N,N′-二（-2-羟苄基）取代咪唑烷的合成、表征及抑菌活性研究

利用生物活性叠加原理,将“邻羟苯基”和“咪唑烷”分子片断有机结合,合成了6种N,N′-二（-2-羟苄基）取代咪唑烷类化合物（3a-3f）.以水杨醛和乙二胺为起始原料,经缩合、NaBH4还原制得N,N′-二邻羟苄基乙二胺（2）,进而与芳醛类化合物缩合关环制得目标化合物. 化合物的结构经1H NMR、IR、MS和元素分析等表征确认.结果表明,水杨醛与乙二胺的缩合反应,可专一性地生成对称双缩席夫碱化合物（1）;芳醛上的取代基对缩合关环反应有显著影响,邻、对位吸电基可使芳醛的羰基活化,有利于缩合关环反应的进行,邻、对位供电基可使芳醛的羰基钝化,不利于缩合关环反应进行.抑菌测试表明,质量浓度为0.1%时,N,N′-二（-2-羟苄基）取代咪唑烷化合物对不同菌株的抑菌活性具有明显的特异性,对白色念珠菌、大肠杆菌的抑菌率高达100%,是一类极具潜力的抗真菌、抗革兰氏阴性菌的化合物.     

降压药物的合成研究 Ⅱ.若干氮七环基和氮八环基化合物的合成

1-邻氯苄基氮七环和1-邻氯苄基氮八环与碘乙烷、邻氯苄基溴或对甲苯磺酸甲酯分别反应,生成相应的季铵盐(Ⅲa,b,c,e);N,N-环六亚甲基-N',N'-环七亚甲基-1,2-乙二胺与邻氯苄基溴反应,得到双季铵盐(Ⅲd).1-β-氯乙基氮七环和1-β-氯乙基氮八环与过量的水合肼或氮八环作用,各自得β-取代氨基乙肼(Ⅳa,b)和1,2-乙二胺化合物(Ⅳf). 水合肼与1-氮七环基乙醛缩合,生成的连氮化合物用氢化铝锂还原得N,N'-双-(β-1-氮七环基乙基)肼(Ⅳc).由1,2-二溴乙烷与氮七环或氮八环反应,得对称乙二胺衍生物(Ⅳd,e).借1-β-氯乙基氮七环双分子环合季铵化和1,2-乙二胺衍生物与二溴代烷的反应,得螺环双季铵盐(Ⅳ).     

卤代邻羟苄基谷氨酸(酯)的合成、表征及抑菌活性

分别用氯代水杨醛、溴代水杨醛与L-谷氨酸及其酯反应,首先制得水杨醛缩谷氨酸类席夫碱(2),再经硼氢化钠还原制得邻羟苄基取代谷氨酸及其酯(3),化合物的结构经IR、1H NMR、MS与元素分析表征确认. 测试表明,在质量浓度为0.05%时,卤代邻羟苄基谷氨酸对大肠杆菌具有高的抑菌活性,抑菌率高达97%,对白色念珠菌、金黄色葡萄球菌的抑菌效果较差,但其甲酯化产物卤代邻羟苄基谷氨酸甲酯对白色念珠菌具有高的抑菌活性,抑菌率高达100%,对大肠杆菌、金黄色葡萄球菌的抑菌效果较差,说明该类衍生物对菌株的抑杀作用具有明显的专一性和特异性,氯代邻羟苄基谷氨酸甲酯、溴代邻羟苄基谷氨酸甲酯是白色念珠菌的优良抗菌化合物。     

离子液体功能化二氧化硅催化Knoevenagel反应

在100 ℃, 无外加溶剂条件下, 离子液体功能化二氧化硅催化一系列芳醛和活泼亚甲基化合物进行Knoevenagel 缩合反应, 以高产率生成相应产物. 当反应底物为水杨醛与氰基乙酸乙酯的时候, 产物为3-乙氧基羰基香豆素, 这是水杨醛和氰基乙酸乙酯缩合关环, 再发生氰基醇解的产物. 采用离子液体功能化二氧化硅作为反应催化剂, 反应后催化剂可回收再利用.     

