A novel three-component reaction of 1, 1-dicyano-2-(trifluoromethyl)ethylenes,primary arylamines,and ketones

1, 1-Dicyano-2, 2-bis(trifluoromethyl)ethylene and 3, 3-dicyano-2-(trifluoromethyl)acrylates react with primary arylamines in the presence of ketones to form 1, 1-aryl-1, 4-dihydropyridme derivatives under mild conditions. The mechanism of this three-component reaction includes the formation of Schiffs bases as intermediates. 1, 4-Dihydropyridine derivatives, which are the products of three-component heterocyclization, were also obtained by reaction the corresponding Schiffs bases with 1, 1-dicyano-2-(trifluoromethyl)ethylenes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 552–559, March, 1993.For preliminary communication see Ref. 1.     

2-芳酰氨基-5-(5-苄基四唑-2-亚甲基)-1,3,4-噻二唑的合成

1,3,4噻二唑环类衍生物具有抗菌,杀虫,除草,调节植物生长,消炎止疼等广泛的生理活性。本文在浓硫酸催化下将1-(5-苄基四唑-2-乙酰基)-4-芳酰基氨基硫脲(1)环化为2-芳酰氨基-5-(5-芳基四唑-2-亚甲基-1,3,4-噻二(2)。2 的结构经元素分析、红外、核磁振波谱以及质谱方法确定。     

New N1-(4-aryloxybenzyl)uracils containing N3-positioned 4-(trimethyleneoxy)benzoic acid moiety,and study of their antiviral activity against SARS-CoV-2 and influenza virus

New title uracil derivatives, 4-{3-[2,6-dioxo-3-(4-aryl-oxybenzyl)-3,6-dihydropyrimidin-1(2H)-yl]propoxy}benzoic acids and their butoxy homologues, were obtained in three steps using 2,4-bis(trimethylsilyloxy)pyrimidine, 4-aryloxy-benzyl bromides and methyl 4-(ω-bromoalkoxy)benzoates as the key reactants. The compounds were studied as inhibitors of H1N1 influenza virus and SARS-CoV-2 R replication in MDCK and Vero E6 cell cultures, respectively, which revealed that the tested compounds had high levels of anti-SARS-CoV-2 activity.     

Synthetic access of new 6-purineselenyl and 8-(1,3,4-thiadiazolyl)-7-benzyl-1, 3-dimethyl-1H-purine-2,6-(3H,7H)-dione derivatives

Abstract

New 6-purineselenyl, 1, 3, 4-thiadiazols bearing 7-benzyl-1,3-dimethyl-1H-purine-2,6-(3H,7H)-diones and (8-[2-(3-phenyl-5-substituted-1,3,4-thiadiazol-2(3H)-ylidene) hydrazinyl)-7-benzyl-1,3-dimethyl-1H-purine-2,6-(3H,7H)-diones derivatives were synthesized. The structures of the newly synthesized compounds were elucidated by spectroscopic methods (1H-NMR, 13C-NMR, and MS spectrometry) and elemental analysis.     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

Synthesis of 6- to 10-membered ring (E)-hydroxyiminohydroazaazoniabenzocycloalkenes derivative from cyclization of 2-nitromethylene-1-(ω-phenylalkyl)imidazolidine or 2-nitromethylene-1-(ω-phenylalkyl)hexahydropyrimidine in trifluoromethanesulfonic acid

In trifluoromethanesulfonic acid, 2-nitromethylene-1-(ω-phenylalkyl)imidazolidine or 2-nitromethylene-1-(ω-phenylalkyl)hexahydropyrimidine derivatives undergo an intramolecular cyclization to afford (E)-hydroxyiminohydroazaazoniabenzocycloalkenes, in their trifluoromethanesulfonate salt form. The reaction probably occurres via the formation of an electrophilic transient hydroxynitrilium ion (or O-protonated nitrile oxide). The yields are generally good, except for the higher-membered ring derivatives.     

New reactivity of 1-(2-pyridyl)-2-propen-1-ol with nitro derivatives

1-(2-Pyridyl)-2-propen-1-ol showed an unprecedented reactivity behaving as Hantzsch ester 1,4-dihydropyridine mimic for the metal-free reduction of the nitro group of electron-deficient aromatic and heteroaromatic nitro compounds to the corresponding amino function. The redox mechanism is part of a domino process involving a direct trapping of the amino derivatives through aza-Michael addition to the vinyl ketone intermediate leading to the one-pot formation of new functionalised aminoacylpyridines.     

