取代8-羟基喹啉钌络合物催化Friedl?nder反应合成喹啉衍生物

Friedl?nder喹啉合成法是以邻胺基芳基醛或酮与有α-亚甲基的酮环化制备喹啉的反应,报道了一种喹啉钌络合物催化Friedl?nder法合成喹啉的方法.首先,以8-羟基喹啉钌络合物为催化剂,对模板反应邻氨基苯甲醇和苯乙酮合成2-苯基喹啉进行了反应条件优化实验.重点对比研究了8-羟基喹啉钌络合物配体上不同取代基对反应收率的影响,其中5-甲基-8-羟基喹啉(1e)钌络合物催化邻氨基苯甲醇和苯乙酮合成2-苯基喹啉获得了73%的最高收率.结合IR, UV以及密度泛函理论(DFT)计算讨论了配体结构与催化性能之间的关系.提出了β-H消除形成醛过渡态,交叉aldol反应再亚胺环化,最后脱水生成目标产物的可行机理.以(1e)₃Ru为催化剂,在优化的反应条件下进行了底物扩展研究,以69%～94%的收率合成了32个不同取代的喹啉衍生物,验证了方法的普适性.     

8-羟基喹啉-2-醛缩芳香酰肼Ni(Ⅱ)配合物的合成及表征

合成并表征了8-羟基喹啉-2-醛缩苯甲酰肼、8-羟基喹啉-2-醛缩水杨酰肼以及8-羟基喹啉-2-醛缩对羟基苯甲酰肼Ni(Ⅱ)配合物,并利用黏度滴定、紫外光谱和荧光光谱法研究了它们与CT-DNA相互作用情况.结果表明,这些配合物均为良好的DNA插入试剂,它们与DNA的结合常数(Kb)分别为1.006× 105 M-1、9...     

甲酰基-8-羟基喹啉的合成

以8-羟基喹啉为原料,通过Reimer-Tiemann反应合成了5-甲酰基-8-羟基喹啉(收率15.0%)和7-甲酰基-8-羟基喹啉(收率21.5%),其结构经1HNMR和IR表征。     

6-羟基-3,4-二氢喹啉-1(2H)-羧酸叔丁基酯的合成研究

以6-羟基喹啉为原料,使用钯碳催化加氢和硼氢化钠还原两种方法合成了6-羟基-1,2,3,4-四氢喹啉化合物,考察反应温度与碱性条件对6-羟基-3,4-二氢喹啉-1(2H)-羧酸叔丁基酯合成收率的影响,10℃反应温度下,以碳酸氢钠作碱是合成的最佳反应条件。     

7-硝基-8-羟基喹啉的合成

以8-羟基喹啉为原料,经硝化和脱磺酸基保护两步反应合成了7-硝基-8-羟基喹啉,总收率69％,纯度高于99％.其结构经1H NMR,13C NMR和HR-MS确证.     

8-羟基喹啉-7-醛缩氨基硫脲衍生物的微波合成及抗肿瘤活性研究

以8-羟基喹啉-7-醛和一系列芳基及烷基取代氨基硫脲为原料,合成了15种8-羟基喹啉缩氨基硫脲类化合物。缩合反应在绿色溶剂水中进行,微波辐射下15-30 min内反应完全,操作简单,收率高。化合物结构经1H NMR、IR和高分辨质谱确证。部分化合物经抗肿瘤活性初步测试结果表明,多数化合物对细胞周期分裂蛋白25B(CDC25B)抑制率达到90%以上,具有潜在的抗肿瘤活性。     

7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉及其金属配合物的合成与荧光性能

以7-甲酰基-8-羟基喹啉和邻苯二胺为原料,经缩合反应合成了一种新型的配体——7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉(H2L);H2L分别与醋酸锌和三氯化铝经配位反应合成了两种新型的金属配合物Zn L·H2O(1)和Al_2L_3·3H_2O(2),其结构和性能经UV-Vis,1H NMR,IR,元素分析及FL表征。1和2的λem分别为514 nm(λex=400 nm)和525 nm(λex=401 nm)。     

7-(4-安替吡啉偶氮)-8-羟基喹-5-磺酸的合成及其与铜的显色反应

7-(4-安替吡啉偶氮)-8-羟基喹啉为安替吡啉单偶氮类试剂中的一种,该试剂可与镓(Ⅲ)、铟(Ⅲ)、铋(Ⅲ)、钯(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)、铜(Ⅱ)、铁(Ⅱ)等离子发生显色反应[1,2].本文在其5位引入磺酸基,合成了7-(4-安替吡啉偶氮)-8-羟基喹啉-5-磺酸(分子式为C20H17N5O5S)试剂.该试剂分子的共轭体系增大,分析功能基及成键原子的电荷密度大大提高,可提高显色反应的灵敏度.文献[3～5]研究表明,8-羟基喹啉-5-磺酸-7-偶氮化合物可能是一类较有价值的光度分析试剂.本文以4-氨基安替吡啉的重氮盐为重氮组分与8-羟基喹啉-5-磺酸进行偶合反应,合成了7-(4-安替吡啉偶氮)-8-羟基喹啉-5-磺酸,产物的结构用红外光谱进行了表征,并研究了该试剂与铜的显色反应.     