5-溴-2-羟基苯甲酰基取代芳醛腙的合成、表征及抑菌活性

以水杨酸甲酯为原料,先经溴化反应制得5-溴水杨酸甲酯,再经肼解反应制得5-溴-2-羟基苯甲酰肼,再与取代芳香醛缩合反应,制得7种5-溴-2-羟基苯甲酰基取代芳醛腙,其中3种为新化合物. 化合物的结构经IR、1H NMR、MS与元素分析测试技术表征确证. 抑菌测试表明,该类化合物对不同菌株的抑菌活性具有明显的选择性;在质量浓度为0.05%时,上述化合物对白色念珠菌、枯草芽孢杆菌的抑菌率高达100%,具有强抑菌活性,是一类极具潜力的抗真菌、抗革兰氏阳性菌的化合物. 5-溴-2-羟基苯基-3′,5′-二溴-2-羟基苯甲醛腙的抗菌活性接近广谱高效杀菌剂三氯生. 构效分析表明,化合物的抑菌活性与Ar环及其取代基性质有关,引入呋喃环、Ar环邻、对位引入-OH、-OCH_3等供电基容易导致化合物抑菌活性降低,Ar环的间位引入Cl、Br等卤素原子能够提高化合物的抑菌活性.     

1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物的合成及抑菌活性

将邻羟苯基引入1,2,3-三唑结构中, 设计合成了10个1-(4-取代苯基)-4-苯基-5-取代-1,2,3-三唑类衍生物. 首先, 以对位取代的芳胺为原料, 经重氮化、叠氮化、闭环和缩合反应制得1-(4-取代苯基)-4-苯基-5-水杨醛亚胺-1,2,3-三唑类衍生物(3a~3e), 再用硼氢化钠还原制得1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物(4a~4e). 目标化合物的结构经核磁、IR及元素分析确认. 抑菌活性测试表明, 当质量浓度为0.1 mg/L时, 除化合物3e和4e外, 所有化合物对白色念球菌的抑菌率均达95%以上, 对大肠杆菌的抑菌率达85%以上, 具有强抑菌活性, 表明该类化合物在抗菌药物开发方面有重要应用价值.     

5-溴-邻羟苯基芳基取代酰腙的合成、表征及抑菌活性研究

以水杨酸甲酯为原料,先经溴化反应制得5-溴水杨酸甲酯,再经肼解反应制得5-溴-2-羟基苯甲酰肼,再与取代芳香醛缩合反应,制得7种5-溴-2-羟基苯甲酰基取代芳醛腙,其中3种为新化合物。 化合物的结构经IR、¹H NMR、MS与元素分析测试技术表征确证。 抑菌测试表明,该类化合物对不同菌株的抑菌活性具有明显的选择性;在质量浓度为0.05%时,上述化合物对白色念珠菌、枯草芽孢杆菌的抑菌率高达100%,具有强抑菌活性,是一类极具潜力的抗真菌、抗革兰氏阳性菌的化合物。 5-溴-2-羟基苯基-3′,5′-二溴-2-羟基苯甲醛腙的抗菌活性接近广谱高效杀菌剂三氯生。 构效分析表明,化合物的抑菌活性与Ar环及其取代基性质有关,引入呋喃环、Ar环邻、对位引入-OH、-OCH₃等供电基容易导致化合物抑菌活性降低,Ar环的间位引入Cl、Br等卤素原子能够提高化合物的抑菌活性。     

N,N'-(对位取代苯基)乙二胺的质子化及其与Cu(Ⅱ)配位的滴定量热测定

对于乙二胺及其C-取代衍生物体系的质子化反应及其与Cu(Ⅱ)配位反应的热力学研究已有文献报道,N,N'-脂肪基取代乙二胺的热化学研究亦有报道。前文用pH法对N,N-'(对位取代苯基)乙二胺体系(p-RPh)_2en)的质子化反应及其与Cu(Ⅱ),Ni(Ⅱ)配     

