2-甲基苯并咪唑基异黄酮衍生物的合成及抗氧化活性

建立了2-甲基苯并咪唑类异黄酮衍生物的合成方法. 其中脱氧安息香3以间苯二酚和取代苯乙酸为原料用微波促进法合成, 化合物3再与醋酐反应得到化合物4, 其在酸性条件下转化成化合物5. 化合物5分别与1,2-二溴乙烷和1,3-二溴丙烷在丙酮溶液中回流得到化合物6和7, 最后目标化合物分别由化合物6和化合物7与2-甲基苯并咪唑在无水碳酸钾催化下丙酮中回流得到. 利用IR, ¹H NMR, ¹³C NMR, 元素分析等对目标化合物的结构进行了表征. 在目标化合物的合成中, 不仅对C-O键和C-N键建立的反应条件进行了优化, 而且将微波促进法成功地应用到了目标化合物的合成中, 极大地缩短了反应时间. 目标化合物抗氧化活性研究表明, 12种目标化合物均具有较强的清除羟基自由基的能力.     

Synthesis and Reaction of 2-Mercapto-3-Arylpropanoic Acids

Abstract

Two synthetic pathways for the preparation of 2-mercapto-3-arylpropanoic acids were developed. First, by the reaction of arenediazonium bromides with acrylic esters in the presence of CuBr, alkyl (2-bromo-3-aryl)propanoates were formed. Their cyclization with thiourea produced 5-(R-benzyl)-2-imino-4-thiazolidinones, which yielded 3-aryl-2-mercaptopropanoic acids by alkaline hydrolysis. Second, direct Meerwein arylation of acrylates in the presence of S-nucleophile (NaSH) allowed isolation of 3-phenyl-2-mercaptopropanoic acid in 8% yield. Such acids were used for cyclization with cyanoguanidine and phenyl isothiocyanate yielding 1-[5-(R-benzyl)-4-oxo-1,3-thiazolidin-2-ylidene]guanidines and new 5-(R-benzyl)-3-phenyl-2-thioxo-1,3-thiazolidin-4-one (rhodanine) derivatives correspondingly.     

邻羧基苯甲醛苯甲酰腙稀土配合物的合成和抗氧化活性

通过邻羧基苯甲醛与苯甲酰肼在苯中的缩合反应制备了邻羧基苯甲醛苯甲酰腙 (H2 L)。在水中合成了H2 L的 6种稀土配合物 ,并采用元素分析IR ,UV ,1 HNMR和DTA TG对配合物进行了表征。配合物的分子式为RE(HL2 )·4H2 O (RE =La ,Pr,Nd ,Eu ,Gd和Er) ,配体以四齿参与配位 ,配合物是八配位结构。此外用紫外光谱法测定了配合物对O2 -·自由基的清除率。结果表明邻羧基苯甲醛苯甲酰腙稀土配合物有一定的抗氧化活性 ,对O2 -·自由基的清除率在 8%～ 2 5 %范围内     

大黄酸金属配合物的合成、表征及抗氧化活性研究

以天然大黄酸为原料合成了三种大黄酸金属配合物. 通过元素分析、摩尔电导、紫外光谱、红外光谱、热重差热、核磁共振氢谱和荧光分析测定配合物的组成和性质. 结果表明配合物组成为ML₂•2H₂O [M＝Cu(II), Fe(II), Mn(II)|L＝rhein(失去1-OH中质子)]. 并对配体和配合物进行了清除超氧自由基(O )、羟自由基(•OH)、DPPH•自由基的对比研究. 抗氧化试验结果表明, 金属配合物抗氧化活性均强于配体.     

Synthesis of Some Novel S- and N,S-Substituted Chlorobutadienes

Abstract

Mono(thio)substituted nitrodienes were synthesized by reactions of 2-nitro-pentachloro-1,3-butadiene with some thiols [(tert-butylbenzyl)thio- and 2,3,5,6-tetra-fluorophenylthio-] either directly or in ethanol in the presence of sodium hydroxide. N,S-Substituted 1,3-butadienes were obtained from the reaction of the mono(thio)substituted nitrodienes with morpholine and some piperazine derivatives in dichloromethane. Also mono- and di(thio)substituted perchlorobutadienes were synthesized from the reactions of hexachloro-1,3-butadiene with o-aminothiophenol in ethanol in the presence of sodium hydroxide. The structures of the new compounds were characterized by microanalysis and spectroscopic data.     