2-(2-苯并呋喃基)-6-氯-3-喹啉甲酸衍生物的简便合成

以6-氯-2-氯甲基-3-喹啉甲酸乙酯(1)为底物,在无水碳酸钾作为缚酸剂、乙腈作为溶剂、聚乙二醇-400作为相转移催化剂的条件下分别与水杨醛(2a~2i)、邻羟基苯乙酮(2j~2o)及2-羟基-1-萘醛(2p)经"三步一锅法"在超声辅助下回流反应,成功的合成了2-(2-苯(萘)并呋喃基)-6-氯-3-喹啉甲酸衍生物(3a~3p).所合成化合物的结构均通过红外光谱、核磁共振氢谱、核磁共振碳谱和高分辨质谱得以证实.     

Microwave-enhanced synthesis and antitumor activity of 8-hydroxyquinoline-7-aidehyde thiosemicarbazones

以8-羟基喹啉-7-醛和一系列芳基及烷基取代氨基硫脲为原料,合成了15种8-羟基喹啉缩氨基硫脲类化合物.缩合反应在绿色溶剂水中进行,微波辐射下15-30 min内反应完全,操作简单,收率高.化合物结构经1H NMR、IR和高分辨质谱确证.部分化合物经抗肿瘤活性初步测试结果表明,多数化合物对细胞周期分裂蛋白25B(CDC25B)抑制率达到90％以上,具有潜在的抗肿瘤活性.     

Synthesis of 1-substituted-7-hydroxyquinolinium salts

The reaction of 7-acetoxyquinoline with trifluorosulfonate esters of primary alcohols in methylene chloride or acetonitrile, followed by acid hydrolysis, provides a general synthesis of 1-substituted-7-hydroxyquinolines, whose phenolate anions are fluorescent.     

Catalytic enantioselective protonation of cobalt–enolate equivalents generated by 1,4-reduction with borohydride

In the presence of a catalytic amount of the optically active β-ketoiminato cobalt(II) complex and borohydride modified with appropriate alcohols, the 1,4-reduction of α-substituted-α,β-unsaturated carboxamides followed by in situ enantioselective protonation proceeded smoothly to afford optically active α-substituted carboxamides with good enantiomeric excess.     

Efficient selective oxidation of alcohols to aldehydes catalyzed by a morpholinone nitroxide

Efficient chemoselective oxidation of primary alcohols to the corresponding aldehydes is described. The transformation is promoted by a catalytic morpholinone nitroxide radical catalyst which can be easily synthesized. A broad range of substrates including aromatic and aliphatic primary alcohols are converted with excellent yields under mild conditions. The control experiments reveal that the morpholinone nitroxide can be used as a selective oxidant for primary alcohols in the presence of secondary alcohols.     

Enantioselective addition of diethylzinc to aldehydes catalyzed by a new chiral β-amino alcohol derived from d-mannitol

A new chiral β-dialkylamino alcohol 1 prepared from d-mannitol has been used as a highly effective chiral catalyst for the enantioselective addition of diethylzinc to unhindered aliphatic aldehydes to afford the product alcohols in up to 94% ee.     

Synthesis of new β-hydroxy amide ligands and their Ti(IV) complex-catalyzed enantioselective alkynylation of aliphatic and vinyl aldehydes

Three new chiral β-hydroxy amide ligands were synthesized via the reaction of benzyl chloride and amino alcohols derived from l-tyrosine. The titanium(IV) complex of chiral ligand 8b was found to be an effective catalyst for the asymmetric alkynylation of aliphatic, vinyl and aromatic aldehydes. The propargyl alcohols were obtained in highly enantiomeric excesses (up to 96% ee) under optimized conditions.     

Utility of 5-Diazo-1,2,4- Triazol-3-Carboxylic Acid for Colorimetric Determination of Certain 8-Hydroxyquinolines

Abstract

A colorimetric method for the determination of certain 8-hydroxyquinolines has been developed. The method is based on the coupling of 8-quinolinols with diazotriazole carboxylic acid in the presence of sodium carbonate (0.5% w/v) at ambient temperature (around 30°C). The resulting azo dyes are stable and give intense absorption in the range of 486–540 nm. Beer's law is valid in the concentration ranges of 1 – 8, 2.5 – 17.5, 5 – 35, 2 – 20, and 2 – 20 mcg/ml for 8-hydroxyquinoline (HQ), 5,7-diiodo-8-hydroxyquinoline (DIQ), 5,7-dibromo-8-hydroxyquinoline (DBQ), 5-chloro-7-iodo-8-hydroxyquinoline (CIQ) and 8-hydroxy-7-iodo-5-quinoline sulfonic acid (SIQ), respectively. The proposed method has been successfully applied for the determination of the studied compounds in pure form and in commercial formulations. The obtained results are in good agreement with those obtained from reported methods.     

