1,3-(oxytetraethylenoxy)-1,3,5,5-tetrachloro-cyclotriphosphazatriene | 200011-80-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3-(oxytetraethylenoxy)-1,3,5,5-tetrachloro-cyclotriphosphazatriene
• 英文别名: 1,3-(oxytetraethylenoxy)-1,3,5,5-tetrachlorocyclotriphosphazen；1,15,17,17-Tetrachloro-2,5,8,11,14-pentaoxa-16,18,19-triaza-1lambda5,15lambda5,17lambda5-triphosphabicyclo[13.3.1]nonadeca-1(19),15,17-triene；1,15,17,17-tetrachloro-2,5,8,11,14-pentaoxa-16,18,19-triaza-1λ5,15λ5,17λ5-triphosphabicyclo[13.3.1]nonadeca-1(19),15,17-triene
• CAS: 200011-80-9
• 化学式: C₈H₁₆Cl₄N₃O₅P₃
• 分子量: 468.965
• InChiKey: YXXZLWFIRYHKLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  83.2
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,3-(oxytetraethylenoxy)-1,3,5,5-tetrachloro-cyclotriphosphazatriene 在 sodium hydroxide 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 34.0h， 生成 1-{2-[1,3-(oxytetraethylenoxy)-3,5,5-tri(phenyloxy-2-carboxaldehyde)cyclotriphosphazatrien-1-yl]aminoethylamino}anthraquinone
  参考文献：
  名称：

  一些新的1,3-（氧四亚乙基氧基）环三磷腈衍生物的合成和体外抗白血病活性。

  摘要：

  具有2-氯乙胺或水杨醛（2-羟基苯甲醛）或其席夫碱（在与2-氯乙胺缩合后）单元并且还具有2-萘基或蒽醌基团作为取代基的一系列新的1,3-（氧四乙氧基）环三磷腈衍生物合成的。已经研究了这些化合物对四种癌细胞系的体外细胞毒性活性。在合成试剂的国际标准（4微克/毫升）的范围内，大多数化合物对选择用于测试的MOLT4，L 1210，HL-60和P388细胞系均具有抗增殖活性。

  DOI：

  10.1021/jm0490078
• 作为产物：
  描述：

  三缩四乙二醇 在 六氯环三磷腈 、 sodium hydride 作用下， 以23.5%的产率得到1,3-(oxytetraethylenoxy)-1,3,5,5-tetrachloro-cyclotriphosphazatriene
  参考文献：
  名称：

  New Lariat Ether-Type Macrocycles with Cyclophosphazene Subunits

  摘要：

  New side-armed ligands of lariat ether type 6-13 have been synthesized by the respective phenolysis and naphtholysis reactions of the parent isomeric ansa (2, 4) and spiro (3, 5) macrocyclosubstituted cyclophosphazenes of general formula N3P3Cl4[O(CH2CH2O)(n)] (where n = 4, 5), separated by column chromatograhy, and characterized by mass spectrometry and H-1 and P-31 NMR spectroscopies. The synthesized side-armed ligands 6-13, as well as their respective functional chlorine-containing precursors 2-5, represent crown ethers with cyclophosphazene subunits and may thus be considered as diphosphaza[16]crown-6 or PNP16C6 (2, 6, 10), diphosphaza[19]crown-7 or PNP19C7 (4, 8, 12), phospha[14]crown-5 or P14C5 (3, 7, 11), and phospha[17]crown-6 or P17C6 (5, 9, 13). The one-pot method of synthesis developed for (aryloxy)-crowns 6-13, with the phenolysis (or naphtholysis) performed in situ immediately after completing the formation of the respective chlorine-containing macrocycles 2-5, made it possible to obtain high yields of the corresponding 16- and 19-membered ansa-PNP-cyclosubstituted side-armed diphosphaza-crowns PNP16C6 and PNP19C7 (6, 8, 10, 12) and to isolate the stable 14- and 17-membered spiro-P derivatives P14C5 and P17C6 (7, 9, 11, 13), inaccessible by other synthetic routes. The diphosphaza-crowns thus obtained with beta-naphthoxy substituents (10, 12) offer promising prospects as new Ligands of the P-pivot lariat ether type, capable of complexing both alkali and transition metal cations and of potential catalytic activity in phase and electron-transfer processes.

