2,4-Dichloro-6-[[2-[(3,5-dichloro-2-oxidophenyl)methyl-methylamino]ethyl-methylamino]methyl]phenolate;propan-2-olate;titanium(4+)

• 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: 2,4-Dichloro-6-[[2-[(3,5-dichloro-2-oxidophenyl)methyl-methylamino]ethyl-methylamino]methyl]phenolate;propan-2-olate;titanium(4+)
• 英文别名: 2,4-dichloro-6-[[2-[(3,5-dichloro-2-oxidophenyl)methyl-methylamino]ethyl-methylamino]methyl]phenolate;propan-2-olate;titanium(4+)
• 化学式: C₂₄H₃₂Cl₄N₂O₄Ti
• 分子量: 602.221
• InChiKey: JKTRIWBVHUQBSN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  98.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  吡啶-2,6-二甲酸 、 2,4-Dichloro-6-[[2-[(3,5-dichloro-2-oxidophenyl)methyl-methylamino]ethyl-methylamino]methyl]phenolate;propan-2-olate;titanium(4+) 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以86%的产率得到(2,2′-(ethane-1,2-diylbis((methylimino)methylene))bis(4,6-dichlorphenolato))(pyridine-2,6-dicarboxylato-N,O,O′)-titanium(IV)
  参考文献：
  名称：

  庚七配体Salan（ONNO）和Thiosalan（OSSO）钛（IV）配合物：稳定性和细胞毒性研究

  摘要：

  根据salan（ONNO）和thiosalan（OSSO）钛（IV）烷氧基与2,6-吡啶二甲酸（dipic）及其衍生物的异双螯合稳定概念，合成了七种七配位钛（IV）配合物。通过X射线衍射在固体中和通过NMR光谱在溶液中研究所得化合物。可以分离出一个硫代（OSSO）钛（IV）配合物，并通过1 H NMR光谱显示了其通过二元构象的构象稳定性，即使在室温下，也能导致无通量的行为。通过紫外可见监测的水解研究（> 5 Mio），在pH 1.9、6.8和12.1下评估了选定配合物的稳定性。当量的水。即使在pH 12.1时，[L 1 Ti（dipic）1 ]仍显示出t超过2天的1/2。在两种人类癌细胞系中研究了所有化合物的细胞毒性。除[L 4 Ti（dipic）1 ]外，所有测试的化合物均达到顺铂范围的IC 50值，事实证明该化合物无毒。因此，二斜肽的功能性被很好地耐受，并且既不影响杂合剂复合物的稳定性也没有细胞毒性。

  DOI：

  10.1021/acs.inorgchem.5b00690
• 作为产物：
  描述：

  titanium(IV) isopropylate 、 N,N'-dimethyl-N,N'-bis[(3,5-dichloro-2-hydroxyphenyl)methylene]-1,2-diaminoethane 以 四氢呋喃 为溶剂， 生成 2,4-Dichloro-6-[[2-[(3,5-dichloro-2-oxidophenyl)methyl-methylamino]ethyl-methylamino]methyl]phenolate;propan-2-olate;titanium(4+)
  参考文献：
  名称：

  N-甲基化对Salan Ti（IV）配合物的细胞毒性和水解的主要影响：空间和电子学交织†

  摘要：

  制备了一系列包含具有NH配位的二氨基双（酚基）“ salan”型配体的Ti（IV）配合物，并对其水解和细胞毒性进行了分析，并与N-甲基化的类似物进行了比较。用H原子取代高活性和稳定的Ti（IV）salan配合物的配位氮供体上的甲基有两个主要结果：水解速率增加和细胞毒性活性降低。此外，用H取代Me的微小修饰会导致产生不同的主要水解产物，其中获得具有两个桥联氧代配体的双核Ti（IV）络合物，如X射线晶体学表征的，而不是三核的簇。还通过结晶学分析了包含单个氧代桥的部分水解产物。

  DOI：

  10.1039/c1dt11108f

文献信息

• Major impact of N-methylation on cytotoxicity and hydrolysis of salan Ti(IV) complexes: sterics and electronics are intertwined
  作者：Sigalit Meker、Cesar M. Manna、Dani Peri、Edit Y. Tshuva

  DOI：10.1039/c1dt11108f

  日期：——

  A series of Ti(IV) complexes containing diamino bis(phenolato) “salan” type ligands with NH coordination were prepared, and their hydrolysis and cytotoxicity were analyzed and compared to the N-methylated analogues. Substituting methyl groups on the coordinative nitrogen donor of highly active and stable Ti(IV) salan complexes with H atoms has two main consequences: the hydrolysis rate increases and

