两相法合成取代水杨酸二茂钛配合物

水杨酸配合物;两相法合成取代水杨酸二茂钛配合物     

一个简便合成二茂钛二芳氧基和水杨酸配合物的方法

用两相法合成了二茂钛二(五氯苯氧基)配合物,并对二茂钛(环取代)水杨酸配合物的合成法进行了改进,产率为70%-90%。     

苯甲酰丙酮存在下含水体系中合成二茂钛取代水杨酸配合物

Four titanocene complexes were prepared in aqueous or two-phase medium by the reaction of benzoylacetone titanocene with substituted salicylic acid, respectively. Based on the UV-Vis spectra, we studied the accelerating effect of the benzoylacetone on the reaction rate quantificationally. The results demonstrated that the presence of it not only stabilizes the “Cp₂Ti” species and accordingly makes pH value of the aqueous solution of substituted salicylic acid increased but also prompts the reaction due to the presence of its conjugation structure and oleophyllic group. Furthermore, the presence of benzoylacetone is in favor of the simplification of the products.     

二茂钛二羧酸配合物的合成与性能

作者曾报道了一些二茂钛二羧酸衍生物的合成及结构,本文选择具有一定空间位阻并具有某些药理作用的羧酸配体进行相应的二茂钛二羧酸配合物的合成,并首次报道该类配合物在活性氢化钠存在下对已烯-1的催化加氢行为。     

水相法合成二氯二甲茂钛与水杨酸类配合物

Ｃｐ2 ＴｉＣｌ2 具有很好的抗癌活性 ,已成为第三代抗癌药物[1 - 3] 。为了寻求活性更高的抗癌药物 ,探索抗癌机理 ,我们用 (ＭｅＣｐ) 2 ＴｉＣｌ2 、水杨酸或其衍生物 ,按水相法合成了甲茂钛的水杨酸类配合物。合成路线如下图所示 :其中 :Ⅰ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =Ｈ的产物 ;Ⅱ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =ＮＯ2 的产物 ;Ⅲ为ｐＨ >6 ,Ｘ =ＮＯ2 ,Ｙ =ＮＯ2 ,Ｚ =Ｏ的产物 ;Ⅳ为ｐＨ >6 ,Ｘ =Ｈ ,Ｙ =Ｈ ,Ｚ =Ｓ的产物。 (Ⅰ～Ⅳ为新化合物 )1　实验部分1 .1　仪器与试剂水杨酸、ＴｉＣｌ4,ＡＲ ;5 -硝基水杨酸、3,5 -二硝基水杨酸、5 -磺基…     

二茂钛氨基酸配合物的合成新方法

二茂钛衍生物在催化烯烃聚合、氢化、异构化等领域具有重要应用价值[1] ,同时 ,因该类衍生物还具有良好的抗癌性能 ,且其毒性远远低于顺铂类化合物[2 ] ,使人们对这类配合物的研究一直非常重视 .有文献报道 [3] ,以具有生物活性的配体取代二氯二茂钛中的氯原子 ,可以改善其生物利用率 ,提高二茂钛的抗癌活性 .二茂钛配合物的合成绝大多数都是在无水无氧的有机相中进行的 ,在两相(水相 /有机相 ) [4 ,5] 中则很少 .我们曾经在有机相和水相中合成了一些新的二茂钛氨基酸配合物 [6] ,但操作繁杂 ,反应速度慢 ,影响因素多 ,产率低等是这两种体系…     

有水条件下合成二茂钛取代邻苯二甲酸配合物

最近二、三年 ,含水体系中的金属有机化学反应研究因其具有操作简单 ,对环境污染减少等优势 ,已成为化学研究领域的热点之一[1 ] ,二茂钛衍生物在作为单活性点催化剂催化烯烃聚合以及作为抗肿瘤药物等方面所体现的重要应用价值[2～4] ,使得该类配合物的研究一直倍受关注。然而 ,绝大多数二茂钛衍生物至今仍然在无水无氧等苛刻的有机相中进行催化反应 ,究其原因 ,除结构方面造成在空气中或有水条件下不稳定外 ,其合成方法的限制也是主要因素之一。因此 ,在有水条件下 ,研究二茂钛衍生物的合成及其方法是很有意义的。我们曾在含水介质中合成了…     

8-羟基喹啉存在下水相(两相)中合成取代水杨酸二茂钛配合物

在8-羟基喹啉存在下,分别采用水相法和两相法简便合成了5种取代水杨酸二茂钛配合物,并用元素分析、IR及 1H NMR等手段对配合物进行了结构表征,发现配合物中均不含8-羟基喹啉配体,而是形成以取代水杨酸为双齿配体的六元杂环化合物.用电子吸收光谱分别对两相反应体系(H2O/CHCl3)的水相和有机相进行了动态监测,发现8-羟基喹啉首先通过两相界面与有机相中的二氯二茂钛形成水溶性的过渡性配合物,然后该过渡性配合物再与有机相中的取代水杨酸作用形成了目标配合物.     

