​步骤中容易地将不同的官能团引入三联吡啶的4'-位，即与金属结合位点相反。在此处报道的官能化 2,2':6',2''-三联吡啶中包括胺（包括手性实例）、羧酸、具有不同链长的简单烷氧基链三联吡啶和二苯乙烯官能化三联吡啶。此外，两种重要的已知物质的合成得到了显着改善。还报道了（氨基戊氧基）三联吡啶与二硫杂环戊烷官能团顺序官能化的一个例子。对于两个烷基链官能化的三联吡啶，获得了单晶 X 射线晶体学数据。最后，使用 STM 观察 HOPG 上烷基取代的三联吡啶的有序单层。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Synthesis, Spectroscopic Properties, and Photoinduced CO-Release Studies of Functionalized Ruthenium(II) Polypyridyl Complexes: Versatile Building Blocks for Development of CORM–Peptide Nucleic Acid Bioconjugates
  作者：Caroline Bischof、Tanmaya Joshi、Aakanksha Dimri、Leone Spiccia、Ulrich Schatzschneider

  DOI：10.1021/ic400746n

  日期：2013.8.19

  series of ruthenium(II) dicarbonyl complexes of formula [RuCl2(L)(CO)2] (L = bpyCH3,CH3 = 4,4′-dimethyl-2,2′-bipyridine, bpyCH3,CHO = 4′-methyl-2,2′-bipyridine-4-carboxyaldehyde, bpyCH3,COOH = 4′-methyl-2,2′-bipyridine-4-carboxylic acid, CppH = 2-(pyridin-2-yl)pyrimidine-4-carboxylic acid, dppzcH = dipyrido[3,2-a:2′,3′-c]phenazine-11-carboxylic acid), and [RuCl(L)(CO)2]+ (L = tpyCOOH = 6-(2,2′:6′,2″-ter

  一系列式[RuCl 2（L）（CO）2 ]的钌（II）二羰基配合物（L = bpy CH3，CH3 = 4,4'-二甲基-2,2'-联吡啶，bpy CH3，CHO = 4 '-甲基-2,2'-联吡啶-4-羧醛，bpy CH3，COOH = 4'-甲基-2,2'-联吡啶-4-羧酸，CppH = 2-（吡啶-2-基）嘧啶- 4-羧酸，dppzcH =二吡啶基[3,2-a：2'，3'-c]吩嗪-11-羧酸）和[RuCl（L）（CO）2 ] +（L = tpy COOH合成了6-（2,2'：6'，2''-叔吡啶-4'-酰氧基）己酸）。此外，还开发了高产率的含有2-（吡啶-2-基）嘧啶配体的肽核酸（PNA）单体的合成方法，并将该化合物用于制备第一个Ru（II）二羰基配合物，将[RuCl 2（CPP-L-PNA）（CO）2 ]，（CPP-L-PNA =叔丁基- ñ - [2-（ñ -9-芴）氨基乙基]
• 4′-Functionalized 2,2′:6′,2″-terpyridines as building blocks for supramolecular chemistry and nanoscience
  作者：Ulrich S Schubert、Christian Eschbaumer、Oliver Hien、Philip R Andres

  DOI：10.1016/s0040-4039(01)00796-1

  日期：2001.7

  Different mono- and bis-terpyridines were synthesized utilizing nucleophilic substitution of 4′-chloro-2,2′:6′,2″-terpyridine. In the case of the mono-functionalized ligands, different functional groups opposite to the metal binding site could be introduced; with the bis-functionalized ligands building blocks for metal-containing polymers with a tailored alkyl-chain length were accessible. As examples

  利用4'-氯-2,2'：6'，2''-叔吡啶的亲核取代合成了不同的单-和双-吡啶。在单官能化配体的情况下，可以引入与金属结合位点相反的不同官能团；例如，具有双官能化的配体的结构单元可用于具有定制的烷基链长度的含金属聚合物。作为实例，制备了官能化的三联吡啶镉（II）配合物以及富勒烯衍生物。
• Identification of efficient and sequence specific bimolecular artificial ribonucleases by a combinatorial approach
  作者：Marcin Kalek、Peter Benediktson、Birte Vester、Jesper Wengel

  DOI：10.1039/b712532a

  日期：——

  Chemically modified nucleotide monomers were incorporated into adjacent terminal positions of two separate oligonucleotides complementary to an RNA target; all possible combinations of the catalytic units were tested, resulting in an artificial nuclease that showed high activity and catalytic turnover.

  将经过化学修饰的核苷酸单体加入与 RNA 目标互补的两个独立寡核苷酸的相邻末端位置；对催化单元的所有可能组合进行了测试，最终得到了一种具有高活性和高催化周转率的人工核酸酶。
• Insertion of an internal dipeptide into PNA oligomers: Thermal melting studies and further functionalization
  作者：Tim Kersebohm、Srec̀ko I. Kirin、Nils Metzler-Nolte

  DOI：10.1016/j.bmcl.2006.02.071

  日期：2006.6

  The solid phase synthesis of PNA oligomers with the internal dipeptide Gly-Phe is presented and the interaction with complementary DNA investigated. UV absorbance melting experiments with different but complementary DNA sequences show that stable PNA x DNA duplexes are only obtained when there is no DNA base opposite the dipeptide unit. Instead, the dipeptide spacer forms a loop-like structure within

  提出了具有内部二肽Gly-Phe的PNA低聚物的固相合成，并研究了其与互补DNA的相互作用。使用不同但互补的DNA序列进行的UV吸收熔解实验表明，只有当二肽单元对面没有DNA碱基时，才能获得稳定的PNA x DNA双链体。相反，二肽间隔物在双链体中形成环状结构。描述了用N-杂环配体的进一步官能化。在固相合成过程中，引入对硝基苯丙氨酸代替苯丙氨酸，随后将其还原为对氨基苯丙氨酸。与活化酸的反应提供了高产率和高纯度的配体结合物。该策略为在PNA化学中进行大量内部取代开辟了一条通用途径。