Cp2TiCl2催化下Grignard试剂与芳醛反应的研究

Meunier 等曾研究了 Cp_2TiCl_2催化下,格氏试剂对卤代烷和羰基化合物的还原反应,并报道了与芳环或碳-碳双键或碳-碳三键共轭的羰基化合物不被格氏试剂还原。我们却发现,在较低温度下,这些芳醛或与碳-碳重键共轭的羰基化合物也会被还原,特别是在芳环上有吸电子取代基时,还原产物的产率很高。     

碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应

合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b),研究了其反应性能.结果表明,化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应,完全转移了4个碳的异丁基和正丁基单元,基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法;化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元,生成不同基团取代的N,N,N'-三取代乙二胺盐;化合物5a在Na BH4作用下可发生还原反应,在Na OH水溶液中可发生水解反应,也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应,生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物,探索了此类化合物的简易合成方法.这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能,并将其扩展到4个碳原子单元,获得了可应用于有机合成的新方法和新试剂.     

不对称Schiff碱镍(Ⅱ)配合物的合成及其晶体结构

合成了3个具有不对称结构的Schiff碱配体H2Ln(n=1、2、3)。H2L1由乙酰丙酮、乙二胺和水杨醛缩合作用得到,H2L2由乙酰丙酮、(1R,2R)-环己二胺和水杨醛缩合作用得到,H2L3由苯甲酰丙酮、乙二胺和水杨醛缩合作用得到,每个反应中3个反应物的物质的量之比均为1∶1∶1。配体H2Ln分别与Ni(OAc)2.4H2O进行配位反应得到3个单核Ni(Ⅱ)配合物1,2和3。分别采用1H NMR、FTIR和元素分析对化合物进行了表征,并通过X-射线单晶衍射技术测定了3个配合物的晶体结构。     

Organic Electrosynthesis as a New Facile and Green Method for One‐pot Synthesis of Nanosized Particles of Octahydro‐imidazo[1,2‐a]quinolin‐6‐one Derivatives via a Multicomponent Reaction

Organic electrosynthesis as a new facile and green method was applied for one‐pot synthesis of octahydro‐imidazo[1,2‐a]quinolin‐6‐one derivatives, via a three component condensation of a dimedone, an aldehyde and 2‐(nitromethylene)imidazolidine in propanol in an undivided cell in the presence of sodium bromide as an electrolyte at room temperature. In this study, the anion of dimedone that was produced on the cathode reacted with aromatic aldehydes through the Knoevenagel reaction and then the product condensed with 2‐(nitromethylene)imidazolidine that resulted in a highly efficient formation of octahydro‐imidazo[1,2‐a]quinolin‐6‐one with 50–96% substance yields.     

Synthesis, spectroscopic, antimicrobial, DNA binding and cleavage studies of some metal complexes involving symmetrical bidentate N, N donor Schiff base ligand

The Schiff base ligand, N,N′-bis-(4-isopropylbenzaldimine)-1,2-diaminoethane (L), obtained by the condensation of 4-isopropylbenzaldehyde and 1,2-diaminoethane, has been used to synthesize the complexes of the type [ML₂X₂] [M = Co(II), Ni(II) and Zn(II); X = Cl and OAc]. The newly synthesized ligand (L) and its complexes have been characterized on the basis of elemental analyses, mass, ¹H and ¹³C-NMR, molar conductance, IR, UV–vis, magnetic moment, CV and thermal analyses, powder XRD and SEM. IR spectral data show that the ligand is coordinated to the metal ions in a bidentate manner. The geometrical structures of these complexes are found to be octahedral. Interestingly, reaction with Cu(II) ion with this ligand undergoes hydrolytic cleavage to form ethylenediamine copper(II) complex and the corresponding aldehyde. The antimicrobial results indicate that the chloro complexes exhibit more activity than the acetato complexes. The complexes bind to CT–DNA by intercalation modes. Novel chloroform soluble ZnL₂Cl₂ complex exhibits tremendous antimicrobial, DNA binding and cleaving properties.     