1,4-苯基双氨基膦酸酯的绿色合成及生物活性

在不加任何溶剂和催化剂条件下,通过微波辅助一锅法合成了9种1,4-苯基双氨基膦酸酯.该反应时间短(4～6min),后处理简单,环境友好,产率达到85%～95%,是一种高效绿色的合成方法.通过1H NMR、13C NMR和元素分析确定了目标化合物的结构.生物活性测试表明,该类化合物对革兰氏阳性菌(金黄色葡萄球菌)有很好的...     

氨噻肟酸稀土配合物的合成、抗氧化性及抗菌活性的研究

合成了１２种稀土氨噻肟酸（ＨＬ）固体配合物,其通式为ＲＥＬ３（ＲＥ＝Ｌａ,Ｃａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｔｂ,Ｅｒ、Ｔｍ,Ｙｂ,Ｙ）。利用元素分析、红外光谱、核磁共振氢谱、摩尔电导、热分析等测试手段对配合物进行了表征,研究了ＮｄＬ３、ＥｒＬ３配合物在ＤＭＳＯ溶液中电子吸收光谱,计算了电子云伸效应参数β,共价参数　和键合参数ｂ＾１／２,讨论了配合物的共价成键情况,并对其抗氧化及抗菌活性做了研究     

1,4-二氧喹喔啉甲醛亚胺的合成和抑菌活性

1;4-二氧喹喔啉甲醛亚胺的合成和抑菌活性;二氧喹喔啉甲醛亚胺;合成;结构表征;抑菌活性     

Synthesis of 1,4-Thiazepane-Based Curcuminoids with Promising Anticancer Activity

Curcumin, the main component of turmeric (Curcuma longa) is known to display an interesting bioactivity profile, including pronounced anticancer properties. However, its low bioavailability, metabolic instability and nonspecific activity are concerns that have to be addressed before curcuminoids can be considered for therapeutic applications. Within that framework, intensive research has been carried out in the last decades to develop new curcumin derivatives, generally centered on standard modifications of the sp² curcumin framework, with the aim to augment its bioavailability while maintaining or improving its anticancer properties. To find potential hit molecules by moving away from the classical flat curcumin framework, we investigated an unexplored modification to produce novel, out-of-plane 1,4-thiazepane-based curcuminoids and assessed the impact of this modification on the biological activity. In this way, 21 new, structurally diverse thiazepane scaffolds (4-aryl-1-(7-aryl-1,4-thiazepan-5-ylidene)but-3-en-2-ones) were synthesized, as well as some biologically interesting unexpected reaction products (such as 5-aryl-6-arylmethylene-3-ethoxycyclohex-2-en-1-ones and 4-acetyl-5-aryl-2-(3-arylacryloyl)-3-methylcyclohex-2-en-1-ones). All these analogues were subsequently tested on their antioxidant capacity, their cytotoxicity properties and their ROS (reactive oxygen species) production. Many compounds demonstrated interesting activities, with ten curcuminoids, whereof eight 1,4-thiazepane-based, showing better antiproliferative properties compared to their mother compounds, as well as an increased ROS production. This unprecedented 3D curcumin modification has thus delivered promising new hit compounds with good activity profiles eligible for further exploration.     

1,4—二苯基—2—苯氧基—1,4,2—二氮磷杂环戊—5—酮的合成及其除草活性研究

利用１，３－二苯基脲与亚磷酸三苯酯和取代苯甲醛进行的类Ｍａｎｎｉｃｈ反应合成了１，４－二苯基－２－苯氧基－１，４，２－二氮磷杂环戊－５－酮（２），所有新化合物的结构均经元素分析、ＮＭＲ、ＭＳ证实。对目标化合物进行的除草活性测试结果表明，２对阔叶杂草具有较好的选择性除草活性。     

1,4-苯醌衍生物的合成、氧化还原电位和生物活性的研究

合成了一系列具有不同的醌环结构(醌环上的取代基不同,如甲基、甲氧基、氢、氯和溴,或取代基的排列位置不同)的6-正癸基-1,4-苯醌衍生物。系统地研究了它们的结构、氧化还原电位和在线粒体琥珀酸-细胞色素 c 氧化还原晦中生物功能的关系。     

Synthesis of 2-Chloromethyl-1,4-Dihydropyridines

The title compounds were prepared by condensation of aldehydes with alkyl 3-aminocrotonate and 4-chloroacetoacetate.     