新型二茂钛氧杂环络合物的合成与结构

有机钛杂环化合物的研究是有机钛化学的重要方面。我们在合成取代环戊二烯基钛络合物的过程中,发现一类新型钛杂环化合物的合成方法:     

5－磺基水杨酸催化两相法合成某些二茂衍生物

首次利用5－磺基水杨酸作为催化剂合成了9种二茂钛衍生物,经元素分析,UV－vis,IR及^1HNMR等对配合物结构进行了表征,并利用电子吸收光谱对取代水杨酸参与反应的机理进行了探讨,同时发现,5－磺基水杨酸水溶液也可用于二氯二茂钛的分离,并且非常有效。     

肌肉醇取代苯甲酸盐的合成及生物活性

本文以硫脲和硫酸二甲酯为原料反应生成S-甲基异硫脲硫酸盐,再与2-甲基氨基乙醇反应生成肌肉醇硫酸盐,分离出肌肉醇碱,最后与具有生物活性的取代苯甲酸反应生成了7种肌肉醇取代苯甲酸盐。化合物结构经IR,1H NMR和元素分析进行表征,初步室内生测结果表明该类化合物具有一定的抑菌活性。     

The preparation of a substituted titanocene-supported polymer and its application in catalytic reactions

A series of polymer-supported RCpCpTiCl₂ (Cp = η⁵  C₅H₅; RCp=η⁵  RC₅H₄) has been prepared and reduced by i-C₃H₇MgBr in situ, then used as catalysts in hydrogenation of styrene, isomerization of 1,5-cyclooctadiene and 1,5-hexadiene, and reduction of carbonyl compounds. In some cases, the introduction of a polymer ligand on the Cp ring restricts the aggregation of active sites and the formation of the inactive dimer of the titanocene species, and results in an increase of activity. Regeneration of polymer-supported titanocene catalysts was performed and the results are presented and briefly discussed.     

双（取代环戊二烯基）二氯化钛的晶体结构分析

报道了双（１－正戊基环己基茂）二氯化钛［（η５－Ｃ５Ｈ４Ｃ（ＣＨ２）５（Ｃ５Ｈ１１－ｎ］２ＴｉＣｌ２（Ｉ）及双（１－甲基－１－（α－噻吩基）乙基环戊二烯基）二氯化钛［η￣５－Ｃ５Ｈ４Ｃ（ＣＨ３）＿２－］２ＴｉＣｌ２（Ⅱ）的晶体结构和分子结构。二者均系单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，晶胞参数ａ＝１４．１８０（２），ｂ＝６．５６２（１），ｃ＝１７．０４６（３），β＝９９．６３（１）°，Ｚ＝２，Ｖ＝１５６３．８，Ｄｘ＝１．１８８ｇ／ｃｍ３，Ｆ（０００）＝５９６，Ｍｒ＝５５３．５６，λ＝０．７１０７３μ＝４．５９ｃｍ－１，Ｒ＝０．０５８，Ｒｗ＝０．０６６；（１）的空间群为Ｃ２／ｃ，晶胞参数ａ＝２５．７１３（１），ｂ＝６．６１７（１），ｃ＝１３．５９１（１），β＝９２．７８（２）°，Ｚ＝４，Ｖ＝２３０９．８，Ｄｘ＝１．４３０ｇ／ｃｍ３，Ｍｒ＝４９７．４１，λ＝０．７１０７３，μ＝７．８２２ｃｍ－１，Ｆ（０００）＝１０３２，Ｒ＝０．０５５，Ｒｗ＝０．０７２。茂环上取代基对茂环金属化合物的结构产生较大影响，空间阻碍的增大使得取代基与茂环相连Ｃ－Ｃ单键增长。     

The chemistry,properties, and characterization of organotin(IV) complexes of 2-(N-naphthylamido)benzoic acid

2-(N-naphthylamido)benzoic acid was synthesized by the reaction of phthalic anhydride with naphthylamine in glacial acetic acid at room temperature. Complexes 1–9 were synthesized under reflux in good yield with general formula R_{4? n} SnL _n (R = Me, n-Bu, Ph, n-Oct, Bz and n = 2, 3), which were studied by microanalysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn), and mass spectrometry. Cytotoxicity of the synthesized compounds was checked against Brine-shrimp larvae. In vitro activities against some Gram-positive and Gram-negative bacteria and fungi were also determined. Antimicrobial activities show that species with tetrahedral geometry in solution are more toxic.     