Design,Synthesis, and Antimicrobial Evaluation of some Novel Pyridine,Coumarin, and Thiazole Derivatives

Treatment of 2‐cyano‐N′‐(1‐(pyridin‐2‐yl)ethylidene)acetohydrazide 1 with aromatic/heterocyclic aldehydes 2a–f gave arylidene derivatives 3a–f . Polysubstituted pyridine derivatives 4a,b were prepared either from reaction of arylidene 3a,b with malononitrile or from reaction of acetohydrazide 1 with arylidenemalononitrile 5a,b . Cyclocondensation of acetohydrazide 1 with salicylaldehyde derivatives and acetylacetone furnished pyrido‐coumarins 6,7 and 2‐pyridone‐3‐carbonitrile 8, respectively. In addition, pyrido‐thiazoles 13 and 15 were obtained through reaction of 2‐(1‐(pyridin‐2‐yl)ethylidene)hydrazinecarbothioamide 11 with hydrazonyl chlorides and α‐haloketones, respectively. The structures of synthesized compounds were elucidated with spectral and elemental data. The antimicrobial activity of the synthesized compounds was studied.     

Bismuth triflate：A highly efficient catalyst for the synthesis of bio-active coumarin compoundsvia one-pot multi-component reaction

A series of coumarin-chalcone hybrid compounds and coumarins linked to pyrazoline was synthe-sized in good yield and short time using a simple and efficient method. This method involved the one-pot reaction of salicylaldehyde, an α-ketoester and an aromatic aldehyde (in the case of the coumarin-chalcone derivatives) in addition to hydrazine hydrate (in the case of the pyrazolyl cou-marins) in the presence of a catalytic amount of bismuth triflate [Bi(OTf)3, 5 mol%]. The synthesized compounds showed scavenging activity towards the free radical 2,2-diphenyl-1-picrylhydrazyl. All compounds were characterized using IR,1H NMR and13C NMR spectroscopy.     

超支化聚酰胺-胺破乳剂的合成及应用

以N-丙烯酰-1,2-乙二胺盐酸盐(ADE)合成为基础,通过ADE的Michael加成反应制备阳离子超支化聚合物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),并对其结构进行了表征。研究表明,50℃下,HADE破乳剂(质量浓度为200 mg/L)对含煤油质量分数5%的水包油(O/W)煤油乳液的除油率可高达95.6%,显示了产品在乳液破乳除油方面良好的发展前景。     

Synthesis of unsaturated derivatives of 2,5-dimethyl-4-phenylpyridine and 3-methyl-2-azafluorene

A substituted butadiene — 1-phenyl-4-(5-methyl-4-phenyl-2-pyridyl)buta-1,3-diene with a trans, trans configuration — was obtained by condensation of 2,5-dimethyl-4-phenylpyridine with cinnamaldehyde. Two 3-methyl-9-cinnamylidene-2-azafluorene isomers are formed as a result of condensation of the same aldehyde with 3-methyl-2-azafluorene. Data from the PMR and IR spectra were used to prove the configuration of the compounds obtained. It was established that the condensation of 3-methyl-2-azafluorene with salicylaldehyde gives 3-methyl-9-(2-hydroxybenzylidene)-2-azafluorene, which has a zwitterionic structure, and 1,2-bis(3-methyl-2-aza-9-fluorenylidene)ethane. Ideas regarding the chemical mechanism of the formation of the latter are presented. The preparation of an unsaturated alcohol — 3-methyl-9-allyl-2-aza-9-fluorenol — is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–86, January, 1978.     

One-pot approach to the synthesis of novel 12H-chromeno[2′,3′:4,5]imidazo[1,2-a]pyridines in aqueous media

The chromeno-imidazo[1,2-a]pyridine scaffold was generated in an one pot condensation/cyclization reaction involving a salicylaldehyde and 1-(cyanomethyl)pyridinium chloride, in aqueous sodium carbonate solution. These novel compounds were isolated in 47-71% yield. The reaction pathway was followed by ¹H NMR spectroscopy allowing a clear understanding of the side reactions involved in the process.Different mono-substituted pyridinium chlorides were synthesized and reacted with mono-substituted salicylaldehydes and a detailed discussion of the scope of the synthetic method is also presented.