Crystal Structure of 1-(N-Dichlorophosphoryl-N- cyclohexyl)-amino-1-dichlorophosphinyl-chloromethane

1 INTRODUCTION The substituted aminomethylenediphosphonic acids as well as their derivatives are extensively used in treating various bone diseases, such as osteoporosis, Paget抯 disease and hypercalcemia due to malignancy[1]. They also have activiti…     

Study on the Cyclization Methods of 3-[1-(Phenyl-hydrazono)ethyl]-chromen-2-ones

Some new methods, such as air oxidation, catalytic oxidation, and solvent-free synthesis, are developed for the synthesis of 3-methyl-1-phenylchromeno[4,3-c]pyrazol-4(1H)-ones(2) from the cyclization of 3-[1-(phenyl-hydrazono)ethyl]-chromen-2-ones(1). Compared with air oxidation, catalytic oxidation can increase the rate of the cyclization of compound 1, and the solvent-free synthesis showed advantages of no organic solvent pollution, elevated reaction rate, and higher selectivity.     

Synthesis and antiproliferative activity of (1R,2R)-N1-(2-butyl)-1,2-cyclohexanediamine platinum(II) complexes with malonate derivatives

Three new platinum(II) complexes of (1R,2R)-N¹-(2-butyl)-1,2-cyclohexanediamine with malonate derivatives as leaving groups have been synthesized and spectrally characterized. They were tested in vitro against four human cancer cell lines. [(1R,2R)-N¹-(2-butyl)-1,2-cyclohexanediamine-N,N′](2-ethylmalonato-O,O′)platinum(II) turned out to be more active (IC₅₀ = 4.65 μM) than oxaliplatin (IC₅₀ = 6.55 μM) against the MCF-7 cell line and is superior to its parent complex, [(1R,2R)-N¹-(2-butyl)-1,2-cyclohexanediamine-N,N′](malonato-O,O′)platinum(II). In addition, agarose gel electrophoresis study revealed that the interaction of the complex with pET22b plasmid DNA had a different behavior from that of cisplatin or oxaliplatin.     

双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1H)-酮的合成与性能研究

设计并合成了一种基于喹诺酮衍生物的双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1 H)-酮.计算发现,化合物的HOMO轨道的电子云位于咔唑基团,LUMO轨道的电子云位于喹诺酮基团,是一种良好的双极材料.化合物的磷光发射峰为515 nm(2.41 eV),符合绿色磷光主体材料的基本要求(>2.4 eV).热失重和差热分析结果表明,该化合物具有较高的热稳定性,分解温度和玻璃化转变温度分别为312℃和105℃.研究结果表明:该新型化合物是一种潜在的具有双极特性的绿色磷光主体材料.     

1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮的合成及三阶非线性光学性质

合成了一种新的有机非线性光学(NLO)材料1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮(PMPAK),通过¹H NMR、IR、HR-MS和元素分析表征其结构。 以Nd:YAG-Laser System作为光源,激光波长450 nm,脉冲宽度4 ns(FWHM),采用4f相位相干成像技术测定了PMPAK的三阶NLO性质并确定了相关参数:非线性折射率n₂=-1.84×10^-16 m²/W,非线性吸收系数β=2.53×10^-9 m/W,非线性极化率χ⁽³⁾=1.137×10^-10 esu。     

Synthesis of 4-Substituted-4-(Diethylphosphono)-2-Methylbuta-2,3-dien-1-oles

Several 4-substituted 4-(diethylphosphono)-2-methylbuta-2,3-dien-1-oles 4a-f were synthesized by a simple and efficient three-step procedure starting from acetylene derivatives.     

Synthesis of amino acid derivatives of 4-(1-adamantyl)benzoic acid obtained by transition metal ion catalyzed oxidation of 4-(1-adamantyl)toluene

An efficient synthesis of 4-(1-adamantyl)benzoic acid based on transition metal ion catalyzed oxidation of 4-(1-adamantyl)toluene has been developed. As a catalytic system, cobalt-manganese bromide with addition of manganese acetate was used. A series of amino acid derivatives of 4-(1-adamantyl)benzoic acid was then synthesized and characterized. These derivatives are novel intermediates potentially useful in the design of therapeutically active peptidomimetics with improved pharmacokinetic and pharmacodynamic parameters.     