  DOI：

  10.1021/jo00128a014

文献信息

• Structure–alkali metal cation complexation relationships for macrocyclic PNP-lariat ether ligandsElectronic supplementary information (ESI) available: diagnostic 31P NMR and 1H NMR spectral data and combustion analyses for new PNP-lariat and bis-lariat ethers. See http://www.rsc.org/suppdata/p2/b1/b110415b/
  作者：Richard A. Bartsch、Eun Kyung Lee、Sangki Chun、Nazar Elkarim、Krystyna Brandt、Iwona Porwolik-Czomperlik、Mariola Siwy、Dariusz Lach、Jerzy Silberring

  DOI：10.1039/b110415b

  日期：2002.2.25

  Water-insoluble, mono- and diarmed PNP-lariat ethers containing various aryloxy and regioisomerically-positioned binaphthylylenedioxy substituents linked to the phosphorus atoms of the cyclophosphazene ring via oxygen atoms are synthesized by regioselective, sodium ion-assisted arylolysis of tetrachloro-16-PNP-6 crown ether 1. Heterogeneously-substituted, mixed aryloxy-amino PNP-lariat ethers and bis-lariat ethers with two different substituents linked to the PNP-macrocycle via an oxygen and a nitrogen atom are prepared by stepwise arylolysis and aminolysis reactions of 1. The alkali-metal cation complexation behavior of the PNP-lariat ethers is evaluated in solvent polymeric membrane electrodes. The PNP-lariat and bis-lariat ethers exhibit pronounced selectivity for large alkali metal cations (Rb+ and Cs+) over small ones (Li+ and Na+). The selectivity is influenced by the configuration of the crown ether ring and the number of oxygen donor atoms in the ligand. For some PNP-lariat ethers, evidence for formation of 2 : 1 (ligand–metal ion) complexes with Rb+ and Cs+ is provided by ESI-MS.

  通过对四氯-16-PNP-6 冠醚 1 进行区域选择性钠离子辅助芳基裂解，合成了含有通过氧原子与环磷苯环的磷原子相连的各种芳氧基和区域异构体位置的双萘二氧基取代基的水不溶性单链和双链 PNP-锂基醚。通过对 1 逐步进行芳基裂解和氨基裂解反应，制备出异质取代的混合芳氧基氨基 PNP-基环醚和双基环醚，其中两个不同的取代基通过一个氧原子和一个氮原子与 PNP 大环相连。PNP-ariat 和双-lariat 醚对大碱金属阳离子（Rb+ 和 Cs+）比对小碱金属阳离子（Li+ 和 Na+）具有明显的选择性。选择性受冠醚环的构型和配体中氧供体原子数的影响。对于某些 PNP-锂基醚，ESI-MS 提供了与 Rb+ 和 Cs+ 形成 2:1（配体â金属离子）络合物的证据。
• Thermodynamic <i>vs</i> Supramolecular Effects in the Regiocontrol of the Formation of New Cyclotriphosphazene-Containing Chiral Ligands with 1,1‘-Binaphthyl Units:  Spiro <i>vs</i> Ansa Substitution at the N₃P₃ Ring
  作者：Krystyna Brandt、Iwona Porwolik-Czomperlik、Mariola Siwy、Teobald Kupka、Robert A. Shaw、David B. Davies、Michael B. Hursthouse、Georgia D. Sykara

  DOI：10.1021/ja972372m

  日期：1997.12.1

  ligands (6−9) with 1,1‘-binaphthyl units has been achieved by stepwise dicyclosubstitution of hexachlorocyclotriphosphazene (1), with two sodium cation paired dinucleophiles derived from bis-β-naphthol (2) and tetraethylene glycol (3). The structures of the disubstitution products have been found to be addition order-dependent. In particular, the substitution pattern of the 1,1‘-binaphthalene-2,2‘-dioxy

  通过逐步双环取代六氯环三磷腈 (1) 和衍生自双β-萘酚 (2) 的两个钠阳离子配对双亲核试剂，合成了具有 1,1'-联萘单元的新型含环磷腈的手性配体 (6-9) 和四甘醇 (3)。已发现置换产物的结构与加成顺序有关。特别是，N3P3 环 [spiro (4 → 6, 7) 或 ansa (8, 9)] 中 1,1'-binaphthalene-2,2'-dioxy 取代基的取代模式与冠取代基已预先掺入1中。将相转移催化剂试剂四丁基溴化铵添加到 5 + 2-Na 2 的反应混合物中导致螺 6 和 ansa 8 异构体的平行形成。
• Functional crown ethers with chlorocyclophosphazene sub-units as anion activators and promoters of highly regioselective reactions
  作者：Angelamaria Maia、Dario Landini、Michele Penso、Krystyna Brandt、Mariola Siwy、Grzegorz Schroeder、Blazej Gierczyk

  DOI：10.1039/b102312h

  日期：——

  the transition state, following a ‘push–pull’ mechanism. The results provide strong evidence for the key role of the polyether crown substituent in determining, ia a host–guest interaction with the alkali metal p-nitrophenoxide, both the activation of the anion and the regiocontrol of the chlorine substitution in the phosphazenic ring (‘P-crown’  s. ‘P-non-crown’ substitution). As a consequence of this