Synthesis of Diazadi(and tri)thiacrown Ethers Containing Two 5-Substituent(or 2-methyl)-8-hydroxyquinoline Side Arms

Abstract

Sixteen new diazadi(or tri)thiacrown ethers containing two 5-substituent(or 2-methyl)-8-hydroxyquino-lin-2-ylmethyl side arms have been prepared by a three-step process. First, the appropriate bis(α-chloroamide)s were treated with five dimercaptans in base to form macrocyclic di(or tri)thiadiamides. The macrocyclic diamides were reduced by BH₃-THF to form 1,7-diaza-4-oxa-10,13-dithia-cyclopentadecane (11); 1,7-diaza-4,13-dioxa-10,16-dithiacyclooctadecane (12); 1,7-diaza-4-oxa-10,13,16-trithiacyclooctadecane (13); 1,7-diaza-4,13,16-trioxa-10,19-dithiacycloheneicosane (14); and 1,10-diaza-4,7-dioxa-13,16-dithiacyclooctadecane (15). The diazadi(or tri)thiacrown ethers were then treated with 8-hydroxyquinoline, 8-hydroxy-5-methylquinoline, 5-chloro-8-hydroxyquinoline, and 8-hydroxyquinaldine in the presence of paraformal-delyde in refluxing benzene to form the bis(8-hydroxy-5-substituent(or 2-methyl)quinolin-7-ymethy)-substituted diazadi(or tri)thiacrown ethers 16-31. The crown ethers containing two 8-hydroxyquinoline or 8-hydroxyquinaldine side arms proved to be mixtures of about 90% bis(8-hydroxyquinolin-7-ylmethyl)-substituted crown ethers; 9% mixed (8-hydroxyquinolin-7-ymethyl)-substituted and (8-hydroxyquinolin-5-ylmethyl)-substituted crown ethers; and 1% bis(8-hydroxyquinolin-5-ylmethyl)-substituted crown ethers.     

芳香族及饱和脂肪族醛的制备——苯硫酚催化二甲基亚砜对芳香族及饱和脂肪族醇的氧化反应

A new and convenient synthetic method for aromatic and saturated aliphatic aldehydes with moderate yield via the oxidation of corresponding alcohols by dimethyl sulfoxide in the presence of thiophenol is described.     

Synthesis and Antimicrobial Evaluation of Novel N-Substituted β-Hydroxy Benzimidazole Sulfone Fluoroquinolones by Selective Oxidation Using Ticl4-H2O2

Abstract

The synthesis of N-substituted β-hydroxy benzimidazole sulfones containing 8-methoxy fluoroquinolone has been described and they were evaluated for antimicrobial activities. The compounds of N-substituted β-hydroxy benzimidazole sulfides (4a–e) and N-substituted β-hydroxy benzimidazole sulfones (5a–e) at C-7 of fluoroquinoline exhibited superior activity in vitro. 8-Methoxy fluoroquinolone carboxylic acid (1), reaction with piperizine in acetonitrile in presence of triethylamine under reflux gives 7-piperazinyl-8-methoxyfluoroquinolone (2). The latter is reacted with epichlorohydrine in presence of NaOH in acetone yielded N-substituted epoxide (3), which on treatment with 5-substituted-2-mercaptobenzimidazoles gives N-substituted β-hydroxy benzimidazole sulfides (4). Further, 4 on treatment with TiCl₄-H₂O₂ and in DCM yielded the corresponding N-substituted β-hydroxy benzimidazole sulfone (5).     

4-substituted-1,2,3,4-tetrahydro-3,3-dimethylisoquinolines. II.

A practical synthesis (Scheme I) is described for the preparation of a series of 4-substituted-3,3-dimethyl-1,2,3,4-tetrahydroisoquinolines ( 3 ). Treatment of α-(1-amino-1-methylethyl)arylmethanols or α-(1-amino-1-methylethyl)heteroarylmethanols ( 5 ) with aromatic aldehydes gave imines 7 from which amino alcohols 8 were derived by reduction with potassium borohydride. Acid catalyzed cyclization of 8 yielded 3 . An acyl substituent was installed by Friedel-Crafts acylation as a final step. The biological activities of 3a (1) are briefly described.