An effective method for the synthesis of carboxylic esters and lactones using substituted benzoic anhydrides with Lewis acid catalysts

An efficient mixed-anhydride method for the synthesis of carboxylic esters and lactones using benzoic anhydride having electron withdrawing substituent(s) is developed by the promotion of Lewis acid catalysts. In the presence of a catalytic amount of TiCl₂(ClO₄)₂, various carboxylic esters are prepared in high yields through the formation of the corresponding mixed-anhydrides from 3,5-bis(trifluoromethyl)benzoic anhydride and carboxylic acids. The combined catalyst consisting of TiCl₂(ClO₄)₂ together with chlorotrimethylsilane functions as an effective catalyst for the synthesis of carboxylic esters from free carboxylic acids and alcohols with 4-(trifluoromethyl)benzoic anhydride. Various macrolactones are prepared from the free ω-hydroxycarboxylic acids by the combined use of 4-(trifluoromethyl)benzoic anhydride and titanium(IV) catalysts together with chlorotrimethylsilane under mild reaction conditions. The lactonization of trimethylsilyl ω-(trimethylsiloxy)carboxylates using 4-(trifluoromethyl)benzoic anhydride is also promoted at room temperature in the presence of a catalytic amount of TiCl₂(ClO₄)₂. An 8-membered ring lactone, a synthetic intermediate of cephalosporolide D, is successfully synthesized according to this mixed-anhydride method using 4-(trifluoromethyl)benzoic anhydride by the promotion of a catalytic amount of Hf(OTf)₄.     

New tin(IV) complexes with sterically hindered o‐iminobenzoquinone ligand: Synthesis and structure

The reduction of 4,6‐di‐tert‐butyl‐N‐(2, 6‐di‐iso‐propylphenyl)‐o‐iminobenzoquinone (imQ) by tin amalgam in hexane solution leads to new six‐coordinated o‐iminoquinonato tin(IV) complex (iSQ)₂SnAP ( 1 ) (where iSQ and AP are o‐iminosemiquinolate and dianion o‐amidophenolate, respectively). Variable temperature magnetic susceptibility measurements of 1 have shown that this complex possesses a weak ferromagnetic exchange between o‐iminosemiquinonate ligands. The oxidation of 1 with air oxygen produces new o‐iminoquinonolate tin(IV) derivatives [(iSQ)Sn(AP)]₂O ( 2 ) and (iSQ)₂Sn(OH)₂ ( 3 ) containing μ‐oxo‐ and hydroxo‐ligands, respectively. The electronic structure of 1 was examined by DFT analysis. Complexes 1–3 have been investigated using single‐crystal X‐ray diffraction. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:332–340, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20555     

The preparation of the sterically hindered alcohol tris(trimethylsilyl)methanol

The alcohol (Me₃Si)₃COH, with potential for use in the preparation of sterically hindered metal alkoxides, has been prepared by hydrogen peroxide oxidation of the boronic acid (Me₃Si)₃CB(OH)₂.     

Synthesis,characterization and biological studies of alkenyl‐substituted titanocene(IV) carboxylate complexes

The carboxylate compounds [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})(O₂CCH₂SXyl)₂] (2; Xyl = 3,5‐Me₂C₆H₃) and [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})(O₂CCH₂SMesl)₂] (3; Mes 1 = 2,4,6‐Me₃C₆H₂) were synthesized by the reaction of [Ti(η⁵‐C₅H₅)(η⁵‐C₅H₄{CMe₂(CH₂CH₂CH?CH₂)})Cl₂] (1) with 2 equivalents of xylylthioacetic acid or mesitylthioacetic acid, respectively. Compounds 2 and 3 were characterized by spectroscopic methods. The cytotoxic activity of 1–3 was tested against human tumor cell lines from four different histogenic origins—8505C (anaplastic thyroid cancer), DLD‐1 (colon cancer) and the cisplatin sensitive A253 (head and neck cancer) and A549 (lung carcinoma)—and compared with those of the reference complex [Ti(η⁵‐C₅H₅)₂Cl₂] (R1) and cisplatin. Surprisingly, the cytotoxic activities of the carboxylate derivatives were lower than those of their corresponding dichloride analogue (1). However, complexes 1–3 were more active than titanocene dichloride against all the studied cells with the exception of complex 2 against A253 and A549 cell lines. DNA‐interaction tests were also carried out. Solutions of all the studied complexes were treated with different concentrations of fish sperm DNA, observing modifications of the UV spectra with intrinsic binding constants of 2.99 × 10⁵, 2.45 × 10⁵, and 2.35 × 10⁵ M ^?1 for 1–3. Structural studies based on density functional theory calculations of 2 and 3 were also carried out. Copyright © 2010 John Wiley & Sons, Ltd.     

The preparation and characterization of acetylacetonato-bis(η-methylcyclopentadienyl)titanium(IV) complexes

Summary A series of [L₂TiL]⁺X^–compounds where L is the conjugate base of acetylacetone, L=-MeC₅H₄ and X^–= ClO ₄ ^– , BF ₄ ^– , FeCl ₄ ^– , ZnCl₃(H₂O)^–, SnCl ₃ ^– , CdCl ₄ ^2– , HgCl ₄ ^2– , Br^– or I^–, have been prepared by adding X^– to the aqueous solution of [L₂TiL]⁺Cl^–. Conductivity measurements in nitrobenzene for all compounds indicate that these complexes are electrolytes. The i.r. frequencies for various vibrational modes have been assigned. The ligand L appears to be chelating and the titanium atom is essentially tetracoordinate. The bonding in these complexes is discussed.On study leave from S. D. College, Muzaffar Nagar, U.P., India.