Qualitative Characteristics and Spot Analysis of 1, 3, 4-alkylderivatives of 5-Aminopyrazol

Abstract

Rapid spot analysis of three aminopyrazol derivatives is described: 1-β-(pyridyl-4) -ethyl -3 -methyl-5 -aminopyrazol dichloride (I) 1-isopropyl-3-methyl-5-aminopyrazol (II), and 1-isopropyl-3-ethyl-4-methyl-5-aminopyrazol (III). Sensitivity, maximum dilution and analytical procedure is presented.     

Novel,Simple, and Efficient Synthesis of 3-(2-(5-(Benzylideneamino)-3-phenyl-1H-pyrazol-1-yl)thiazol-4-yl)-4-hydroxy-6-methyl-2H-pyran-2-one Derivatives via a One-Pot,Four-Component Condensation Reaction

The synthesis of 3-(2-(5-(benzylideneamino)-3-phenyl-1H-pyrazol-1-yl)thiazol-4-yl)-4-hydroxy-6-methyl-2H-pyran-2-one derivatives was achieved through a one-pot, four-component reaction involving condensation of 3-(2-bromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one, thiosemicarbazide, phenacylcyanaide, and various aryl aldehydes in dry alcohol and few drops of acetic acid under reflux condition. This four-component reaction has some advantages such as ease of handling, good yields, and easy workup. All structures of newly prepared compounds were confirmed by analytical and spectral data.     

Synthesis and antitumor activity of 6- and 2- （ 1-acyl sulfanylalkyl）-5,8-dimethoxy- 1,4-naphthoquinones

Sixteen novel 6- and 2-（1-acylsulfanylalkyl）-5,8-dimethoxy-l,4-naphthoquinones were designed and synthesized. Their cytotoxicities were evaluated in vitro against BEL-7402, HT-29 and SPC-Al cell lines. The pharmacological results showed that most of the prepared compounds displayed the excellent selectivity for HT-29 cell line. Compound lab exhibited the most potent antitumor activity among the tested compounds.     

3-Ferrocenyl-3-(1-naphthyl)cyclopropene. Synthesis, structure, and chemical transformations

Crystalline 3-ferrocenyl-3-(1-naphthyl)cyclopropene was prepared by dehydrobromination ofZ- andE-2-bromo-1-ferrocenyl-1-(1-naphthyl)-cyclopropanes by Bu^tOK in DMSO. The resulting compound and the startingZ-monobromocyclopropane were characterized by X-ray diffraction analysis. The obtained cyclopropene reacts with 1,3-diphenylisobenzofuran to give a [4+2]-cycloadduct. The small ring opens upon treatment with HBF₄ etherate to afford isomericZ- andE-prop-1-enes and 1-ferrocenyl-3H-benzo[e]indene. Thermolysis of this cyclopropene results in the formation of 1-ferrocenyl-9bH-benzo[e]indene. In all cases, opening of the small ring is accompanied by exclusive alkylation of the naphthalene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 499–506, March, 1998.     

Chemical behaviours of 3-[1′-chloro-3′-(2″-phenyl-1″,3″-oxazol-5″-one=4″-ylidene)propen-1′-yl]coumarin towards some nucleophilic reagents

The chemical behaviours of 3-[1′-chloro-3′-(2″-phenyl-1″,3″-oxasol-5″-one-4″-ylidene)-propen-1′-yl]coumarin towards nucleophilic reagents (such as hydrolysis, aminolysis, hydroxyl-aminolysis, methanolysis and hydrazinolysis) were described.     

A novel reaction of 2-(arylamino)-1-(methylthio)-1-tosylethenes with hydrogen iodide leading to quinoline derivatives

The reaction of 2-(arylamino)-1-(methylthio)-1-tosylethenes (4) with hydrogen iodide in refluxing toluene gave 3-tosyl-2-(tosylmethyl)quinoline derivatives (6) in good yields. In this reaction, hydrogen iodide dose not only reductively removes the methylthio group of 4 to form an intermediary 1-(arylamino)-2-tosylethene (5), but also serves as a protic catalyst for the subsequent dimeric cyclization of 5 to lead to the quinoline derivatives (6).