  制备了一系列包含具有NH配位的二氨基双（酚基）“ salan”型配体的Ti（IV）配合物，并对其水解和细胞毒性进行了分析，并与N-甲基化的类似物进行了比较。用H原子取代高活性和稳定的Ti（IV）salan配合物的配位氮供体上的甲基有两个主要结果：水解速率增加和细胞毒性活性降低。此外，用H取代Me的微小修饰会导致产生不同的主要水解产物，其中获得具有两个桥联氧代配体的双核Ti（IV）络合物，如X射线晶体学表征的，而不是三核的簇。还通过结晶学分析了包含单个氧代桥的部分水解产物。
• <i>C</i>₁-Symmetrical Titanium(IV) Complexes of Salan Ligands with Differently Substituted Aromatic Rings: Enhanced Cytotoxic Activity
  作者：Hagai Glasner、Edit Y. Tshuva

  DOI：10.1021/ic500001j

  日期：2014.3.17

  Diaminobis(phenolato) (“salan”) titanium(IV) complexes of differently substituted aromatic rings were synthesized, and their hydrolytic stability and cytotoxicity were analyzed and compared to those of the C2-symmertrical analogues and their equimolar mixtures. The hydrolytic stability of the asymmetrical complexes was in between those of the symmetrical analogues, implying an additive influence of the ligand structural

  合成了不同取代的芳环的二氨基双（酚基）（“ salan”）钛（IV）配合物，并对其水解稳定性和细胞毒性进行了分析，并与C 2-对称类似物及其等摩尔混合物进行了比较。不对称复合物的水解稳定性介于对称类似物的水解稳定性之间，这暗示了配体结构参数的累加影响。相对于对称类似物及其混合物，大多数混合的卤化/硝化复合物显示出明显的细胞毒性，IC 50为值低至<1μM，相当于活性超过顺铂高达30倍。相反，具有相似性质的取代的不对称复合物揭示了两者的附加影响，并且在对称类似物之间具有细胞毒性。在假定活性物质通常是多核水解产物的前提下，总体看来，特定的配体设计和包括亲水性和疏水性在内的影响参数的微调对于最大限度地提高生物效率至关重要。
• A Marked Synergistic Effect in Antitumor Activity of Salan Titanium(IV) Complexes Bearing Two Differently Substituted Aromatic Rings
  作者：Hagai Glasner、Edit Y. Tshuva

  DOI：10.1021/ja208219f

  日期：2011.10.26

  Salan titanium(IV) complexes of differently substituted aromatic rings, where one ring is para-nitrated and another is ortho,para-halogenated, demonstrate exceptionally high anticancer activity, with IC50 values of <1 mu M, exceeding that of cisplatin by similar to 30-fold. Whereas an additive effect in hydrolytic stability was detected for these highly stable complexes, an unexpected synergistic effect in anticancer activity makes these hybrid complexes substantially more active than both their symmetrical analogues alone and their equimolar mixture.
• Cationic phenolato titanium(IV) complexes of enhanced solubility as active and biologically accessible anti-tumor compounds
  作者：Hagai Glasner、Sigalit Meker、Edit Y. Tshuva

  DOI：10.1016/j.jorganchem.2015.04.023

  日期：2015.7

  Cationic titanium(IV) phenolato complexes with a pyridinium ligand were synthesized from their iso-propoxo precursors, and featured improved solubility in water/DMSO solutions. High cytotoxicity was recorded toward HT-29 cells, often higher than that of cisplatin. Marked activity enhancement was observed upon substitution with pyridinium ligand, which improved the complexes biological accessibility. (C) 2015 Elsevier B.V. All rights reserved.
• Phosphino-functionalised acetals of polyvinyl alcohol as the matrix for the immobilisation of Rh-based pre-catalysts for interfacial catalysis
  作者：Martin Ahlmann、Olaf Walter、Melany Frank、Wilhelm Habicht

  DOI：10.1016/j.molcata.2005.12.044

  日期：2006.4

  Use of polyvinyl alcohol (PVA) to support the immobilisation of phosphines shall be presented. Phosphino functionalisation is introduced in the polymer by a one-step transacetalation reaction and high acetalation degrees are reached. By complexation of the phosphino groups to a [(COD)RhCl] complex fragment, [Rh]-modified polymers are obtained with Rh contents of higher than 15% and the transition metal in a defined molecular environment. The phosphino or [Rh]-modified PVAs are characterised unambiguously by comparing their spectroscopic data with those of model compounds, the syntheses of which are reported as well. Use of the [Rh]-modified polymers as pre-catalysts will be presented with the hydroformylation of 1-octene being taken as an example. It leads to a selectivity in the product distribution that is identical to that of the model complexes. Recycling experiments were performed and the catalyst rest state on the polymer was identified after 10 consecutive runs. Adsorption of the [Rh]-modified PVA on an inorganic support leads to the formation of stable polymer layers on its surface, which cannot be mobilised by extraction with organic solvents. The stability of these layers, together with their tuneable polarity, allow for their application in interfacial catalysis comparable to SAPC or SILC. (c) 2006 Elsevier B.V. All rights reserved.