桑色素金属(Ⅱ)固体配合物的抗氧性研究

本文报道了五种金属(Ⅱ)桑色素固体配合物的合成。通过元素分析、溶解度、摩尔电导、红外光谱、热重差热、核磁共振氢谱和荧光分析测定了配合物的组成和性质,结果表明配合物组成为ML₂·nH₂O[M=Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ);L=Morin(失去2′-OH中质子);n=2或3]。并对配体、配合物进行了脂质过氧化物生成的抑制和清除O₂^-·自由基的对比研究。     

Synthesis of 2-Mercapto- and 2-Hydroxy-Substituted Diphenylphosphines for use as Dianionic Bidentate Ligands and Polydentate Ligand Precursors

Abstract

As part of our studies into the synthesis of polydentate phosphine-containing ligands, we have investigated the preparation of the phosphines (4; X[dbnd]O) and (4; X[dbnd]S). These are of interest both as potential dianionic bidentate ligands and as useful precursors of more complex polydentate ligand systems. A synthesis of the thiol system (4; X[dbnd]S) from 1,2-dinitrobenzene has been previously reported [1], but the observation [2], that 2-bromoaryl esters of phosphoric acid rearrange to give esters of arylphosphonic acids in the presence of alkyl lithiums, led us to consider whether a similar type of rearrangement might provide a convenient approach to both (4; X[dbnd]S) and (4; X[dbnd]O).     

The Effect of 2-Mercapto-5-Methyl-1,3,4-Thiadiazole on Enzymatic Synthesis of Cefazolin

The effect of unreacted residual 2-mercapto-5-methyl-l,3,4-thiadiazole (MMTD), the reagent for 3-[5-methyl-l,3,4-thiadiazole-2-yl]-7-aminocephalosporanic acid (M-7-ACA) synthesis, on the enzymatic acylation of M-7-ACA by the methyl ester of 1,2,3,4-tetrazol-1-acetic acid (MeTzAA) to produce cefazolin (CEZ) was studied. In the two-step process of synthesizing CEZ from 7-aminocephalosporanic acid (7-ACA), one of the key parameters controlling the overall CEZ yield was the ratio of MMTD to 7-ACA in M-7-ACA synthesis. The increase of the ratio showed opposing effects by increasing the M-7-ACA yield in the first step, while decreasing CEZ yield in the subsequent enzymatic reaction by the inhibitory effect of the increased content of MMTD as an impurity in the M-7-ACA preparation. It was revealed that the decrease of CEZ yield in the enzymatic reaction was caused by the selective retardation of the rate of CEZ synthesis reaction by a typical competitive inhibition, while not affecting the rate of MeTzAA hydrolysis reaction. The optimum MMTD-to-7-ACA ratio rendering the highest overall CEZ yield over 7-ACA was 1.2:1.     

含唑基的1，4－戊二烯－3－酮类的合成及生物活性研究

由简单的芳醛经３步反应合成了３６种未见报道的含唑基的１，４－戊二烯－３－酮类化合物，经ＩＲ、１ＨＮＭＲ、ＭＳ测定和元素分析证实了其结构．生物活性试验表明，该类化合物具有不同程度的杀菌活性．     

Synthesis and transformations of 1,4-diethynyl-2-nitrobenzene

Heating 2-nitro-1,4-bis(1,3,3-trimethylindolin-2-ylideneacetyl)benzene with POCl₃ followed by treatment with an aqueous solution of NaOH gave 2-nitro-1,4-diethynylbenzene. Some transformations involving this product were considered. 2-Acetylamino-1,4-diethynylbenzene and its dimorpholinomethyl derivative underwent heterocyclization, resulting in the terminal and methine carbon-substituted indolylacetylenes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2505–2508, November, 2005.     

Synthesis of New Substituted 2,3-Dihydro-1,4-dioxin-2-ones and 1,4-Dioxan-2-ones

3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of zinc(II) chloride to give the corresponding 3-alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded 3-alkyl-6-methyl-1,4-dioxane-2,5-diones. Successive chlorination and dechlorination of 6-hydroxymethyl-1,4-dioxan-2-ones yielded 6-methylene-1,4-dioxan-2-ones.     

Synthesis of New Substituted 2,3-Dihydro-1,4-dioxin-2-ones and 1,4-Dioxan-2-ones

3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of zinc(II) chloride to give 5-acetyl-3-alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded 3-alkyl-6-methyl-1,4-dioxane-2,5-diones. Chlorination of 6-hydroxymethyl-1,4-dioxan-2-ones with thionyl chloride and subsequent dehydrochlorination led to formation of 6-methylene-1,4-dioxan-2-ones.     

三唑酰胺1,4-戊二烯-3-酮衍生物的合成及生物活性

以丙酮和水杨醛为起始原料,设计合成了9个新型含氟1,2,4-三唑酰胺姜黄素类化合物,通过¹H NMR、¹⁹F NMR、IR及元素分析等技术手段对目标化合物进行了结构表征。 采用Airbrush喷雾法进行生物活性测试,结果表明部分化合物具有不同程度的杀虫活性。