  金属离子对区域化学结果的影响已在二磷杂[16] crown-6与一系列低极性碱金属对硝基苯酚的亲核取代反应中得到揭示。溶剂 （氯苯，THF）在固液非均相条件下。而锂和钠盐如果仅给出“ P-冠”取代产物，则发现与相应的钾盐和铯盐优先形成单-和“ -P-非冠”衍生物。鉴于盐分的不同参与，已合理化了观察到的改变盐的区域化学。阳离子遵循“推挽”机制，在过渡态的稳定过程中处于稳定状态。结果提供了聚醚冠醚取代基的确定，关键作用的有力证据IA与碱金属主-客体相互作用p -nitrophenoxide，阴离子的两者的激活和氯取代的在环phosphazenic的区域控制（” P-crown  的。“ P-non-crown”替代）。这种超分子控制的结果是，可以将反应模式在与之成对的位置上朝着电子和空间上不利的区域选择性取代的方向切换。大循环 （“ P冠”取代），可以轻松访问其他物种，而这些物种很难遵循经典的磷腈化学法则获得。
• Supramolecular Assistance to Regioselectivity in the Reactions of Chlorocyclophosphazenes with Sodium Oxyanions:  Macrocyclic Effect and Anion Dependence
  作者：Krystyna Brandt、Mariola Siwy、Iwona Porwolik-Czomperlik、Jerzy Silberring

  DOI：10.1021/jo001725o

  日期：2001.8.1

  of the respective sterically and electronically favored nongem-naphthoxydiethoxy derivative as the major product, isolated as the mixture of cis and trans isomers 8 + 9, the corresponding reaction of crown substrate 2 resulted in highly regioselective formation of the gem-to-macrocycle substituted mononaphthoxy PNP-crown derivative 11a. The importance of the PNP-crown related effects for the regio- and

  带有冠的四氯环三磷腈2及其无环类似物nongem-dithoxytetrachlorocyclotriphosphazene 5（为本研究的目的以纯顺式形式合成和分离）的萘解比较研究表明，该取代基对两个N（3）P（3）环中氯取代的动力学和区域化学。尽管用环氧化钠取代5可以适度地获得作为主要产物的空间和电子位置偏爱的非晶型萘氧基二乙氧基衍生物，并以顺式和反式异构体8 + 9的混合物形式进行分离，但冠底物2的相应反应导致了高度区域选择性到大环取代的单萘氧基PNP-冠衍生物11a的形成。根据环氧基取代基之间的超分子钠阳离子辅助相互作用，讨论了NNP（3）P（3）环中氯原子的取代和立体控制的PNP冠相关效应的重要性。 ）和引入的氧阴离子。为了解决区域选择性的阴离子依赖性问题，在PNP冠底物2与衍生自β-萘酚（10a）和苯酚（10b）的芳基钠的反应中进行了比较，以等摩尔浓度或相对于2，100％过量的
• Mass Spectrometry Reveals Complexing Properties of Modified PNP-Lariat Ether Containing Benzyl Derivative of (S)–Prolinamine
  作者：Natalia Gutowska、Piotr Seliger、Jarosław Romański、Magdalena Zięba、Grazyna Adamus、Marek Kowalczuk

  DOI：10.3390/molecules25010136

  日期：——

  concerning the complexing properties of the new ligand towards Ag+, Cu2+, Co2+, Ni2+, and Zn2+ ions. The formation of non-covalent complexes of 1:1 stoichiometry with the Cu2+, Co2+, Ni2+, and Zn2+ ions have been confirmed by mass spectrometry. Due to the previous work and application possibilities, a large emphasis was put on the investigation of the complexation ability of lariat ether with silver (I) cation

  在此处介绍的研究中，描述了从四吡咯烷基-PNP-冠醚大环修饰获得的新套索醚衍生物的合成。多异位分子共受体由具有旋光性的 (S)-(1-benzylpyrrolidin-2-yl) 甲胺取代氯原子组成。通过使用元素分析、质谱和核磁共振光谱证实了结构。这项工作涵盖了有关新配体对 Ag+、Cu2+、Co2+、Ni2+ 和 Zn2+ 离子络合特性的结果。质谱法证实了与 Cu2+、Co2+、Ni2+ 和 Zn2+ 离子的化学计量比为 1:1 的非共价复合物的形成。由于之前的工作和应用的可能性，重点研究套索醚与银 (I) 阳离子的络合能力，以通过直接电位法确定稳定性常数。在这种情况下，已经证明了四种不同形式的配合物 AgL、Ag2L、Ag3L 和 Ag4L 的形成。观察到的通过来自环外取代基的氮原子的不寻常结合可能为构建新的配位聚合物提供结构单元。